SYNTHESIS and INVESTIGATION of STABILITY and CHEMICAL KINETICS of CROWN ETHERS and THEIR COMPLEXES with 3D TRANSITION METALS

SYNTHESIS AND INVESTIGATION OF STABILITY AND CHEMICAL KINETICS OF CROWN ETHERS AND THEIR COMPLEXES WITH 3d TRANSITION METALS

Submitted By IMDAD HUSSAIN 2008-Ph.D-Chemistry-03

Supervisor

Prof. Dr. Syeda Rubina Gilani

DEPARTMENT OF CHEMISTRY University of Engineering & Technology, Lahore-Pakistan (2015)

Synthesis and Investigation of Stability and Chemical Kinetics of Crown Ethers and Their Complexes With 3d Transition Metals

IMDAD HUSSAIN (2008- Ph.D Chemistry-03)

Department of Chemistry University of Engineering and Technology, Lahore

Supervisor: Dr. Syeda Rubina Gilani

A dissertation submitted to University of Engineering & Technology Lahore in accordance with requirements of the degree of Ph. D in Faculty of Science.

(2015)

Synthesis and Investigation of Stability and Chemical Kinetics of Crown Ethers and Their Complexes With 3d Transition Metals

This Research Thesis Is Submitted To the Department Of Chemistry, University Of Engineering & Technology Lahore for the Fulfillments for the Degree of

DOCTOR OF PHILOSOPHY

CHEMISTRY

Approved on ______

Internal Examiner: Signature: ______(Supervisor) Name: Prof. Dr. Syeda Rubina Gilani

External Examiner: Signature: ______Name: ______

Chairperson of the Department: Signature: ______Name: Prof. Dr. Syeda Rubina Gilani

DEPARTMENT OF CHEMISTRY UNIVERSITY OF ENGINEERING & TECHNOLOGY LAHORE

iii

FORM FOR THE RELEASE OF RESEARCH THESIS FOR

EXAMINATION

Declaration by the Candidate

I, IMDAD HUSSAIN, declare that the thesis titled “Synthesis and Investigation of Stability and Chemical Kinetics of Crown

Ethers and Their Complexes With 3d Transition Metals” is my own work and has not been submitted previously in whole or in part in respect of any other academic award.

______Signature of Candidate Date

I approved that the above thesis can be submitted for examination.

______Signature of Supervisor Date (Prof. Dr. Syeda Rubina Gilani)

DEPARTMENT OF CHEMISTRY UNIVERSITY OF ENGINEERING & TECHNOLOGY LAHORE

Author’s Declaration

I declare that the work in this dissertation was carried out in accordance with the regulations of the University of Engineering and Technology Lahore. This work is original, except where indicated by special reference in the text. And no part of the dissertation has been submitted for any other academic award. All views expressed in the dissertation are those of the author and in no way represent those of the University of Engineering and Technology. The dissertation has not been presented to any other University for examination in Pakistan or overseas.

Signed: …………………… Date: …………………….

Dedicated To My

Respectable & Beloved Parents

Lovely Son Khuzaima

Beloved Wife

Brothers and Sisters

ACKNOWLEDGEMENTS All the praises for Allah Who guides me in lacerate and congenial circumstances and Whose mercy and help is the pinnacle of my desires and wishes. All respects are for His Holly Prophet Hazrat Muhammad (Pease Be Upon Him) Who showed me the path of knowledge and for His love to humanity. It is a matter of great pleasure and honour for me to express my deep sense of gratitude to Prof. Dr. Syeda Rubina Gilani, Chairperson, Department of Chemistry, University of Engineering and Technology Lahore for accepting me in her research group as a Ph.D student and for guidance, support and enthusiasm during my Ph.D study. I am also thankful to all worthy Professors of Chemistry Department, U.E.T Lahore for providing me guidance time to time when needed. I would like to thank to respected and honorable Prof. Vickie McKee, whose scholarly guidance, keen interest and encouragement has been a source of great help throughout my research at Loughborough university, Loughborough, UK. I am also thankful to Dr. Muhammet Kose for very good moments, chats, laughs and for his skilled guidance and encouraging attitude throughout my research work. With deep emotions of gratitude, I am also grateful to Mrs. Pauline King who provided me support, advice and training during the research and for running microanalysis for all my samples. It is very difficult to pay thanks in words to my class fellows especially Zulfiqar Ali, Habib Hussain, Dr. Amin Abid, Dr. Faiz Rubani and Dr. Asif Ali Tahir, for their incredible help, fraternal collaborations and sincere suggestions throughout my study and research work. I would also like to thank Higher Education Commission (H.E.C.) of Pakistan for funding my Ph.D degree. I am also grateful to my friends Aamir Ali Bajwa, M. Naeem Akhtar, M. Aamir Tufail, Asif Islam, Mahmood bajwa, Ghulam Akbar, Abid Hussain, Javed Iqbal and Chacha Sarfraz for their moral support. At the end, I acknowledge that my all success is due to my parents, my wife, my lovely son Khuzaima Ahmad, brothers and Sisters. It is due to their prayers that I am able to achieve this glory of success. Imdad Hussain 2008-Ph.D.Chemistry-03

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IN THE NAME OF ALLAH

The Most Gracious The Most Merciful

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TABLE OF CONTENTS

Chapter No. Title Pages CHAPTER 1: INTRODUCTION 01-30 1.1 Supramolecular chemistry 2 1.2 A brief history of crown ether chemistry 3 1.3 Classification and nomenclature of macrocyclic polyethers 5 1.4 Biological macrocyclic complexes 7 1.5 Macrocyclic ligands 8 1.6 Chemical kinetics of macrocyclic ligands for complex formation with metals 9 1.6.1 Chelate effect 10 1.6.2 Macrocyclic effect 11 1.6.3 Coordination template effect 13 1.6.4 Effect of donor atoms on coordination bond formation 15 1.6.5 Soft and hard acid and base theory (SHAB) 17 1.6.6 Effect of guest cation on coordination bond formation 18 1.6.7 Template synthesis and transmetallation reactions 19 1.7 Synthesis of macrocycles 22 1.8 The formation of macrocyclic complexes 23 1.9 Crown ethers 26 1.10 Spectroscopic analysis of ethers 28 1.11 Applications of crown ethers 28 1.11.1 In organic chemistry 28 1.11.2 In analytical chemistry 28 1.11.3 In inorganic chemistry 29 1.11.4 In electrical engineering 29 1.11.5 In electronics 29 1.11.6 In biology and medicine 29 CHAPTER 2: EXPERIMENTAL WORK 31-52 2.1 Introduction 32 ix

2.2 General conditions 32 2.2.1 Solvents and reagents 32 2.2.2 Instrumentation 32 2.3 Synthesis of 18-Crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) 33 2.3.1 Purification of crude 18-Crown-6 34 2.3.2 Flow Sheet Diagram for the Synthesis of 18-Crown-6 34 2.4 Synthesis of Ni-18-Crown-6 complex [IHCNi] 36 2.5 Synthesis of Cu-18-Crown-6 complex [IHCCu] 36 2.6 Synthesis of Zn-18-Crown-6 complex [IHCZn] 37 2.7 Preparation of activated manganese dioxide 37 2.8 Synthesis of 2, 2-methylene-bis-[(6-hydroxymethyl)-4-tert-butylphenol]

(H2mhtbp) 38

2.9 Oxidation of H2mhtbp to 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) 39 2.10 Synthesis of macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)- 4-tert-butylphenol] and 1, 2-Bis-[2-aminoethoxy]ethane [L-1] 39 2.11 Synthesis of macrocyclic ligand based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [L-5.1] 40 2.12 Synthesis of macrocyclic ligand based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and Bis-[2-aminoethyl]-amine [L-2] 40 2.13 Synthesis of macrocyclic ligand based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol [IR-2] 41 2.14 Synthesis of a homo-nuclear complex of calcium with a macrocycle based

on (H2mftbp) and 1, 3-diamino-2-propanol [IR-4/ IR-2] 42 2.15 Synthesis of a homo-nuclear complex of Zinc with a macrocycle based on

(H2mftbp) and 1, 3-diamino-2-propanol [ IR-5B ] 42 2.16 Synthesis of a hetro-nuclear complex of Manganese and Barium with a

Macrocycle based on (H2mftbp) and 1, 3-diamino-2-propanol [CE-25] 43 2.17 Synthesis of a hetro-nuclear complex of Calcium and Zinc with a

Macrocycle based on (H2mftbp) and 1, 4-diaminobutane [CE-24] 43 2.18 Synthesis of a hetro-nuclear complex of Lead and Copper with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-1] 43 2.19 Synthesis of a hetro-nuclear complex of Barium and Nickel with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-3] 44 x

2.20 Synthesis of a hetro-nuclear complex of La and Cu with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy] ethane [CE-7] 44 2.21 Synthesis of a hetro-nuclear complex of Ba and Cu with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-9] 45 2.22 Synthesis of a hetro-nuclear complex of Barium and Zinc with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-13] 45 2.23 Synthesis of a hetro-nuclear complex of La and Ni with a macrocycle based

on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-15] 46 2.24 Synthesis of a hetro-nuclear complex of Ca and Ni with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-17] 46 2.25 Synthesis of a hetro-nuclear complex of Calcium and Zinc with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-19] 46 2.26 Synthesis of a homo-nuclear complex of Copper with a macrocycle based

on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-20/27] 47 2.27 Synthesis of a homo-nuclear complex of Nickel with a macrocycle based

on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-26] 47 2.28 Synthesis of a homo-nuclear complex of Calcium with a macrocycle based

on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-5] 48 2.29 Synthesis of a hetro-nuclear complex of Ba and Ni with a macrocycle

based on (H2mftbp) and triethylene tetramine [CE-22] 48 2.30 Synthesis of a hetro-nuclear complex of Ca and Cu with a macrocycle

based on (H2mftbp) and triethylene tetramine [CE-23] 49 2.31 Synthesis of a hetro-nuclear complex of Ba and Ni with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-2] 49 2.32 Synthesis of a homo-nuclear complex of Calcium with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-4] 49 2.33 Synthesis of a homo-nuclear complex of Copper with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-8] 50 2.34 Synthesis of a hetro-nuclear complex of La and Zn with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-10] 50 2.35 Synthesis of a hetro-nuclear complex of Ba and Zn with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-12] 51 2.36 Symthesis of a hetro-nuclear complex of Calcium and Zinc with a

Macrocycle based on (H2mftbp) and diethylenetriamine [CE-18] 51 xi

2.37 Symthesis of a homo-nuclear complex of Nickel with a macrocycle based

On (H2mftbp) and diethylenetriamine [CE-29] 51 CHAPTER 3: RESULTS & DISCUSSION 53-149 3.1 Introduction 54 3.2 List of synthesized macrocyclic ligands 54 3.3 List of synthesized macrocyclic complexes with metals 55 3.4 Physical properties of 18-crown-6 and its complexes with metals (Table-3.1) 57 3.5 Solubility of Crown ether and its complexes 58 3.5.1 Non polar solvents (Table-3.2) 58 3.5.2 Polar solvents (Table-3.3) 58 3.6 Atomic absorption spectroscopic studies for nickel, copper and zinc complexes with 18-crown-6 58 3.6.1 Instrumental parameters 59 3.7 U.V. Studies of 18-crown-6 ligand and its complexes with Ni, Cu and Zn 60 3.8 Stability determination of 18-crown-6 ligand and its complexes with Ni, Cu and Zn by UV-Study 60 3.8.1 Stability determination of 18-crown-6 ligand 60 3.8.2 Stability determination of Ni-complex of 18-crown-6 62 3.8.3 Stability determination of Cu-complex of 18-crown-6 64 3.8.4 Stability determination of Zn-complex of 18-crown-6 66 3.9 TGA of Ni, Cu and Zn complexes with 18-crown-6 68 3.9.1 TGA of Ni-18-crown-6 complex 68 3.9.2 TGA of Cu-18-crown-6 complex 69 3.9.3 TGA of Zn-18-crown-6 complex 69 3.10 Characterization of 2, 2-methylene-bis-[(6-hydroxymethyl)-4-tert-

butylphenol] (H2mhtbp) 71 3.11 Characterization of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) 72

3.12 Characterization of macrocyclic ligand based on (H2mftbp) and 1, 2-Bis-[2-aminoethoxy]ethane [L-1] 75 1 3.12.1 H NMR Studies of macrocyclic ligand based on (H2mftbp) and 1, 2-Bis-[2-aminoethoxy]ethane [L-1] 75

3.12.2 ESI-MS Studies of macrocyclic ligand based on (H2mftbp) and xii

1, 2-Bis-[2-aminoethoxy]ethane [L-1] 76

3.12.3 IR Studies of macrocyclic ligand based on (H2mftbp) and 1, 2-Bis-[2-aminoethoxy]ethane [L-1] 77

3.13 Characterization of macrocyclic ligand based on (H2mftbp) and triethylene tetramine [L-5.1] 77 1 3.13.1 H NMR Studies of a macrocyclic ligand based on (H2mftbp) and triethylene tetramine [L-5.1] 78

3.13.2 ESI-MS Studies of a macrocyclic ligand based on (H2mftbp) and triethylene tetramine [L-5.1] 79

3.13.3 IR-Studies of a macrocyclic ligand based on (H2mftbp) and triethylene tetramine [L-5.1] 79

3.14 Characterization of a macrocyclic ligand based on (H2mftbp) and Bis-[2-aminoethyl]-amine [L-2] 80 1 3.14.1 H NMR Studies of a macrocyclic ligand based on (H2mftbp) and Bis-[2-aminoethyl]-amine [L-2] 80

3.14.2 ESI-MS Studies of a macrocyclic ligand based on (H2mftbp) and Bis-[2-aminoethyl]-amine [L-2] 81

3.14.3 IR Studies of a macrocyclic ligand based on (H2mftbp) and Bis-[2-aminoethyl]-amine [L-2] 82

3.15 Characterization of a macrocyclic ligand based on (H2mftbp) and 1, 3-diamino-2-propanol [IR-2] 83

3.15.1 ESI-MS Studies of a macrocyclic ligand based on (H2mftbp) and 1, 3-diamino-2-propanol [IR-2] 83

3.15.2 IR Studies of a macrocyclic ligand based on (H2mftbp) and 1, 3-diamino-2-propanol [IR-2] 84 3.16 Electrospray ionization mass spectrometery study 85 3.17 ESI-MS studies of Ni, Cu and Zn complexes of 18-crown-6 86 3.17.1 MS Studies of Nickel complex of 18-Crown-6 [IHCNi] 86 3.17.2 MS studies of Copper complex of 18-Crown-6 [IHCCu] 87 3.17.3 MS Studies Zinc complex of 18-Crown-6 [IHCZn] 87 3.18 MS studies of metal complexes of macrocycles derived from

(H2mftbp) and 1, 3-diamino-2-propanol 88 3.18.1 MS Study of a homo-nuclear complex of calcium with a macrocycle

Based on (H2mftbp) and 1, 3-diamino-2-propanol [IR-4/ IR-2] 89 xiii

3.18.2 MS Studies of a homo-nuclear complex of Zinc with a macrocycle

based on (H2mftbp) and 1, 3-diamino-2-propanol [ IR-5B ] 89 3.18.3 MS Studies of a complex of Mn and Ba with a macrocycle based on

(H2mftbp) and 1, 3-diamino-2-propanol [CE-25] 91 3.19 MS Studies of a homo-nuclear complex of Calcium and Zinc with a

macrocycle based on (H2mftbp) and 1, 4-diaminobutane [CE-24] 92 3.20 ESI-MS studies of metal complexes of macrocycles derived from

(H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane 93 3.20.1 MS study of a hetro-nuclear complex of Pb and Cu with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-1] 93 3.20.2 MS Studies of a hetro-nuclear complex of Ba and Ni with macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-3] 94 3.20.3 MS study of a hetro-nuclear complex of La and Cu with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy] ethane [CE-7] 95 3.20.4 MS study of a hetro-nuclear complex of Ba and Cu with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-9] 96 3.20.5 MS study of a hetro-nuclear complex of Ba and Zn with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-13] 96 3.20.6 MS study of a hetro-nuclear complex of La and Ni with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-15] 96 3.20.7 MS study of a hetro-nuclear complex of Ca and Ni with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-17] 97 3.20.8 MS study of a hetro-nuclear complex of Ca and Zn with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-19] 97 3.20.9 MS Studies of a homo-nuclear complex of Cu with a macrocycle based

on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-20/27] 97 3.20.10MS Studies of a homo-nuclear complex of Nickel with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-26] 98 3.20.11MS study of a heomo-nuclear complex of Calcium with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-5] 99 3.21 ESI-MS studies of metal complexes of macrocycles derived from

(H2mftbp) and triethylene tetramine 100 3.21.1 MS study of a hetro-nuclear complex of Ba and Ni with a macrocycle

based on (H2mftbp) and triethylene tetramine [CE-22] 100 xiv

3.21.2 MS Studies of a hetro-nuclear complex of Ca and Cu with a macrocycle

based on (H2mftbp) and triethylene tetramine [CE-23] 100 3.22 ESI-MS studies of the metal complexes of macrocycles derived from

(H2mftbp) and diethylenetriamine 102 3.22.1 MS study of a hetro-nuclear complex of Barium and Nickel with a

macrocycle based on (H2mftbp) and diethylenetriamine [CE-2] 102 3.22.2 MS study of a homo-nuclear complex of Calcium with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-4] 103 3.22.3 MS study of a homo-nuclear complex of Copper with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-8] 103 3.22.4 MS Studies of a hetro-nuclear complex of Lanthanum and Zinc with a

macrocycle based on (H2mftbp) and diethylenetriamine [CE-10] 103 3.22.5 MS study of a hetro-nuclear complex of Barium and Zinc with a

macrocycle based on (H2mftbp) and diethylenetriamine [CE-12] 104 3.22.6 MS Studies of a hetro-nuclear complex of Calcium and Zinc with a

macrocycle based on (H2mftbp) and diethylenetriamine [CE-18] 105 3.22.7 MS Studies of a homo-nuclear complex of Nickel with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-29] 106 3.23 Infra Red Spectroscopic study 107 3.24 IR Spectroscopic studies of Ni, Cu and Zn complexes of 18-crown-6 107 3.24.1 IR Studies of Ni-complex of 18-Crown-6 [IHCNi] 107 3.24.2 IR Studies of Cu-complex of 18-crown-6 108 3.24.3 IR Studies of Zn-complex of 18-Crown-6 108 3.25 IR Spectroscopic studies of metal complexes of macrocycle derived from

(H2mftbp) and 1, 3-diamino-2-propanol 109 3.25.1 IR Studies of a homo-nuclear complex of Ca with a macrocycle based

on (H2mftbp) and 1, 3-diamino-2-propanol [IR-4/IR-2] 109 3.25.2 IR Studies of a homo-nuclear complex of Zinc with a macrocycle

based on (H2mftbp) and 1, 3-diamino-2-propanol [ IR-5B ] 110 3.25.3 IR Studies of a hetro-nuclear complex of Mn and Ba with macrocycle

based on (H2mftbp) and 1, 3-diamino-2-propanol [CE-25] 110 3.26 IR Studies of a homo-nuclear complex of Calcium and Zinc with a

macrocycle based on (H2mftbp) and 1, 4-diaminobutane [CE-24] 111 3.27 IR Spectroscopic studies of metal complexes of macrocycles derived from xv

(H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane 112 3.27.1 IR study of a hetro-nuclear complex of Pb and Cu with macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-1] 113 3.27.2 IR Studies of a hetro-nuclear complex of Ba and Ni with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-3] 113 3.27.3 IR study of a hetro-nuclear complex of La and Cu with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy] ethane [CE-7] 114 3.27.4 IR study of a complex of Ba and Cu with macrocycle based

on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-9] 114 3.27.5 IR study of a hetro-nuclear complex of Ba and Zn with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-13] 115 3.27.6 IR study of a hetro-nuclear complex of La and Ni with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-15] 115 3.27.7 IR study of a hetro-nuclear complex of Ca and Ni with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-17] 115 3.27.8 IR study of a hetro-nuclear complex of Ca and Zn with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-19] 116 3.27.9 IR Studies of a homo-nuclear complex of Cu with macrocycle based

on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-20/27] 116 3.27.10 IR Studies of a homo-nuclear complex of Ni with a macrocycle based

on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-26] 117 3.27.11 IR study of a homo-nuclear complex of Calcium with a macrocycle

based on (H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane [CE-5] 117 3.28 IR Spectroscopic studies of the metal complexes of macrocycles derived

from (H2mftbp) and triethylene tetramine 118 3.28.1 IR study of a hetro-nuclear complex of Ba and Ni with a macrocycle

based on (H2mftbp) and triethylene tetramine [CE-22] 118 3.28.2 IR studies of a hetro-nuclear complex of Ca and Cu with macrocycle

based on (H2mftbp) and triethylene tetramine [CE-23] 118 3.29 IR Spectroscopic studies of the metal complexes of macrocycles derived

from (H2mftbp) and diethylenetriamine 119 3.29.1 IR study of a hetro-nuclear complex of Ba and Ni with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-2] 120 3.29.2 IR study of a homo-nuclear complex of Calcium with a macrocycle xvi

based on (H2mftbp) and diethylenetriamine [CE-4] 120 3.29.3 IR study of a homo-nuclear complex of Copper with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-8] 121 3.29.4 IR Studies of a hetro-nuclear complex of La and Zn with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-10] 121 3.29.5 IR study of a hetro-nuclear complex of Ba and Zn with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-12] 122 3.29.6 IR Studies of a hetro-nuclear complex of Ca and Zn with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-18] 122 3.29.7 IR Studies of a homo-nuclear complex of Nickel with a macrocycle

based on (H2mftbp) and diethylenetriamine [CE-29] 123 3.30 Single Crystal X-Ray Analysis 124 3.30.1 Single crystal X-ray of Cu-18-Crown-6 complex 124

3.30.2 Single crystal X-ray of a macrocyclic ligand based on (H2mftbp) and 1, 2-Bis-[2-aminoethoxy]ethane 131 3.30.3 Single crystal X-ray of a Dizinc(II) complex of a Pseudocalixarene

macrocycle based on (H2mftbp) and 1, 3-diamino-2-propanol 139 3.31 Conclusion 147 3.32 Further Work 149 CHAPTER 4: REFERENCES 150-160 APPENDIX-I ESI-MS Spectra 161-168 APPENDIX-II IR Spectra 169-177 APPENDIX-III Conferences and Publications 178-181

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Abbreviations and Symbols σ softness, Pearson scale χ absolute electronegativity, Pearson scale η absolute hardness, Pearson scale λ wavelength δ chemical shift in ppm ν stretching frequency ° degree °C degree centigrade μ micro 10-6 μL microlitre, 10-6 litre Å Angströng unit 10-10 meter Approx. approximately Ar Aryl substituent b broad ca. circa calc. calculated CHN Carbon, Hydrogen and Nitrogen microanalysis cm-1 wavenumber d doublet DNA Deoxyribonucleic Acid ESI-MS Electrospray Ionization Mass Spectrometry Equiv. equivalent et al. and others Fig. Figure(s) g gram(s) h. hour(s)

H2mftbp 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol

H2mhtbp 2, 2-methylene-bis[(6-hydroxymethyl)-4-tert-butylphenol HPLC High Pressure Liquid Chromatography SHAB Soft Hard Acid Base IR Infrared k kilo 103

xviii

L Litre Log K formation constant m multiplet M Metal or molar m medium m/z mass to charge ratio MHz Megahertz, 106 sec-1 min. minute(s) mL milliliter(s) mol mole mmol millimole, 103 mole NMR Nuclear Magnetic Resonance O ortho p para pet petroleum ppm part per million

Rf Retention factor s singlet s strong sec second(s) T Temperature tert tertiary THF Tetrahydrofuran TLC Thin Layer Chromatography V Volt w weak

xix

Abstract The research work in this Ph.D. thesis is concerned with the synthesis of macrocyclic ligands and their complexes with metals and characterization by using different analytical techniques. Ligand, which was synthesized in this research work, is 1, 4, 7, 10, 13, 16- Hexaoxacyclooctadecane commonly called as 18-Crown-6 ether. This ligand was synthesized by the reaction of Triethylene glycol and 1, 2-bis (2-chloroethoxy) ethane and was purified by making acetonitrile complex. This ligand was used to make complexes with Ni(II), Cu(II) and Zn(II). My research also contains the synthesis of macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) and 1, 3-diamino-2-propanol, a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) and 1, 4-diaminobutane, a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol](H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane, a macrocycle based on 2,

2-methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) and triethylene tetramine and a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol](H2mftbp) and diethylene triamine. These macrocycles were further used to synthesize mono-nuclear and polynuclear complexes with different combinations of metals. These complexes may be homo-nuclear or hetro-nuclear.

2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) was prepared by the oxidation of 2, 2 –methylene-bis-[(6-hydroxymethyl)-4-tert-butylphenol](H2mhtbp).

And 2, 2–methylene-bis-[(6-hydroxymethyl)-4-tert-butylphenol](H2mhtbp) was prepared by refluxing 4-tert-butylphenol and formaldehyde in the presence of NaOH under nitrogn atmosphere at 60 oC. Different aspects of synthesized ligands and its complexes were studied by using various spectroscopic and thermal techniques.

UV studies of 18-Crown-6 ether and its copper complex showed that λ max of ligand increases after making complex with metal ions. In IR studies, C-H, C-O, C-C, peaks appeared in their respective regions. So the presence of these bonds is confirmed. The qualitative and quantitative estimation of metals present in complexes was done by Atomic Absorption Spectroscopy. Stability of 18-Crown-6 ether and its complexes with Copper, Nickel and Zinc were studied by using UV and TGA techniques and found stable in solid as well as in solution form over the whole period.

Single X-Ray spectroscopic study was done of various synthesized novel ligands and complexes.

xxi

Macrocyclic Ligands reffered to in the thesis

CH3 CH3 CH3 CH3 H3C CH3 H3C CH3 H3C CH3 H3C CH3

N OH OH N N OH OH N

O O NH HN

OH OH N N N OH OH N

H C CH H C CH 3 3 3 3 H3C CH3 H3C CH3 CH CH 3 3 CH3 CH3

(C58H80O8N4) (C58H84O4N8)

CH3 CH3 CH3 CH3 H3C CH3 H3C CH3 H3C CH3 H3C CH3

N OH OH N N OH OH N

HN NH HO OH

N OH OH N N OH OH N

H3C CH3 H3C CH3 H3C CH3 H3C CH3 CH CH CH 3 3 3 CH3

(C54H74O4N6) (C52H68O6N4)

O O

(C12H24O6)

xxii

Chapter 1

Introduction

Chapter 1 INTRODUCTION

1.1 Supramolecular chemistry The synthesis of super-molecules requires recognition phenomenon between the receptor and substrate and may result in specific functions and properties. When the receptor possesses additional reactive groups it may effect the chemical transformation of the bound substrate and therefore acts as a catalyst. The lipophilic receptor may behave as a carrier and change the location of the bound substrate. Recognition chemistry is also viewed as host-guest chemistry, where the host compound can be defined as chemical species which retains convergent binding sites and the guest molecules has divergent binding sites. The supramolecular Noble Prize laureate Cram describes the various structural relationships, which take place in such complexes [1], hydrogen bonding, ion pairing, π-acid to π-base interactions, metal to ligand binding, Vander Waal‘s attractive forces, solvent reorganization and partially made or broken covalent bonds (transition states). Examples of some hosts used in supramolecular chemistry are given in Figure-1.1.

O O O O Crown Ether [2-5] M O O O O

O O O O N O O N N N Cryptand [7-6] M O O O O

Podand [8] N N NH M NH2 NH 2 NH2 2 H2N NH2

O O O O O N Lariat Ether [9] N OMe M O O O O O MeO

Figure-1.1 some types of host molecules used in supramolecular chemistry

Chapter 1 INTRODUCTION

Supramolecular chemistry, the chemistry of designed intermolecular interaction is still expanding with its current emphasis placed on: a) Biological interface (enzyme mimics [10-13], membrane transport processes [14-16], base pairing and DNA recognition [17-18]) b) Separation and extraction chemistry [19-22] c) Physical and materials chemistry (supramolecular polymers [23-24], molecular machines [25-27], single molecule magnets [28-33], molecular electronic memories [34]) d) Self-assembly processes (chemistry in coordination cages [35-37], self-sorting systems of subcomponents [38-40]) Although supramolecular chemistry lies at an intersection of many science disciplines, the basic principles of coordination chemistry are important in the formation of the host guest complexes. Thus, the macrocyclic effect, the coordination template effect and Pearson‘s soft and hard acids and bases theory (SHAB) are being briefly discussed in this chapter together with one particular type of host molecules, Crown ethers.

1.2 A brief history of crown ether chemistry The chemistry of macrocyclic coordination complexes has gained a lot interest and these complexes have been broadly studied in current years [41]. Remarkable improvement has been done in the field of macrocyclic chemistry because of its a variety of applications [42] in bioinorganic chemistry. The synthesis of macrocyclic ligands and their metal complexes is an emerging field of research in bioinorganic and inorganic chemistry in vision of their presence and importance in many biologically major systems. Macrocyclic metal complexes are measured to be the model of metallocorrins and metalloporphyrins because of their basic structural properties. Currently, metal complexes are being studied widely because these metal complexes are similar to the macrocyclic metal complexes found in biological systems. Examples of these naturally occurring complexes are the hemes, found in hemoglobin, cytochromes, catalase and peroxidase, and the corrins, found in chlorophyll (in which the metal is Mg (II) and in vitamin B-12 {in which the metal is Co (III)}. Because for many reasons, these molecules are very complicated and difficult to study directly as these are generally linked with proteins. So one approach

Chapter 1 INTRODUCTION used by the chemists to understand these complex molecules and processes is, to make model compounds that have similar characteristics to the naturally occurring macromolecules. Synthesised model compounds can often provide insight into the important factors of the structure of naturally occurring complexes and these compounds may give information about the design of the systems. These models are low molecular weight complexes that take off either the structure or function of the naturally occurring molecules [43]. This chemistry started in late 1960s when Pedersen published his work on cyclic polyethers and their metal complexes [2-5]. However Lehn was the first who introduced the term supramolecular in 1978 [44] and shared noble prize for work in this field with Cram and Pedersen. Lehn defined supramolecular chemistry as chemistry of molecular assemblies and intermolecular interactions or more colloquially as ‗‘ chemistry beyond the molecule‘‘ [45]. In 1967, Pedersen succeeded to publish about 48 cyclic polyethers that were derivative of aromatic vicinal diols and discovered [46] beginning of a new area of chemistry that is known as crown ether chemistry. First cyclic polyether, 12-Crown-4, was prepared 10 years before Pedersen‗s discovery [47] but his most significant achievements were as bellow;  For the first time, Pedersen showed that these crown ethers have strong complexing ability for metal cations that include alkali metals, alkaline earth metals and transition metal ions.  Pedersen was first one who tried to disclose connection among the structure and complexation properties that was proved by his further work [48, 49, 50].

O O O

O O O O O O

O O O O O O O O

18-Crown-6 Dibenzo-18-Crown-6 15-Crown-5

Figure-1.2 Some of Pedersen‘s synthesized cyclic polyethers [46]

Chapter 1 INTRODUCTION

Soon after Pedersens‘s discovery, J. M. Lehn [51] verified that atoms of oxygen in crown ethers could be replaced with atoms of nitrogen and resultantly, two dimensional monocyclic structures can be transferred into three dimensional structures of bicycle and tricycle. These three dimensional structures of bicycle and tricycle have much stronger complexation ability and higher selectivity for metal cations [51, 52]. Lehn‘s research promoted importance of crown ether chemistry and provided further understanding about link among structure and complexation property.

N N N N O O H O O O O O O O O N N O O O O O O O O O O O O H N N N N

[2.2.1]-Cryptand [2.2.2]-Cryptand Cavitand I 1,10-Diaza-18-Crown-6 Figure-1.3 Lehn‗s molecules [51, 52]

1.3 Classification and nomenclature of macrocyclic polyethers Systematic nomenclature (IUPAC) looks to be difficult for naming cyclic polyethers. Vogtle and Weber [53, 54] recommended bellow non-systematic conventions for classification and nomenclature; Coronand: These macrocyclic systems of medium size have only one ring and any heteroatom. (18-crown-6 in Figure-1.2 and 1, 10-diaza-18-crown-6 in Figure-1.3) Crown ether: Coronands that have only oxygen as hetroatoms are called Crown ethers. (Figure-1.2) Potand: Acyclic analogs of Coronands or crown ethers are called Potands. (Figure- 1.4) Cryptand: Bicyclic or polycyclic compounds having any hetroatom are called Cryptands. (Figure-1.3) Cryptate: A complex made between a cryptand and a substrate is called Cryptate. (Figure-1.4) Coronate: A complex made between a coronand and a substrate is called Coronate. (Figure-1.4)

Chapter 1 INTRODUCTION

O O

O + - N N X O O M + M - X O O O O H3C O O O O O CH3 O O O

A Podand A Coronate [55] Cryptate [51] Figure-1.4 Examples of a podand, a Coronate and a Crypate Nomenclature suggested by Pedersen [46] contains two numbers i.e. fist number reveals total number of atom in ring and second number specifies number of heteroatoms in ring. Term ―Crown‖ is put between these two numbers to make full name. Common examples of crown ethers include 18-crown-6 and 15-crown-5 (Figure-1.2). Term ―Crown‖ was purposed because of the fact that macrocycle ―crowned‖ the cations just as ―a regal crown adorns the monarch‘s brow‖ [46]. Term azacrown is a rational addition that ensures the presence of at least one atom of nitrogen in ring. In practice, nomenclature of azacrown ethers is a mixture of systematic and non-systematic nomenclature. In nomenclature of azacrown ethers, the basic frame for crown ether is adopted and position of nitrogen atoms is specified, e.g. 1, 10-diaza-18-crown-6 (Figure-1.3). Lehn [51] recommended use of cryptands and cryptates as bicyclic and tricyclic macrocycles encapsulating cationic guests inside their cavity. Lehn supposed that atoms of nitrogen are present at bridgehead positions in his structures. Different cryptands were named by indicating the numbers of heteroatoms (usually oxygen atoms) in ethylenoxy links, e.g. [2.2.2]-cryptand and [2.2.1]-cryptand (Figure-1.3). Gokel and coworkers introduced the term ―lariat ether‖ [56a]. These types of macrocycles generally have one or more pendent arms with donor atoms. Name indicates that complexed cation is bound by both macrocyclic ring and by sidearm in same fasion as a lasso binds an animal. In fact, lariat ethers bind cations in a three dimensional style just like a cryptand.

+ + + M + M M

Figure-1.5 Binding pattern of lariat ethers 6

Chapter 1 INTRODUCTION

At first, lariat ether binds a guest cation with its macro ring with fast kinetics. Later the participation of side arms renders complex three dimensional. (Modified from reference [56b])

1.4 Biological macrocyclic complexes Metal complexes have an important position in life processes. Macrocyclic compounds are present broadly in nature, playing a vital role in some very important biological processes. The conversion of sun light energy into electrical and chemical energy, in photosynthesis, depends on a magnesium containing macrocycle found in chlorophyll. Similarly the macrocycle found in methanogenic bacteria, converts carbon dioxide into methane. As examples, three biological macrocyclic complexes are presented here [57];  The first example is chlorophyll, from world of plants. Chlorophyll is a macrocyclic complex of magnesium, found in leaves of green plants. In presence of chlorophyll, plants use energy of sun light in photosynthesis i.e. to prepare organic substances from water and cabon dioxide.

Figure-1.6 [57]

 Second example of hemoglobin is from world of animals. Hemoglobin is a protein in blood that transports oxygen. The unit ―Heme‖ found in hemoglobin is a red complex of iron. The hemoglobin transport oxygen from lungs to the cells. Heme, the active site in the hemoglobin, is a porphyrin containing iron. The unit ―heme‖ is a part of hemoglobin, myoglobin, cytochromes and numerous enzymes. There are many types of hemoglobin and these vary by the proteins surrounding the heme [57].

Chapter 1 INTRODUCTION

Figure-1.7 [57]

 Vitamin B12, contains a corrin ring.

Figure-1.8 [57]

1.5 Macrocyclic ligands A macrocycle is defined as "a cyclic macromolecule or a macromolecular cyclic portion of a molecule"[58]. Macrocyclic ligands are organic molecules and contain a number of atoms (donor atoms) with lone pair of electrons as part of a large ring of atoms. The donor atoms have an ability to bond to a variety of metal ions through their lone pair of electrons. These macrocycles usually place the metal at the center of the ring. In literature, organic chemist may consider any molecule to be macrocyclic that contains a ring of seven, fifteen or any randomly large number of atoms. Coordination chemists define a macrocycle as a cyclic molecule that have three or more potential donor atoms in a ring of atleast nine atoms [59]. Macrocycle is defined by IUPAC as "a cyclic macromolecule or a macromolecular cyclic portion of a molecule"[60]. 8

Chapter 1 INTRODUCTION

Macrocyclic ligand is a cyclic compound with nine or more members including all hetroatoms and with three or more donor atoms [61]. Donor atoms in macrocycles are usually located in such a way that upon coordination with metal ion, preferably five or six membered chelate rings are formed. Total number of atoms in macrocyclic ring determines cavity size of a macrocyclic ring. Backbone rigidity, and the nature and hybridization of donor atoms, too affect size of cavity. Central metal atom usually has a positive charge that is stabilised by donation of lone pair (negative charges) from the ligands. Therefore, ligands act as a Lewis base by donating one or more electron pairs to central atom and central atom acts as Lewis acid by gaining one or more elctron pairs. Neutral or negatively charged (anions) centers are generally stabilized by donating electrons density back to ligand in a process known as ―back bonding‖. If directly bonded ligands (―inner sphere‖ ligands) do not balance the charge, this may be done by purely an ionic interaction with another set of counter ions (―outer sphere‖ ligands). Complex, along with its counter ions, is called a coordination compound. Inner sphere ligands arrange themselves in certain geometry i.e. linear, tetrahedral, and square planar or octahedral. Arrangement is specific for a given complex but in some cases, it is changeable by a reaction that forms another stable isomer.

1.6 Chemical kinetics of macrocyclic ligands for complex formation with metals The kinetics and mechanism of complex formation of synthetic macrocyclic polyethers with metal ions have been broadly studied [183-184]. The major focus of study is on complexation of monovalent alkali metal ions in nonaqueous solution using NMR techniques [185-188]. Although the ultrasonic absorption kinetic studies have been reported elucidating the detailed mechanism of complexation in various solvents [189-193]. Relatively less attention has been paid to the complexation reactions of divalent alkaline earth metal ions with crown ethers [194]. Following major factors control the chemical kinetics of macrocyclic ligands for complexation with metal ions;  Chelate effect  Macrocyclic effect  Coordination template effect  Effect of donor atoms on coordination bond formation

Chapter 1 INTRODUCTION

 Soft and hard acid and base theory (SHAB)  Effect of guest cation on coordination bond formation  Template synthesis and transmetallation reactions

1.6.1 Chelate effect The word ‗chelate‘ is derived from a Greek word ‗chela‘ that refers to the great claws of lobster or other crustaceans. Morgan [62] introduced about metal-organic or inorganic systems in which calliper like groups bind the central metal to produce heterocyclic rings. The resulting complexes has greater stability than metal with monodentate ligand system [63-64]. Usually five membered or six membered chelate rings are the most stable ones. According to a simple model, the chelate effect is mostly an entropy effect. Example: 2+ 2+ [Cd (OH2) 6] + 2H2NCH3 [Cd (OH2) 4(H2NCH3) 2] + 2H2O  S O = - 5.7 J.mol-1.K-1 2+ 2+ [Cd (OH2) 6] + H2NCH2CH2NH2 [Cd (OH2) 4(en)] + 2H2O  S O = - 5.7 J.mol-1.K-1 Considering close similarity of Cd-N bonds in both complexes is not surprising, that enthalpy of both reactions is same (Ho = -29.3 kJ/mol). In second reaction, substitution of solvent H2O by bidentate ligand, increases number of free particles as it goes from two to three but in first reaction, number of free particles does not change and therefore disorder increases in second reaction, hence the entropy increases due to contribution of T*. Hence, G0 of first reaction is -27.6 kJmol-1 while G0 of second reaction is -33.5 KJmole-1. Relation between free energy and equilibrium constant is as follow; G 0 = -R*T*ln K For first reaction K= 6.9 x 104 and for second reaction K= 7.4 x 105 Above relationship follows for bellow reaction:

+2 +2 [Cd(OH2)4(H2NCH3)2] + H2NCH2CH2NH2 [Cd(OH2)4(en)]

+ 2H2NCH3

= -5.9 kJmol-1 and K= 10.7. It indicates that equilibrium of reaction (chelate ligand replaces corresponding monodentate ligands) is on the side of chelate complex.

Chapter 1 INTRODUCTION

1.6.2 Macrocyclic effect Macrocyclic effect is the most significant property of macrocyclic molecules. Macrocyclic effect as an expansion of chelate effect is an increased thermodynamic and kinetic stability of macrocyclic complexes with metal ions in comparison to their open chain analogs. It was first reported by Cabbiness and Margerum [65-66] who found that the Cu(II) complex with cyclic compound meso-5,7,7,12,14,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane (tet a) has 10,000 higher formation constant than for the complex with non-cyclic ligand but a similar sequence of chelate rings (Figure-1.9). Thermodynamic stabilisation of macrocyclic complex has both, enthalpic and entropic contributions [67-70]. Relative significance of these two contributions varries from case to caes.

Thermodynamic Stability

2+ 2+ CH3 H3C CH3

N N N N

Cu Cu

N N N N H H H3C CH3 CH3 +2 +2 [Cu(2,3,2-tet)] [Cu(tet a)] Log K = 28 log K = 23.9

+2 +2 Cu (aq) + L(aq) [Cu(L)] (aq)

Figuer-1.9 Thermodynamic stability of cyclic and noncyclic Cu(II) complex

The enthalpy is related to number of factors (e.g. solvation effects, geometrical preferences, strength of metal-ligand bonds etc. enthalpic contribution can be either favourable or unfavourable. The single most important factor seems to be the relative size of the metal ion and the macrocyclic cavity. Cu(II) ion forms more stable complex with macrocyclic cyclam ligand than Ni(II) and Zn(II) as a result of better fit between the cation size and macrocyclic cavity (Figure-1.10).

Chapter 1 INTRODUCTION

2+ 2+ 2+

N N N N N N

Zn Ni Cu

N N N N N N

log K = 15.34 log K = 22.2 log K = 27.2 Better match between metal ion size and macrocyclic cavity

results with increased thermodynamic stability Figure-1.10 Stability of [M(Cyclam)]+2 complexes (Where M=Cu, Ni, Zn)

The entropic contribution arises from the fact that the macrocycle is less conformationally flexible so loses fewer degree of freedom when makes a metal complex. In simple words, macrocyclic ligand is already preorganised for complexation and requires less energy for any conformational changes prior to bind the guest molecule. Therefore, entropy contribution always favours the formation of a macrocyclic complex over formation of an equivalent non-macrocyclic complex. The macrocyclic complexes are also kinetically stabilised in comparison with the linear chain ligands. This is observed mostly in the dissociation step, as the rates of dissociation for macrocyclic complexes are much slower than the open noncyclic complex. The acid dissociation rate of [Cu(tet a)]2+ is measured to be 3.6 x 10-7 [sec-1] where the open chain analog [Cu(2,3,2-tet)]2+ has 4.1 [sec-1] (Figure-1.11). The [Cu(tet a)]+2 complex doen not has any terminal donor to start dissociation, so the complex needs to fold and before this all bonds must break more or less together and process requires higher activation energy than for open chain ligand. The bicyclic ligands show even stronger macrocyclic effect for the same reason as described above and it is often called macrobicyclic or cryptate effect [7]. Kinetic stability

2+ 2+ CH3 H3C CH3

N N N N

Cu Cu

N N N N H H

H3C CH3 CH3 +2 +2 [Cu(tet a)] [Cu(2,3,2-tet)] -7 -1 -1 ka = 3.6 x 10 [sec ] ka = 4.1 [sec ]

+2 +1 k +n [Cu(L)] nH a +2 (aq) + Cu (aq) + HnL (aq)

Figure-1.11 Kinetic stability of mscrocyclic and acyclic complex

Chapter 1 INTRODUCTION

1.6.3 Coordination template effect The coordination template effect is an effect in which metal ion employed in the reaction allows access to certain ligands which would be hard to synthesize otherwise. Thompson and Busch published the first reports of this phenomenon in 1960s [71-74]. They reported a dramatic example of the role played by a metal ion in the condensation between α-diketones and β-mercaptoethylamine. They suggested that the role of the metal ion was to bring the reactants together in the product form that is most favourable for complexation (Figure-1.12)

SH H H R N N N + S R S R R R N O H2N non template conditions Major product + 2 SH Diimine produced in very low yield R O HS Ni(II) template R N S Ni

R N S

Major product Figure-1.12 Ni(II) Template condensation studied by Thompson and Busch

Busch and Thompson also distinguished between two classes of template processes, the equilibrium displacement and the kinetic template process. The equilibrium displacement is also known as thermodynamic template effect and is what they observed in the condensation between diketones and mercaptoethylamine. Ni(II) as a template ion picks the complementary ligand from the equilibrium mixture and shifts the equilibrium towards chelated product . The second class of template effect is the kinetic template effect. It involves construction of cyclic intermediate around the metal centre, which promotes the formation of cyclic product. Metal is necessary to form the product in the kinetic effect. Figure-1.13 shows the example of kinetic template effect studied by Thompson and Busch.

Chapter 1 INTRODUCTION

R N S R 2+ Ni

R N SH +RX slow X +RX 2 slow R N S R R N SH + 2+ Ni A Ni + 2RX 2 R N S R R N SH

1 X 3

R N S 2+ Ni

R N S rapid Br slow Br H Br S R N SH 4 R N 2+ 2+ B Ni + Ni R N SH R N S Br 1 Br 5 Figure-1.13 Kinetic template effect [74]

Directive influence of Ni(II) metal centre on formation of macrocyclic complex (compound 5) is what Busch and Thompson called the kinetic template effect. In reaction A, Ni(II) is not involved in template process. The Ni(II) complex (compound 1) reacts with a monofunctional halide in two reasonably slow steps. In the first, monosubstituted thioether is produced (compound 2) which in the second step is again S-alkylated into the final product (compound 3). In contrast, in reaction B, when Ni(II) complex is reacted with α, α-dibromo-o-xylene only the first step is slow. After combining the first sulfur with the reagent, the intermediate compound is produced (compound 4). Then, the remaining sulfur and bromine, oriented for cyclisation, rapidly give rise to macrocycle 5. The ring closure reaction is promoted by the central metal ion which holds both mercapto groups in cis positions. Measurable concentrations of the intermediate compound 4 were not observed which Busch and Thompson called ‗‘the essence of the kinetic coordination effect‖ [74]. 14

Chapter 1 INTRODUCTION

Perhaps, the synthesis of crown ethers in the presence of group I metals studied by Mandolini and Masci [75-77] is a better illustration of the kinetic template effect. A schematic representation of this process is shown in Figure-1.14.

Br O O - OH O O M+ cyclisation O O + MBr Base O O O O O O O O Br Figure-1.14 Schematic representation of the M(I) template synthesis of the benzo-15- crown-5

The key step in the template synthesis of this benzo-15-crown-5 is the formation of an intermediate compound in which the functional group (-O-) and (-Br) are brought together close to each other by chelating to the metal ion. When functional groups are held in close proximity, they cyclise readily because the nucleophilic phenolate oxygen attacks the positive dipole on the carbon atom of CH2-Br fragment. The intermediate pre-crown complex is found to bind metal more strongly than the reactant or product. In general, association between alkali metal ion and the crown ethers are dependent upon the nature of the metal and the ring size of the crown ether, which is related to the length of polyether chain. In simple terms, if a host to selectively bind an alkali metal ion is desired, then this ion should be used as template for its formation. The driving force for the association between polyether chain and central metal is the coulombic interaction between them. The metal ion by chelating the appropriate terminal atom from the side chain allows the rest of the oxygen donors to wrap around, which additionally stabilises the intermediate complex. In fact, the metal is acting as kind of a catalyst which stabilises the cyclic intermediate and therefore increases the rate of formation of the crown product. This is why this phenomenon is known as kinetic template effect.

1.6.4 Effect of donor atoms on coordination bond formation In addition to oxygen atoms, many donor atoms have been introduced into macrocyclic backbones and these donor atoms include nitrogen [51, 52], sulfur [78] and selenium [79] atoms. These donor atoms (Hetroatoms) affect host guest interaction by influencing preorganization of macrocycles through their basicity, polarity, polarizability and size. For example, different donor atoms affect dipole dipole repulsion and salvation properties of macrocycles in different way. Enhanced 15

Chapter 1 INTRODUCTION donor basicity is one of the major factors responsible for ―macrocyclic effect‖ [80]. However, explanation of effect of donor atom is not simple, because all properties of donor atoms mentioned above must be considered and properties of guest cation as well. In practice, donor effect has been explained in terms of soft and hard acid and base (SHAB) theory. The decreasing order of softness of donor atoms is as S > N >O. Thus, usually sulfur acts as the best donor for transition metal ions that are generally soft Lewis acids [81]. Oxygen being a hard Lewis base is the best donor for alkali and alkaline earth metal ions that are hard Lewis acids. Depending upon structure of host and property of guest, nitrogen can act as a donor for both hard and soft metal ions [82-84]. In addition to its softness, sulfur is bigger in size than nitrogen and oxygen. Therefore, sulfur produces stronger dipole dipole repulsion into system, thus producing stronger intramolecular strain [85a] due to its larger size that decreases dipole dipole distance. Thus, in sulfur containing macrocycles, sulfur atoms turn to orient their lone pairs of electron away from center of ring [85b]. Thus, sulfur containing macrocycles require additional energy for macrocyclic conformational adjustment during complexation as compared to oxygen containing macrocycles. Sulfur containing macrocycles generally do not form inclusion complexes with alkali and alkaline earth metal ions unless and until energy gained from complexation is enough to compensate for energetic cost for conformational adjustment because metal sulfur interaction is weak due to mismatch between hard acid and soft base [86]. However, sulfur containing macrocycles really make inclusion complexes with transition metal ions, because in this case metal–sulfur interaction is strong and can give enough energy to compensate for conformational adjustment [85c]. It is well known that phenolic oxygen atoms are less basi than alkoxy oxygen atoms and consequently phenolic oxygen atoms are less effective as donors for complexation of alkali and alkaline earth metal cations. It accounts for the fact that introduction of rigid aryl moiety may not increase extent of host guest interaction when a phenolic donor is introduced, despite the fact that rigidity of system is increased [84].

Chapter 1 INTRODUCTION

1.6.5 Soft and hard acid and base theory (SHAB) The soft and hard acid and base theory published by Pearson and Songstad in the late 1960s was originally applied to organic chemistry as an extension to the Lewis acid-base theory [87]. In general, this theory sates that hard acids prefer to interact with hard bases and soft acids prefer to interact with soft bases. The classification of soft and hard acids and bases is shown in Table-1.1.

Table-1.1 Classification of soft and hard acids and bases HARD ACIDS SOFT ACIDS H+, Li+, Na+, K+, Be2+, Mg2+, Ca2+,Sr2+, M0 (metal atoms), Cu+, Ag+, Au+, Tl+, Sn2+, Mn2+, Al3+, Se3+, Ga3+, In3+, La3+, Hg+, Cs+, Pd2+, Cd2+, Pt2+, Hg2+, 3+ 3+ 3+ 3+ 3+ 4+ 4+ 4+ + + + + + + Cr , Co , Fe , As , Ir , Si , Ti , Zr , CH3Hg , RH3, RS , RSe , RTe , I , Br , 2+ 2+ 2+ + + VO , UO2 , (CH3)2Sn , BeMe2, BF3, HO , RO , I2, Br2, Trinitrobenzene, etc. 2– BCl3, B(OR)3, Al(CH3)3, Ga(CH3)3, O, Cl, Br, I, R3C, Co(CN)5 , InCl3, + + + + In(CH3)3, RPO2 , ROPO2 , RSO2 , BH3, RS , Br2, RO(dot), RO2(dot), + 7+ 5+ + + ROSO2 , SO3, I , I , R3C , RCO , CO2, carbenes + 3+ 3+ 3+ NC , N , Cl , Gd , AlCl3 HARD BASES SOFT BASES – – – 3– 2– – – – 2– – H2O, OH , F , CH3CO2 , PO4 , SO4 , R2S, RSH, RS , I , SCN , S2O3 , Br , 2– – – – – CO3 , NO3 ,ClO4 , ROH, RO , R2O, NH3, R3P, R3As, (RO)3P, CN , RNC, CO, – – RNH2, N2H4 C2H4, C6H6, H , R BORDERLINE ACIDS BORDERLINE BASES 2+ – – – HX (Hydrogen bonding molecules), Fe , Pyridine, C6H5NH2, N2, N3 ,Cl , NO2 , 2+ 2+ 2+ 2+ 2+ + 2– Co , Ni , Cu , Zn , Pb , SO2, NO SO3 Soft base donors are defined as atoms of high polarizability or low electronegativity that can be easily oxidised and with low-lying empty orbitals. Hard base donors are of low polarizability, high electronegativity, difficult to oxidise and possess high energy empty orbitals which are to excess. Soft acid acceptors are ions of low positive charge, large size with several easily excited outer electrons. Hard acids have a high positive charge, small size and do not have easily excited outer electrons. As established by Pearson, the electronic properties of the atoms involved in donor acceptor interaction, correlate to their hardness by equation [88];

Chapter 1 INTRODUCTION

χ (I+A)/2, η = (I-A)/2 and σ=1/ η ‗I‘ is the ionisation potential, A is an electron affinity, χ is the absolute electronegativity, η is absolute hardness and σ describes softness.

1.6.6 Effect of guest cation on coordination bond formation Size-fit principle operates well with alkali and alkaline earth metal ions but usually does not work with transition metal ions, especially lanthanides and actinides. Alkali and alkaline earth metal ions do not have available d-orbital and possess a simple spherical geometry that is easily accommodated by host. However, most transition metal ions have partially filled d-orbital. Lanthanides and actinides possess partially filled f-orbbital. Crystal field theory and ligand field theory, both tell that these available d-orbitals or f-orbitals require additional geometric requirements for complexation. As a result, significance of role played by size-fit principle in determining type and extent of host-guest interaction is decreased unless geometric preference of metal ion is met [89]. Coordination number of guest metal ion also plays a significant role in host guest interactions [90, 91, 92]. Preferred coordination number of some cationic guests is given in Table-1.2. To show importance of coordination number, the preferred coordination number of some metal ions presented an example in which selectivity of Ba+2 / K+1 with [2.2.2]-cryptand was compared against [2.2.C8]-cryptand [93] (Figure-1.15). Selectivity is exactly reversed when proceeding from [2.2.2]-cryptand to [2.2.C8]- cryptand. Hence, Coxon et al argued that latter cryptand lacks sufficient donor atoms to satisfy preffered coordination number (8) of Ba+2. However, in this case, two metal ions have different valence states. Other factors, e.g. salvation may also be important. Dillon and co-workers [94] studied complexation properties of [2.2.2]-cryptand and [2.2.1]-cryptand in comparison with their analogs [2.2.C8]-cryptand and [2.2.C5]- cryptand (Figure-1.15) with divalent metal cations. Their results showed clearly that under condition of approximate size-fit, [2.2.2]-cryptand and [2.2.1]-cryptand almost always show higher complexation ability. It should be noted that regular cryptands and their analogs differ not only in number of donor atoms present in them but also differ in other aspects due to differing in degrees of dipole dipole repulsion and degrees of salvation.

Chapter 1 INTRODUCTION

Table-1.2 Coordination (hydration) numbers of IA and IIA metal ions [95]

Cation Li+ Na+ K+ Rb+ Cs+ Be2+ Mg2+ Ca2+ Sr2+ Ba2+ Hydration Number 6 6 6 6 6 4 6 8 8 8

N N

O O O O

N N

[2.2.C5]-Cryptand [2.2.C8]-Cryptand Figure-1.15 Analogs of [2.2.1]-cryptand and [2.2.2]-cryptand [93, 94]

The extent of host-guest interaction is strongly affected by salvation of guest cations. Bushmann and coworkers [170] offered a good example in this respect. They studied complexation behaviour of 18-crown-6 and [2.2.2]-cryptand in the systems of varying ratios of water and chloroform and they established that complexation strongly depend on cation solvation. Effect of cation salvation is so strong that size-fit principle usually does not work with lanthanides and actinides [96a, 96b].

1.6.7 Template synthesis and transmetallation reactions Preparation of cyclic Schiff bases is rather difficult. Different condensation products (polymeric or oligomeric in nature) may be resulted when di- or poly functional precursors are used. This will require another job to purify the desired macrocyclic product and reduces the yield. To overcome this problem, high dilution conditions may be used, in which a large amount of solvent reduces the chances of cross reactions. An alternative way to avoid cross reactions is to use a metal ion in a template reaction. Metal ion is not always necessary on the preparation of Schiff base ligands [171-172]. For example, a [2+3] macrobicycle can be prepared by directly mixing three equivalents of 1, 3-dibenzaldehyde and two equivalents of tren in refluxing methanol (Figure-1.16) [173].

Chapter 1 INTRODUCTION

N N

Methanol 2. TREN N N 3. + O O N N

N N

Figure-1.16 Synthesis of macro-bicyclic ligand [173]

Schiff base condensation reactions with metal template ions are one of the most common methods to prepare macrocyclic systems. A metal ion in a template reaction directs the cyclisation of a ligand. An examples of a Schiff base template reactions is shown in Figure-1.17 [174-176].

Cl N

MnCl2.4H2O N N N H N NH NH NH Mn O O + 2 2 N N

Cl Figure-1.17 Template synthesis [174-176]

When designing the synthesis of a macrocyclic complex via template reactions, size of the metal ion used as template should be taken into account because not all metal ions will fit into a specific macrocyclic cavity [177-179]. The importance of the size of the cation in directing the synthetic pathway is shown with the following example. Schiff base condensation products of 2, 6-diacetypyridine with respectively 1, 8-diamino-3, 6-dioxaoctane or 1, 11-diamino-3,7,9-trioxadecane in the presence of alkaline earth metal cations are shown in Figure-1.18. Only Mg(II) produces [1+1]

N3O2 macrocycle, yet, Mg(II) does not generate [1+1] N3O3 macrocycle. [1+1] N3O3 can be generated when larger cat ions are used as template (Calcium, strontium, barium and lead(II)). These larger cations also generate [2+2] N6O4 macrocycle derivatives [180-181].

Chapter 1 INTRODUCTION

N +4 N N

2+ N 2+ , Pb O O N 2+ , Ba O N N 2+ , Sr Pb O O Ca Pb(II) O O + +2

O O N H2N O O NH2 Pb n N N N N Mg N O O

Figure-1.18 Formations of [1+1] and [2+2] macrocyles

A mechanism for the formation of [1+1] and [2+2] macrocyles was proposed by Nelson and is shown in Figure-1.19. In the mechanism, the initial product of Schiff base condensation was proposed to be mono-carbony mono-amine intermediate. This initial intermediate may undergo intramolecular condensation to give [1+1] macrocycle (step ii) or an intermolecular condensation (steps iii, iv) and ring closure to give [2+2] ring (steps v, vi). Nelson et al. also pointed out that the formation of [1+1] and [2+2] macrocycles depends on the number of factors [180].  If the length of the diamine chain is insufficient to hold two carbony groups, formation of [1+1] is not favoured.  If the size of metal ion is large in related to the size of the [1+1], the formation of [2+2] is favoured.

H C C + H2N N 2 O O (i) M

C C (ii) N M N C C N O [1+1] M diamine

diketone (v ii) NH2 (iv ) (iii)

C C C C N N N O M M

NH2 H N N O 2 C C C C (v i) (v ) N N diamine diketone M

N N C C

[2+2] Figure-1.19 Mechanism for formation of [2+2] and [1+1] macrocycles [180] 21

Chapter 1 INTRODUCTION

Macrocyclic complexes prepared in the presence of a metal ion can undergo transmetallation reactions when treated with different metal salts; these methods allow the formation of the specific systems, which are not accessible in any other methods. An example of transmetallation of barium(II) with manganese(II) is shown in Figure- 1.20 [182].

N N N N N Mn N - MnCl2.4H2O 2Cl O Ba O .2ClO4- O O H H MeOH Mn N N Transmetallation N N

N N

Figure-1.20 Transmetallation of barium(II) with manganese(II) in macrocycle complex [182] 1.7 Synthesis of macrocycles Macrocyclic compounds are usually prepared from smaller, generally linear molecules. To synthesize a macrocycle, either an intermolecular reaction, where two or more molecules come together in a reaction to make a ring, or an intramolecular reaction, in which one molecule reacts with itself to make a ring, must occur. Because chemistry of formation of macrocycles is same as that of polymerization, therefore one must take necessary steps to prevent polymerization. Customarily, that was done by involving high dilution chemistry in which large amount of solvent and low concentrations of reagents are used to avoid polymerization. In addition, reagents needed to be added regularly and slowly. At low concentration, molecule preferably reacts with itself than with another molecule. This is usually inefficient process because large quantities of solvents are used but yield is very low. To obtain high yields of macrocycles at high concentration of reagents, a way to orient reactive sites of reacting molecules was needed. Orientation of reactive sites should be in such a way that they readily undergo cyclisation. Transition metals can induce a ―template effect‖. A metal "template" influences the geometry by binding to linear molecule and can accelerate either intramolecular or intermolecular reaction. Hence, a careful choice of metal ion and relative positions of donor atom would allow a metal to control cyclisation process.

Chapter 1 INTRODUCTION

Template effect further can be divided into two slightly more specific effects as follow:  Kinetic template effect: It describes directive effect of metal ion, which controls steric course of an order of stepwise reactions.  Thermodynamic template effect: In cases where thermodynamic template effect operates, metal ion disturbs an existing equilibrium in an organic system in such a way that required product is produced often in high yield as a metal complex. Kinetic template effect operates in most cases. However an assignment cannot be made in all cases [97].

1.8 The formation of macrocyclic complexes The chemistry of multi-site crown ethers has recently won a remarkable attention because of their charming structures, high abilities to make complex with guest cations [98-108] and their applications in synthetic, medical, host–guest and supramolecular chemistry [109-116]. In recent times, the complexation behavior of crown ethers with alkali metals and other cations has been extensively investigated. When the radius of metal cation is exactly equal to the size of the crown ether unit, it always forms a 1: 1 host/guest complex. Over recent years, there has been very wide interest in the design and synthesis of larger supramolecular and supermolecular receptors for binding both small molecules and ions (both cations and anions) [117]. Both the structural and electronic complementarily between host and guest are responsible for the strength of binding and the degree of ionic or molecular recognition. While practically all host-guest systems presenting molecular recognition, will show both steric and electronic complementarily to some extent. Macrocyclic rings have been used regularly as structural components especially for binding metal ions in both supramolecular and supermolecular systems. In part, this shows the tendency of macrocyclic ligands to synthesize complexes that exhibit both enhanced kinetic and thermodynamic stabilities. It shows that the donor sites in these macrocyclic rings are more or less controlled by the cyclic nature of the ring [118]. One group of this type involves structures composed of covalently linked macrocyclic ligand species that are capable of making bond with transition and other

Chapter 1 INTRODUCTION heavy metal ions. While now there are many examples of such systems, incorporating two linked macrocycles [119-120]. Examples for incorporating three or more linked rings are much less common [121-129]. In crown ethers, generally the oxygens atoms are involved in complexation with various ionic species. This is termed as "host-guest" chemistry, in which the ethers act as host and the ionic species act as guest. One of the major uses of crown ethers is to use as phase-transfer catalysts and as agents to promote solubility of inorganic salts in organic solutions. "Purple benzene" for example, is a solution of benzene, 18-crown-6 and potassium permanganate that is used as an oxidizing agent. In this solution, crown ether dissolves in benzene and the potassium ion complexes with the crown ether and the permanganate is forced to dissolve in the benzene in order to ion pair with the potassium ion. This type of chemistry (host-guest) naturally occurs in cyclodextrins and macrocyclic polyether antibiotics. Non-covalent interactions are currently attracting a lot of interest for research [130-135]. These are important for chemistry, biology and materials science. Taking ð···ð interaction for an example, it contributes to self-assembly or molecular recognition processes and the packing of molecules incorporating aromatic groups in crystals, [136-140] plays a role in the binding and conformations of nucleic acids and proteins [141-143]. ð··ð interaction has also been used in the detection of polycyclic aromatic hydrocarbons [144]. ð··ð can also influence the conductivity of some molecular conductors [145], the behavior of some liquid crystalline materials [146] and the electronic and optical properties of some materials [147]. In solution, polar molecules of solvent surround metal ions. In water, cations of 3d transition metals, in general, are surrounded by six water molecules. They form 2+ hexa aqua-complexes like [Ni(OH2)6] . A ligand added to solution of hydrated metal cations may replace water molecules of aqua complex. Let us consider analogy between transfers of proton in an acid-base reaction

Chapter 1 INTRODUCTION and substitution of an aqua ligand in a complex formation reaction.

Discussing about the complex formation in water, aqua ligands are often not written openly. For example Ni2+ in water is written as Ni+2(aq) or even Ni+2 but not +2 +2 [Ni(H2O)6] . If ammonia replaces one water then it may be written as [NiNH3] +2 instead of [Ni(H2O)5NH3] . As solvate ligands (H2O) are frequently not written when a complex formation reaction in water is described. Reaction looks like an addition but in reality, it is a substitution of an aqua ligand by a new ligand. So, reaction mentioned above is often written in a simplified way excluding free and coordinated solvet (water) molecules.

2+ +2 Cu + NH3 [Cu(NH3)]

Stepwise substitution

In the process of complex preparation, new ligands (e.g. NH3) replace solvent molecules (H2O) one by one. Process of complex formation takes place systematically where every step corresponds to substitution of one H2O by NH3. Each step is characterized by an equilibrium constant Ki, called stepwise stability constant (or stepwise formation constant). Example: +2 [Cu(NH )] 2+ +2 3 4.3 Cu K = = 10 + NH3 [Cu(NH3)] 1 +2 [Cu ][NH3]

+2 [Cu(NH ) ] +2 3 2 3.7 [Cu(NH )] +2 K = = 10 3 + NH3 [Cu(NH 3)2] 2 +2 [[Cu(NH 3)] ][NH 3]

Chapter 1 INTRODUCTION

+2 [Cu(NH ) ] +2 3 3 3.0 [Cu(NH ) ] +2 K = = 10 3 2 + NH3 [Cu(NH 3)3] 3 +2 [[Cu(NH 3)2] ][NH 3]

+2 [Cu(NH ) ] +2 3 4 2.3 [Cu(NH ) ] +2 K = = 10 3 3 + NH3 [Cu(NH 3)4] 4 +2 [[Cu(NH 3)3] ][NH 3]

K1, K2, K3, K4 are stepwise stability constants. These equilibrium constants are described by a general expression:

[ML ] + L n-1 [MLn]

[MLn] Kn = [MLn-1] [L]

Constants decrease with increasing number of ligands. Be aware that complex formation constants are association constants, contrary to acidity constants, which are dissociation constants.

1.9 Crown ethers

Crown ethers are macrohetrocycles containing repeating (–Y–CH2–CH2–)n unit where Y is a hetro atom usually O, S, N, P. The crown ethers are macrocyclic polyethers, which are large enough to encircle the metal cations. These compounds have the cavities, which are able to encapsulate the metal cations. Crown ethers have the ability to form stable and selective complexes with non atomic or molecular ions thus these exhibit the phenomenon of recognition. Crown ethers are flexible host molecule and they can change their conformations to fit in the guest molecule. It is found spectroscopically that the cavities of crown ethers, free from guest cations, are filled with methylene moieties of their own. But when guest ion resides these cavities, the methylene moieties are emerged out. In 1967, Charles J. Pederson at du Pont found that cyclic polyethers can make coordination bond with metal ions such as K+1 in non-polar solvents and thus separating metal cations from their associated anions and rendering their salts soluble in these solvents. When potassium permanganate (KMnO4), a useful oxidizing agent,

Chapter 1 INTRODUCTION was subjected to action of such a cyclic polyether, it became soluble in benzene and was then available for use in an extended range of reactions. Pederson assigned trivial name ―crown ethers‖ to this class of coordination agents, a nomenclature that has become standard. Some typical crown ethers are shown below;

12-crown-4 13-crownn-4 15-crown-5

18-crown-6 27-crown-9 Dicyclohexyl-18-crown-6 Potassium permanganate complex of dicyclohexyl-18-crown-6 (a host-guest complex) has following structures;

Pederson prepared around 60 different crown ethers in 1960s and found that size of central "cavity" of crown ethers determined which metal ions would be complexed most strongly, depending on their size. Donald J. Cram at UCLA then synthesized a large number of functionalized crown ethers of all sizes and shapes and "delineated the principles of molecular architecture needed for optimal binding and specificity" [148].

Chapter 1 INTRODUCTION

1.10 Spectroscopic analysis of ethers [149] Table-1.3 IR data - presence of C-O and C-H Absorbance (cm-1) Interpretation 1200 -1250 (strong, broad) C-O stretch 2800-3049 C-H stretching 1402-1466 cm-1 C-H bending Vibrations

 1H NMR = H-C-O-C unit is the most easily recognized (similar to H-COH of alcohols). H-C-O (deshielding due to O) shows resonance at 3.3 – 4.0 ppm  13C-NMR C-OH typically 57 - 87 ppm (deshielding due to O)  UV-VIS Simple ethers give usually no absorption above 220 nm.  Mass spectrometry Loss of alkyl radicals due to cleavage of branches adjacent to C-O is common.

1.11 Applications of crown ethers 1.11.1 In organic chemistry  Phase transfer catalysts in synthesis of halogen containing organic compounds, nitriles, ethers, carboxylic acids, ketones, amines, amino acids, heterocyclic compounds, elementorganic compounds etc.  Crown ethers are used as catalysts, inhibitor and additives in processes of polymerization, co-polymerization and polycondensation (for example, polybutadiene, polycarbonate, polysulfones etc.)

1.11.2 In analytical chemistry  In separation and extraction of substances (extraction, concentration and chromatography methods)  In determination of cations (extractive photometry, potentiometry, conductometry, polarography, voltamperemetry, chelatometry titration)  Sorbentes in extraction-column, thin-layer, liquid and ion chromatography for separation cations, isotopes, alkaline and alkaline-earth metals, anions of VII group elements  Carrier in ion-selective electrodes

Chapter 1 INTRODUCTION

 In separation of non-salt organic compounds  In determination of water in organic and inorganic compounds  In thin-layer electrophoresis  In Au-Mossbauer spectroscopy and in intermetalic systems (Au-clouds determination in gold bars down to trace quantities)  In ultraviolet absorption determination of proteins

1.11.3 In inorganic chemistry  In separation and concentration of alkaline, rare-earth and alkaline-earth metals and some isotopes  In selective extraction of alkaline, rare-earth and precious metals, actinides, lanthanides etc.  As Ion-exchangers with crown ethers additive groups

1.11.4 In electrical engineering  For different electrical devices (current sources, electrochemical sensors etc.)  Foreing nonaqueous electrolyte in manufacturing of alkaline battery inert to light metals  Additives to solid electrolytes  Component in insulating oils for condensers  In galvanization (for instance in lustrous copper coating)  In materials which electrical resistance is dependant from temperature  For manufacturing of ion-conducting materials

1.11.5 In electronics  Surface modification of matrix plates  In polymeric coating of matrix plates  For creating transparent semiconductors for thermistors  For manufacturing electrochromic materials (metal – crown ether complexes)  Absorbent for surface cleaning in producing of semiconductor devices

1.11.6 In biology and medicine  For studying cation-transportable processes with the aim to create of new medicines

Chapter 1 INTRODUCTION

 For selective elimination of hazardous for organism ions of metals (for example, copper and lead)  Agents on the base of crown ethers with antimicrobial and anticoccidive activity taking effects anticonvulsive, miorelaxative and antihypoxic reaction  Remedy for treatment of circulatory disturbance and ischemic heard disease  For manufacturing of psychotropic and immunotropic remedies on the base of aza- and diaza-crown ethers, their derivatives and cryptands  Container-capsule for medicines, aromatic compounds and physiologic active compounds Crown ethers and other macrocycles proved their practical values shortly after their discovery [150, 151]. So far, these compounds were extensively used to separate isotopes [152], in organic synthesis [153], in biological reaction [154], in environmental analysis [155], in pharmaceutical industry [156], in membrane transport, [157, 158, 159, 160] and as ion selective electrodes [161]. Other applications of macrocycles include their use as surfactants [162], as antibiotic receptors [163], as sensors [164], as enzyme models [165], and as catalysts [166]. These applications work because macrocycles have ability to capture cations and to activate anions with consequent enhancement of basicity or neuclophilicity of anion [167]. Most significant and practical current application of macrocyclic polyethers has been seen in catalysis. In heterogeneous phase transfer catalysis, hydrophilic substrates are moved into organic phase (Figure-1.21). In homogeneous catalysis, macrocycles increase solubility of reactants in a given solvent system [168]. + - + - K (Crown) X + R-Y R-X + K (Crown) Y

+crown Organic Phase

-crown + - + - K X K Y

Solid Phase Figure-1.21 Solid-liquid phase transfer catalysis with crown ethers [169]

Chapter 2

Experimental

Work

Chapter 2 EXPERIMENTAL Work

2.1 Introduction

My research work involes the synthesis of 18-crown-6 and its complexes with nickel, copper and zinc. It also contains the synthesis of a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) and 1, 3-diamino-2-propanol, a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) and 1, 4-diaminobutane, a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol](H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane, a macrocycle based on 2,

2-methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) and triethylene tetramine and a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) and Bis-[2-aminoethyl]-amine (diethylene triamine). These macrocycles were further used to synthesize mono-nuclear and polynuclear complexes with different combinations of metals. These complexes may be homo-nuclear or hetronuclear.

2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) was prepared by the oxidation of 2, 2 –methylene-bis-[(6-hydroxymethyl)-4-tert-butylphenol](H2mhtbp).

And 2, 2–methylene-bis-[(6-hydroxymethyl)-4-tert-butylphenol](H2mhtbp) was prepared by refluxing 4-tert-butylphenol and formaldehyde in the presence of NaOH under nitrogn atmosphere at 60 oC.

2.2 General conditions 2.2.1 Solvents and reagents

Solvents used for preparative chemistry were pure or of HPLC grade and were used without further purification. An absolute ethanol was used in synthesis of macrocycles and in the reactions monitored by ESI-MS unless otherwise stated. Chemicals used in this research work were Analar or reagent grade and were used without further purification.

2.2.2 Instrumentation The synthesized compounds were characterized via UV, NMR, IR, Mass spectrometery, CHN analysis and single crystal X-ray crystallography.

UV spectra were taken on a Spectronic 20 UV-1201 Shiniadzu spectrophotometer. Atomic absorption was taken on a Hitachi Z-8000 Polarized

Chapter 2 EXPERIMENTAL Work

Zeeman Atomic Absorption spectrophotometer. DTA graphs were obtained on a Shimadzu D-40 Thermal Analyzer. -1 Infrared Spectra were recorded as KBr discs in the range 4000-300 cm on Perkin Elmer Paragon 1000 PC Fourier Transform Spectrometer or a Perkin Elmer Spectrum 100 Spectrometer. Elemental analyses were performed by Mrs Pauline King within the chemistry department on an EAI Exeter analytical CE-440 elemental analyzer. 1H NMR spectra (400MHz) were recorded on Bruker AC250FT or DPX-

400MHz spectrometer in CDCl3 unless otherwise stated. Chemical shifts [δ] in ppm are relative to SiMe4. Mass spectra were recorded on a Thermo Fisher Exactive + Triversa Nanomate mass spectrometry (ESI) within the chemistry department of Loughborough University, Loughboro, UK. Single crystal X-ray diffraction data were collected at 150K on Bruker Apex II CCD [195] diffractometer using graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) at Loughborough University, Loughborough, UK. The structures were solved by direct methods and refined by full-matrix squares on F2. The Bruker SHELXTL [196] software was used for structure solution and refinement. All non- hydrogen atoms were refined anisotropically and hydrogen atoms were inserted at calculated positions using a riding model, unless otherwise stated. The crystallography graphics were done using XP [196], Mercury 2.4 [197] and Ortep 3 for Windows [198] and were rendered in POV-Ray software [199].

2.3 Synthesis of 18-Crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane)

22.5 g (20.1 ml.) of Triethylene glycol and 120 ml. of Tetrahydrofuran was refluxed in three-necked flask. To this refluxing solution, 60% solution of potassium hydroxide that is prepared by dissolving 21.8 g (0.389 moles) of potassium hydroxide in 14ml of water, was added. After about 15 minutes of strong stirring, a solution of 28 g of 1, 2-bis (2-chloroethoxy) ethane in 20 ml of Tetrahydrofuran was added in a stream. After the addition is complete, the solution was reflux and stirred vigorously for 18–24 hours. THF was evaporated after cooling the solution and 100 ml of dichloromethane was added to the resulting thick, brown slurry to dilute and filtered through a glass frit. The salts removed by filtration, were again washed with fresh 33

Chapter 2 EXPERIMENTAL Work dichloromethane to remove absorbed crown ether. All the organic filterates were combined and this combined organic solution was dried over anhydrous magnesium sulfate, filtered, evaporated to minimum volume and distilled under high vacuum using a simple vacuum distillation pump. A typical fraction contains 14-17g (38– 44%) of crude 18-crown-6.

2.3.1 Purification of crude 18-Crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane)

To 10 g of the crude 18-crown-6, 20 ml of acetonitrile was added. The resulting slurry was heated on a hot plate to effect solution. The solution was stirred vigorously. As it was allowed to cool to ambient temperature, fine white crystals of crown- acetonitrile complex were deposited. The flask was kept in a freezer for 24–48 hours to precipitate the complex as much as possible. The solid was collected by rapid filtration and was washed once with a small amount of cold acetonitrile. The hygroscopic crystals were transferred to a 200-ml, round-bottomed flask equipped with a magnetic stirring bar and a vacuum takeoff. The acetonitrile was removed from the complex under high vacuum (using vacuum distillation pump), with gentle heating ( 35°C), over 2–3 hours. The pure colorless 18-crown-6 (5-7gm, 56–66%) crystallizes on standing, m.p. 38° C.

2.3.2 FLOW SHEET DIAGRAM FOR THE SYNTHESIS OF 18-CROWN-6 (1,4,7,10,13,16-HEXAOXACYCLOOCTADECANE) Take 22.5g of triethyleneglycol and 120 ml of THF in a three-necked flask equipped with mechanical stirrer, reflux condenser and an addition funnel

Stir and add KOH Soln. (21.8 g = 0.389 moles of KOH in 14.0 ml of H2O) (The Soln. warms slightly)

Chapter 2 EXPERIMENTAL Work

After Stirring vigorously for 15 minutes, the Soln becomes rust brown in color.

Add Soln of 1, 2-bis (2-Chloroethoxy) ethane in THF (28.0 g of 1, 2-bis (2- Chloroethoxy) ethane in 20.0 ml of THF) and reflux the whole mixture while stirring vigorously for 18-24 hours.

Cool the Soln and evaporate THF under reduced pressure to get thick slurry. Dilute the thick slurry with 100 ml of Dichloromethane

Filter and wash the salt removed by filtration with more dichloromethane

Dry the filtrate over anhydrous MgSO4

Filter and evaporate to minimum volume and perform distillation under high vacuum using vacuum distillation pump to get typical fraction containing

14.0 g - 17.0 g (38% - 44%) of crude 18-Crown-6

Purification of crude 18-Crown-6 In 250-ml Erlenmeyer flask, add 20.0 ml of acetonitrile to 10.0 g of crude 18-Crown- 6, stir and heat the resulting thick slurry on hot plate to effect solution.

Stir the solution vigorously while it is cooling to ambient temperature and keep the flask in freezer for 24-48 hours.

Crystals of crown-acetonitrile complex are deposited, filtred and washed the crystals once with small amount of cold acetonitrile.

Transfer the hygroscopic crystals of crown-acetonitrile complex to a 200 ml round bottomed flask having magnetic stirring bar and vacuum take off (vacuum pump)

Chapter 2 EXPERIMENTAL Work

Heat gently ( 35°C) and stir under high vacuum over 2-3 hours to remove acetonitrile from complex.

18-Crown-6 The pure colorless 18-crown-6 (5-7g, 56–66%) crystallizes on standing. Melting point = 38O C

2.4 Synthesis of Ni-18-Crown-6 complex [IHCNi]

Ni Ni(NO 3)2 +

18-Crown-6 Ni-18-Crown-6

The reaction was carried out in 1: 1 molar ratio. A methanolic solution of Nickel nitrate was added to a solution of 18-crown-6 in methanol while stirring. The contents were stirred continuously and refluxed overnight and left for a week. The resultant solid product was filtered off and washed with methanol and dried in vacuum.

Elemental (CHN) analysis was calculated for C12H24O6.Ni+NO3 and found that this complex have 37.44% C, 6.28% H and 3.64% N.

2.5 Synthesis of Cu-18-Crown-6 complex [IHCCu]

Cu Cu(NO 3)2 +

18-Crown-6 Cu-18-Crown-6 36

Chapter 2 EXPERIMENTAL Work

The reaction was carried out in 1: 1 molar ratio. A methanolic solution of Copper nitrate was added to a solution of 18-crown-6 in methanol while stirring. The contents were stirred continuously and refluxed overnight and left for a week. The resultant solid product was filtered off and washed with methanol and dried in vacuum. Single crystal for X-Ray spectroscopy was obtained by vapour diffusion method.

Elemental (CHN) analysis for C12H24O6.2H2O.Cu(NO3)2 was calculated and found that the complex contains 29.54% C, 5.78% H and 5.74% N.

2.6 Synthesis of Zn-18-Crown-6 complex [IHCZn]

Zn Zn(NO 3)2 +

18-Crown-6 Zn-18-Crown-6

The reaction was carried out in 1: 1 molar ratio. A methanolic solution of Zinc nitrate was added to a solution of 18-crown-6 in methanol while stirring. The contents were stirred continuously and refluxed overnight and left for a week. The resultant solid product was filtered off and washed with methanol and dried in vacuum.

+1 Elemental (CHN) analysis for C12H24O6.Zn.H2O.NH4 shows that this complex contains 39.41% C, 8.27% H and 3.83% N.

2.7 Preparation of activated manganese dioxide

Activated manganese dioxide which was used to oxides 2, 2-methylene-bis-[(6- hydroxymethyl)-4-tert-butylphenol](H2mhtbp), was prepared from manganese(II) sulphate and potassium permanganate. 100 g of MnSO4 was dissolved in 125 ml of boiling distilled water and stirred at 70- 80 0C. To the stirred solution, a cold saturated solution containing 90 g of potassium permanganate (KMnO4) in 2.5 L water was added dropwise over 5 hours. When the addition was completed, the MnO2 was filtered off, washed with 3 litters of boiling water to remove all remaining KMnO4

Chapter 2 EXPERIMENTAL Work

0 and dried in the oven for a few days at 150 C to yield 90 g of active MnO2. (Yield was 94%)

Equation: 2KMnO4 + 3MnSO4 + 2H2O 5MnO2 + K2SO4 + 2H2SO4

2.8 Synthesis of 2, 2-methylene-bis-[(6-hydroxymethyl)-4-tert-butylphenol]

(H2mhtbp)

CH3 CH3 CH3

H C CH H3C CH3 H3C CH3 3 3 1. NaOH (10%), N2 8 days, 50 OC + 2HCHO 2. Acetic acid (50%)

OH OH OH OH OH

45 gram (0.30 moles) freshly ground 4-tert-butylphenol and 60 ml of 37% formaldehyde (0.80 moles) were taken in three neck flask under an atmosphere of N2.

Next 140 ml NaOH solution (0.35 moles; 14 g NaOH in 140 ml of H2O) was added and the mixture was heated for 8 days at 50 0C under a nitrogen atmosphere. The resulting yellowish resinous precipitates were filtered off and dissolved in 50 ml of acetone. The white solid precipitating from acetone solution was removed by filtration. The acetone solution was acidified by the addition of 200ml of 50% acetic acid that turned its colour into milky. Then it was diluted with 100ml of water and extracted several times by ca. 300 ml of Diethyl ether (Et2O) and ca. 300ml of ethylacetate. The organic extracts were combined and washed with 200ml of water and dried over anhydrous Na2SO4. The solvents were rotary evaporated to get 30 g of oil which was re-dissolved in toluene, toluene was used in excess and stirred well to ensure that oil has completely dissolved in toluene, and precipitated by addition of light PET ether. The turbid solution was left in a fridge overnight. 16.32 g of 4-tert- butyl phenol dimer (H2mhtbp) was collected by filtration under vacuum. Yield was 29.25%.

Elemental (CHN) analysis for C23H32O4 (H2mhtbp) was calculated and found that this compound contains 74.14% C, 8.94% H.

Chapter 2 EXPERIMENTAL Work

2.9 Oxidation of H2mhtbp to 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) CH CH 3 3 CH3 CH3 H C CH H C CH 3 3 3 3 H3C CH3 H3C CH3

MnO2, Chloroform

Stirring at room temperature

OH OH OH OH O OH OH O

MnO2 (10g) was suspended in 500 ml of Chloroform and stirred for 30 minutes.

To the suspension, 2.0 g of H2mhtbp was added and stirred for 5 hours at room temperature. The MnO2 was filtered off and filter cake was washed with 300 ml of Chloroform followed by 100 ml of acetone. The filtrate was evaporated in rotary evaporator to dryness and washed with hot ethanol to yield 1.0 g of yellow H2mftbp upon cooling. Yield was 50%.

Elemental (CHN) analysis for C23H28O4 (H2mftbp) was calculated and found that this compound contains 74.57% C and 7.72% H.

2.10 Synthesis of macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and 1, 2-Bis-[2-aminoethoxy]ethane [L-1]

CH3 CH3

H3C CH3 H3C CH3

CH3 CH3 N OH OH N H3C CH3 H3C CH3 O O - 4H2O 2 2 O O O O + H2N NH2 N OH OH N O OH OH O

H3C CH3 H3C CH3 CH CH 3 3

0.1g (0.273mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] (H2mftbp) was added in a 250ml round-bottomed flask containing 60 ml ethanol/methanol and refluxed for 30 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023g (0.27 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed overnight to get a clear yellow solution. This clear yellow solution was left for slow evaporation and after one weak from this solution, yellow powder was filtered and

Chapter 2 EXPERIMENTAL Work from the filtrate, yellow crystals were obtained that were characterised by single crystal x-ray spectroscopy. Yield was 0.078gram, 63.06%.

Elemental (CHN) analysis for C58H80O8N4 reveals that this macrocycle contains 72.47% C, 8.39% H and 5.83% N.

2.11 Synthesis of macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and triethylene tetramine [L-5.1]

CH3 CH3

H3C CH3 H3C CH3

CH3 CH3 H C CH H C CH 3 3 3 3 N OH OH N

- 4H O NH HN 2 2 NH NH 2 + H2N NH2 NH HN

O OH OH O N OH OH N

H3C CH3 H3C CH3

CH3 CH3

0.1g (0.273mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] (H2mftbp) was added in a 250ml round-bottomed flask containing 100 ml ethanol/methanol and refluxed for 30 minutes to dissolve H2mftbp completely. To this clear solution, 0.04g (0.27 mmoles) triethylene tetramine was added and refluxed overnight to get a clear yellow solution. This clear yellow solution was left for slow evaporation and after one weak from this solution, 0.244g yellow powder was filtered. Yield was 0.244 gram.

Elemental (CHN) analysis for C58H84O4N8.H2O indicates that this ligand contains 71.42% C, 8.89% H and 11.49% N.

2.12 Synthesis of macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and Bis-[2-aminoethyl]-amine [L-2]

CH3 CH3

H3C CH3 H3C CH3

CH3 CH3

H3C CH3 H3C CH3 N OH OH N

N - 4H2O 2 2 NH NH HN + H2N H 2

N OH OH N O OH OH O

H3C CH3 H3C CH3 CH CH 3 3

Chapter 2 EXPERIMENTAL Work

0.1g (0.273mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] (H2mftbp) was added in a 250ml round-bottomed flask containing 60 ml ethanol / methanol and refluxed for 30 minutes to dissolve H2mftbp completely. To this clear solution, 0.028g (0.2714 mmoles) bis-[2-aminoethyl]-amine was added and refluxed overnight to get a clear yellow solution and after one weak from this solution, yellow powder was filtered and this yellow powder was characterised by different spectroscopic techniques. Yield was 0.055gram.

Elemental (CHN) analysis for C54H74O4N6 tells that this compound have 74.45% C, 8.56% H and 9.65% N.

2.13 Synthesis of macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and 1, 3-diamino-2-propanol [IR-2]

CH3 CH3

H3C CH3 H3C CH3

CH3 CH3

H3C CH3 H3C CH3 N OH OH N - 4H2O NH HO 2 + 2 H2N 2 OH OH N OH OH N O OH OH O

H3C CH3 H3C CH3 CH3 CH3

0.1g (0.273mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] (H2mftbp) was added in a 250ml round-bottomed flask containing 60 ml ethanol / methanol and refluxed for 30 minutes to dissolve H2mftbp completely. To this clear solution, 0.0246g (0.273 mmoles) 1, 3-diamine-2-propanol was added and refluxed overnight to get a clear light yellow solution and after one weak from this solution, light yellow powder was filtered and this yellow powder was characterised by different spectroscopic techniques. Yield was 0.061 gram.

Elemental (CHN) analysis for C52H68O6N4 reveals that this ligand contains 73.90% C, 8.11% H and 6.63% N.

Chapter 2 EXPERIMENTAL Work

2.14 Synthesis of a homo-nuclear complex of calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol [IR-4/ IR-2]

0.1g (0.273mmoles) H2mftbp was added in a round-bottomed flask containing

0.0653g (0.273 mmoles) Ca(ClO4)2 in 60 ml ethanol. It was refluxed for 30 minutes to dissolve H2mftbp completely. To this clear solution, 0.0246g (0.273 mmoles) 1, 3- diamine-2-propanol was added and refluxed for 45 minutes. Then 0.022g (0.55mmoles) NaOH was added to the reaction mixture and it turned into colloidal solution containing yellowish ppt and then it was refluxed overnight. It was filtered after cooling at room temperature to get a yellow powder. Yield is 0.069 gram, 55.2%.

Elemental (CHN) analysis for C52H68O6N4Ca.ClO4 confirms that this compound contains 63.43% C, 6.96% H and 5.69% N.

2.15 Synthesis of a homo-nuclear complex of Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol [ IR-5B ]

0.1g (0.273mmoles) H2mftbp was added in a round-bottomed flask containing

0.0653g (0.273 mmoles) Ca(ClO4)2 in 60 ml ethanol. It was refluxed for 30 minutes to dissolve H2mftbp completely. To this clear solution, 0.0246 g (0.2714 mmoles) 1, 3- diamino-2-propanol was added and refluxed for 45 min and then to this refluxing solution, 1 ml of Et3N was added. After refluxing it overnight, 0.06g (0.2731 mmoles)

Zn(CH3COO)2.2H2O was added and refluxed for further 6 hrs. It was filtered after cooling at room temperature to get a yellow powder. This powder was crystallized by vapour diffusion method using DMF and Diethyl Ether. Yield was 0.078 gram.

Elemental (CHN) analysis for C52H68O6N4Zn2.CH3COO indicates that this complex have 62.67% C, 6.92% H and 5.41% N.

CH CH3 3

H3C CH3 H3C CH3

CH3 CH3

H3C CH3 H3C CH3 CH N O 3 O N - 4H2O NH HO Zn O O Zn OH 2 + 2 H2N 2 + N O O N OH Zn(CH3COO) 2 . 2H 2O O OH OH O

H3C CH3 H3C CH3 CH CH3 3 Dinuclear Complex of Zn

Chapter 2 EXPERIMENTAL Work

2.16 Synthesis of a hetro-nuclear complex of Manganese and Barium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3- diamino-2-propanol [CE-25]

0.1g (0.27mmoles) H2mftbp was added in a round-bottomed flask containing

0.0665g (0.27 mmoles) Mn(CH3COO)2.4H2O in 100 ml of Methanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.0246 g (0.27 mmoles) 1, 3-diamino-2-propanol was added and refluxed for 45 min and then to this refluxing solution, 1 ml of Et3N was added. After refluxing it overnight, 0.106g (0.27 mmoles) Ba(ClO4)2.3H2O was added and refluxed for further 6 hrs. It was filtered after cooling at room temperature to get a 0.254 g dark brown powder. Yield was 0.254 gram.

Elemental (CHN) analysis for C52H68O6N4Mn shows that this complex contains 69.39% C, 7.62% and 6.22% N.

2.17 Synthesis of a hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 4- diaminobutane [CE-24] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0942g (0.2714 mmoles)

Ca(ClO4)2.6H2O in 100 ml ethanol and refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.024g (0.2714 mmoles) 1, 4-diaminobutane was added and refluxed for 45 min and then to this refluxing solution, 1 ml of Et3N was added and refluxed overnight. Then to this refluxing solution, 0.12g (0.543 mmoles)

Zn(CH3COO)2.2H2O was added and refluxed further overnight. 0.223g yellow powder was filtered after cooling the refluxed solution. Yield was 0.223 gram.

Elemental (CHN) analysis for C50H64O4N2CaZn2 shows the presence of 64.72% C, 6.95% H and 3.02% N.

2.18 Synthesis of a hetro-nuclear complex of Lead and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-1] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0258g (0.068 mmoles)

Pb(CH3COO)2.3H2O and 0.0542g (0.2714 mmoles) Cu(CH3COO)2.H2O in 60 ml

Chapter 2 EXPERIMENTAL Work ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 1 ml of Et3N was added and refluxed overnight. 0.126g light green powder was filtered after cooling the refluxed solution. Yield was 0.126 gram.

Elemental (CHN) analysis for C60H86O9N4Pb2 indicates that this complex have 50.69% C, 6.10% H and 3.94% N.

2.19 Synthesis of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-3] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0531g (0.136 mmoles)

Ba(ClO4)2.3H2O and 0.199 g (0.543 mmoles) Ni(ClO4)2.6H2O in 60 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 1 ml of Et3N was added and refluxed overnight. It gave a clear green solution and after one week 0.055 gm light green solid was filtered. Yield is 0.055gram.

Elemental (CHN) analysis for C58H80O8N4Ni3Ba confirms the presence of 55.54% C, 5.92% H and 5.01% N.

2.20 Synthesis of a hetro-nuclear complex of Lanthanum and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy] ethane [CE-7] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.059g (0.136 mmoles)

La(NO3)3.6H2O and 0.0925 g (0.543 mmoles) CuCl2.2H2O in 60 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1 mmoles) NaOH was added and refluxed overnight. 0.18g green solid was filtered after cooling the refluxed solution. Yield is 0.18 gram.

Chapter 2 EXPERIMENTAL Work

Elemental (CHN) analysis for C58H80O8N4LaCu3 indicates that this complex contains 53.97% C, 6.25% H and 4.34% N.

2.21 Synthesis of a hetro-nuclear complex of Barium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-9] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.106g (0.2714 mmoles)

Ba(ClO4)2.3H2O and 0.0925 g (0.543 mmoles) CuCl2.2H2O in 60 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1 mmoles) NaOH was added and refluxed overnight. 0.16g green powder was filtered after cooling the refluxed solution. Yield is 0.16 gram.

Elemental (CHN) analysis for C58H80O8N4BaCu2 shows the presence of 55.23% C, 7.05% H and 5.22% N.

2.22 Synthesis of a hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-13] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.106 g (0.2714 mmoles)

Ba(ClO4)2.3H2O and 0.1192 g (0.543 mmoles) Zn(CH3COO)2.2H2O in 60 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1 mmoles) NaOH was added and refluxed overnight. 0.074 g yellow powder was filtered after cooling the refluxed solution. Yield is 0.074 gram.

Elemental (CHN) analysis for C58H80O8N4BaZn2.H2O reveals that this complex contains 55.84% C, 6.63% H and 4.49% N.

Chapter 2 EXPERIMENTAL Work

2.23 Synthesis of a hetro-nuclear complex of Lanthanum and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-15] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.118g (0.2714 mmoles)

La(NO3)3.6H2O and 0.199 g (0.543 mmoles) Ni(ClO4)2.6H2O in 60 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1 mmoles) NaOH was added and refluxed overnight. 0.121g green solid was filtered after cooling the refluxed solution. Yield is 0.121 gram.

Elemental (CHN) analysis for C58H80O8N4La2Ni4.H20 confirms the presence of 45.89% C, 5.97% H and 4.12% N.

2.24 Synthesis of a hetro-nuclear complex of Calcium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-17] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0942g (0.2714 mmoles)

Ca(ClO4)2.6H2O and 0.199 g (0.543 mmoles) Ni(ClO4)2.6H2O in 60 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1 mmoles) NaOH was added and refluxed overnight. 0.101g solid was filtered after cooling the refluxed solution. Yield is 0.101 gram.

Elemental (CHN) analysis for C58H80O8N4CaNi shows that this complex have 68.25% C, 6.25% H, and 4.96% N.

2.25 Synthesis of a hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-19] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0942g (0.2714 mmoles)

Ca(ClO4)2.6H2O and 0.1192 g (0.543 mmoles) Zn(CH3COO)2.2H2O in 60 ml ethanol.

Chapter 2 EXPERIMENTAL Work

It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2-aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1mmoles) NaOH was added and refluxed overnight. 0.184g yellow powder was filtered after cooling the refluxed solution. Yield is 0.184 gram.

Elemental (CHN) analysis for C58H80O8N4CaZn indicates that this complex contains 64.95% C, 7.12% H, and 5.74% N.

2.26 Synthesis of a homo-nuclear complex of Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-20/27] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.1084 g (0.543 mmoles)

Cu(CH3COO)2.H2O in 100 ml of Methanol. It was refluxed overnight to dissolve

H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2- aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 1 ml Et3N or 0.044 (1.1 mmoles) NaOH was added and refluxed overnight.

NaOH is comparatively better base than Et3N to produce a complex with metals. 0.06 g grey/green powder was filtered after cooling the refluxed solution. Yield was 0.06 gram.

Elemental (CHN) analysis for C58H80O8N4Cu2 shows that this complex has 65.5% C, 6.99% H and 5.05% N.

2.27 Synthesis of a homo-nuclear complex of Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-26] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.395 g (1.08 mmoles)

Ni(ClO4)2.6H2O in 100 ml of ethanol. It was refluxed overnight to dissolve H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2- aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 1 ml Et3N was added and refluxed overnight. 0.221g green powder was filtered after cooling the refluxed solution. Yield was 0.221 gram.

Chapter 2 EXPERIMENTAL Work

Elemental (CHN) analysis for C58H80O8N4Ni4.H2O shows the presence of 57.31% C, 6.84% H and 4.49% N.

2.28 Synthesis of a homo-nuclear complex of Calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-5] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0653 g (0.2714 mmoles)

Ca(ClO4)2.2H2O in 100 ml of ethanol. It was refluxed for 45 minutes to dissolve

H2mftbp completely. To this clear solution, 0.04023 g (0.2714 mmoles) 1, 2-bis-[2- aminoethoxy]ethane was added and refluxed for 45 min and then to this refluxing solution, 0.044 g (1.1 mmoles) NaOH was added and refluxed overnight. 0.04 g yellowish green powder was filtered after one week from yellowish green refluxed solution. Yield was 0.04 gram.

Elemental (CHN) analysis for C58H80O8N4Ca6.H2O reveals that this complex has 57.85% C, 7.11% H and 9.23% N.

2.29 Synthesis of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [CE-22] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.106g (0.2714 mmoles)

Ba(ClO4)2.3H2O and 0.199g (0.543 mmoles) Ni(ClO4)2.6H2O in 100 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04g (0.2714 mmoles) triethylene tetramine was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1mmoles) NaOH was added and refluxed overnight. 0.154g light yellow powder was filtered after cooling the refluxed solution. Yield is 0.154 gram.

Elemental (CHN) analysis for C58H84O4N8Ba4Ni3 was calculated and found that this complex has 4.95% C, 5.16% H and 6.97% N.

Chapter 2 EXPERIMENTAL Work

2.30 Synthesis of a hetro-nuclear complex of Calcium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [CE-23] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0942g (0.2714 mmoles)

Ca(ClO4)2.6H2O and 0.1084g (0.543 mmoles) Cu(CH3COO)2.H2O in 100 ml ethanol.

It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.04g (0.2714 mmoles) triethylene tetramine was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1mmoles) NaOH was added and refluxed overnight. After few days, 0.108g dark green powder was filtered. Yield was 0.108 gram.

Elemental (CHN) analysis for C58H80O8N4 was calculated and found that this complex contains 65.23% C, 7.11% H and 9.95% N.

2.31 Synthesis of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-2] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0531g (0.136 mmoles)

Ba(ClO4)2.3H2O and 0.199g (0.543 mmoles) Ni(ClO4)2.6H2O in 100 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.028g (0.2714 mmoles) diethylenetriamine was added and refluxed for 45 min and then to this refluxing solution, 1 ml of Et3N was added and refluxed overnight. After one week, 0.108 g reddish brown powder was filtered. Yield was 0.108 gram.

Elemental (CHN) analysis for C58H80O8N4 was calculated and found that this complex has 57.60% C, 6.63% H and 7.46% N.

2.32 Synthesis of a homo-nuclear complex of Calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-4] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.1885g (0.543 mmoles)

Ca(ClO4)2 in 100 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.028g (0.2714 mmoles) diethylenetriamine was

Chapter 2 EXPERIMENTAL Work added and refluxed for 45 min and then to this refluxing solution, 1 ml of Et3N was added and refluxed overnight. After two days, 0.264 g yellow powder was filtered. Yield was 0.264 gram.

Elemental (CHN) analysis for C81H111O6N9Ca7 indicates that this complex contains 61.29% C, 7.05% H and 7.94% N.

2.33 Synthesis of a homo-nuclear complex of Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-8] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0925g (0.543 mmoles)

CuCl2.2H2O in 100 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.028g (0.2714 mmoles) diethylenetriamine was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1mmoles) NaOH was added and refluxed overnight. 0.129g green powder was filtered after cooling the refluxed solution. Yield was 0.129 gram.

Elemental (CHN) analysis for C54H80O8N4Cu indicates that this complex contains 68.073% C, 8.04% H and 8.82% N.

2.34 Synthesis of a hetro-nuclear complex of Lanthanum and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-10] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.118g (0.2714 mmoles)

La(NO3)3.6H2O and 0.1192g (0.543 mmoles) Zn(CH3COO)2.2H2O in 100 ml ethanol.

It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.028g (0.2714 mmoles) diethylenetriamine was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1mmoles) NaOH was added and refluxed overnight. A very small amount of light yellow powder was obtained but after few weeks, 0.345g yellow powder was filtered from the refluxed solution. Yield was 0.345 gram.

Elemental (CHN) analysis calculated for C108H148O8N12La2Zn4 shows that this complex has 56.85% C, 6.54% H and 7.34% N.

Chapter 2 EXPERIMENTAL Work

2.35 Synthesis of a hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-12] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.106g (0.2714 mmoles)

Ba(ClO4)2.3H2O and 0.1192g (0.543 mmoles) Zn(CH3COO)2.2H2O in 100 ml of ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.028g (0.2714 mmoles) diethylenetriamine was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1mmoles) NaOH was added and refluxed overnight. 0.12g yellow powder was filtered after cooling the refluxed solution. Yield was 0.12 gram.

Elemental (CHN) analysis for C54H74O4N6BaZn3 reveals that this complex contains 53.84% C, 6.20% H and 6.98% N.

2.36 Symthesis of a hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-18] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.0942g (0.2714 mmoles)

Ca(ClO4)2.6H2O and 0.1192g (0.543 mmoles) Zn(CH3COO)2.2H2O in 100 ml ethanol. It was refluxed for 45 minutes to dissolve H2mftbp completely. To this clear solution, 0.028g (0.2714 mmoles) diethylenetriamine was added and refluxed for 45 min and then to this refluxing solution, 0.044g (1.1mmoles) NaOH was added and refluxed overnight. 0.026g yellow powder was filtered after cooling the refluxed solution. Yield was 0.026 gram.

Elemental (CHN) analysis for C54H74O4N6CaZn was calculated and found that this complex contains 66.41% C, 7.64% H and 8.61% N.

2.37 Symthesis of a homo-nuclear complex of Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE- 29] 0.1g (0.2714 mmoles) 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp) was added in a round-bottomed flask containing 0.395g (1.08 mmoles)

Ni(ClO4)2.6H2O in 100 ml ethanol. It was refluxed for 45 minutes to dissolve

Chapter 2 EXPERIMENTAL Work

H2mftbp completely. To this clear solution, 0.028g (0.2714 mmoles) diethylenetriamine was added and refluxed overnight and then to this refluxing solution, 1 ml of triethylamine (Et3N) was added and refluxed overnight. 0.361g grey powder was filtered after cooling the refluxed solution. Yield was 0.361 gram.

Elemental analysis for C108H148O8N12Ni2 indicates that this complex contains elements in the percentage as 69.75% C, 8.02%H and 9.04% N.

Chapter 3

Results and

Discussion

Chapter 3 RESULTS AND DISCUSSION

3.1 Introduction The synthesized compounds were characterized via UV, NMR, IR, Mass spectrometery, CHN analysis and single crystal X-ray crystallography. UV spectra were taken on a Spectronic 20 UV-1201 Shiniadzu spectrophotometer. Atomic absorption was taken on a Hitachi Z-8000 Polarized Zeeman Atomic Absorption spectrophotometer. DTA graphs were obtained on a Shimadzu D-40 Thermal Analyzer. -1 Infrared Spectra were recorded as KBr discs in the range 4000-300 cm on Perkin Elmer Paragon 1000 PC Fourier Transform Spectrometer or a Perkin Elmer Spectrum 100 Spectrometer. Elemental analyses were performed by Mrs Pauline King within the chemistry department on an EAI Exeter analytical CE-440 elemental analyzer. 1H-NMR spectra (400MHz) were recorded on Bruker AC250FT or DPX-

400MHz spectrometer in CDCl3 unless otherwise stated. Chemical shifts [δ] in ppm are relative to SiMe4. Mass spectra were recorded on a Thermo Fisher Exactive + Triversa Nanomate mass spectrometry (ESI) within the chemistry department of Loughborough University, Loughborough, UK. Single crystal X-ray diffraction data were collected at 150K on Bruker Apex II CCD [195] diffractometer using graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) at Loughborough University, Loughborough, UK. The structures were solved by direct methods and refined by full-matrix squares on F2. The Bruker SHELXTL [196] software was used for structure solution and refinement. All non- hydrogen atoms were refined anisotropically and hydrogen atoms were inserted at calculated positions using a riding model, unless otherwise stated. The crystallography graphics were done using XP [196] Mercury 2.4 [197] and Ortep 3 for Windows [198] and were rendered in POV-Ray software [199].

3.2 List of synthesized macrocyclic ligands In this thesis, following macrocyclic ligands were synthesized and characterized; 1 18-crown-6 2 Macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] and 1, 2-Bis-[2-aminoethoxy]ethane [L-1]

Chapter 3 RESULTS AND DISCUSSION

3 Macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] and triethylene tetramine [L-5.1] 4 Macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] and Bis-[2-aminoethyl]-amine [L-2] 5 Macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] and 1, 3-diamino-2-propanol [IR-2] 6 Macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] and 1, 4-diaminobutane

3.3 List of synthesized macrocyclic complexes with metals In this research, following metal complexes with synthesized macrocyclic ligands were synthesized and characterized; 1 Ni-18-Crown-6 complex 2 Cu-18-Crown-6 complex 3 Zn-18-Crown-6 complex 4 Homo-nuclear complex of calcium with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol [IR-4/ IR-2] 5 Homo-nuclear complex of Zinc with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol [ IR-5B ] 6 Hetro-nuclear complex of Manganese and Barium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2- propanol [CE-25] 7 Hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 4-diaminobutane [CE-24] 8 Hetro-nuclear complex of Lead and Copper with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-1] 9 Hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-3]

Chapter 3 RESULTS AND DISCUSSION

10 Hetro-nuclear complex of Lanthanum and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy] ethane [CE-7] 11 Hetro-nuclear complex of Barium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-9] 12 Hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-13] 13 Hetro-nuclear complex of Lanthanum and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-15] 14 Hetro-nuclear complex of Calcium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-17] 15 Hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-19] 16 Homo-nuclear complex of Copper with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-20/27] 17 Homo-nuclear complex of Nickel with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane [CE- 26] 18 Homo-nuclear complex of Calcium with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-5] 19 Hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [CE- 22] 20 Hetro-nuclear complex of Calcium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [CE- 23]

Chapter 3 RESULTS AND DISCUSSION

21 Hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-2] 22 Homo-nuclear complex of Calcium with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-4] 23 Homo-nuclear complex of Copper with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-8] 24 Hetro-nuclear complex of Lanthanum and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE- 10] 25 Hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-12] 26 Hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-18] 27 Homo-nuclear complex of Nickel with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-29]

3.4 Physical properties of 18-Crown-6 and its complexes with metals Table-3.1 M. P. Compound State Color (O C) Max.

18-Crown-6 (Ligand) Crystalline solid Colorless 38 281

Ni-18-Crown-6 Complex Crystalline solid Green 110 285

Cu-18-Crown-6 Complex Crystalline solid Blue 105 306

Zn-18-Crown-6 Complex Crystalline solid White 155 293

Chapter 3 RESULTS AND DISCUSSION

3.5 Solubility of Crown ether and its complexes 3.5.1 Non polar solvents Table-3.2

Compound C6H14 Acetone CCl4

18-Crown-6 (Ligand) Insoluble Insoluble Insoluble

Compound C6H14 Acetone CCl4

Ni-18-Crown-6 Complex Insoluble Insoluble Insoluble

Cu-18-Crown-6 Complex Insoluble Insoluble Insoluble

Zn-18-Crown-6 Complex Insoluble Insoluble Insoluble

3.5.2 Polar solvents Table-3.3

Compound C2H5OH CHCl3 CH2Cl2 H2O

18-Crown-6 (Ligand) Insoluble Insoluble Insoluble Soluble

Ni-18-Crown-6 Complex Insoluble Insoluble Insoluble Soluble

Cu-18-Crown-6 Complex Insoluble Insoluble Insoluble Soluble

Zn-18-Crown-6 Complex Insoluble Insoluble Insoluble Soluble

3.6 Atomic absorption Spectroscopic studies for nickel, copper and zinc complexes with 18-crown-6 Amount of metal present in the complexes was determined by atomic absorption spectroscopy. Atomic absorption was taken on a Hitachi Z-8000 Polarized Zeeman Atomic Absorption Spectrophotometer. The difference between the calculated amount

Chapter 3 RESULTS AND DISCUSSION and estimated amount of metal was insignificant which is given in the table-3.4, and instrumental parameters of these metals are given in table-3.4.

Table-3.4 Compound Metal To Be Calc. amount Amount of M Difference Estimated of metal estimated by (ppm) (ppm) AAS (ppm)

Ni-18-Crown-6 Nickle 10 8.9 1.1 Complex

Cu-18-Crown-6 Copper 5 4.5 0.5 Complex

Zn-18-Crown-6 Zinc 2 1.16 0.84 Complex

3.6.1 Instrumental parameters Atomic absorption was taken on a Hitachi Z-8000 Polarized Zeeman Atomic Absorption spectrophotometer. Table-3.5 Parameters Ni Cu Zn

Lamp current 10.0 mA 7.5 mA 10.0 mA

Wave length 232.0 nm 324.8 nm 213.8 nm

Slit 0.2 nm 1.3 nm 1.3 nm

Atomizer Standard Burner Standard Burner Standard Burner

Oxidant Air Air Air

Oxidant pressure 1.60 Kg/cm2 1.60 Kg/cm2 1.60 Kg/cm2

Fuel Acetylene Acetylene Acetylene

Fuel pressure 0.25 Ks/cm2 0.30 Kg/cm2 0.20 Ks/cm2

Burner Hight 10.0 mm 7.5 mm 7.5 mm

Atomization Flame Flame Flame

Chapter 3 RESULTS AND DISCUSSION

3.7 U.V. Studies of 18-crown-6 ligand and its complexes with Ni, Cu and Zn

λ max of 18-crown-6 and its complexes with Nickel, Copper and Zinc was measured by using UV Spectrometer and are given in table-3.6 .

Table-3.6

Compound λ max nm

18-Crown-6 (Ligand) 281

Ni-18-Crown-6 Complex 285

Cu-18-Crown-6 Complex 306

Zn-18-Crown-6 Complex 293

3.8 Stability determination of 18-crown-6 ligand and its complexes with Ni, Cu and Zn by UV-Study Ligand and its complexes synthesized were characterized and their stability was determined by U.V studies.

3.8.1 Stability determination of 18-Crown-6 ligand

 λ max of ligand solution in H2O was determined while it was synthesized.

 The above solution was kept for five weeks, its λ max was periodically noted

as following and a graph of λ max was plotted against time. 1. After every 3 hours for first 24 hours. (Graph-3.1) 2. After 24 hours for first week. (Graph-3.2) 3. After 48 hours for rest of the 5 weeks. (Graph-3.3) No change was noted through out the experiment. Every time a fresh

solution was also run for λ max to check its stability in solid crystalline form and

there was also no change in λ max in the fresh solution. Hence, it was found that this ligand is stable both in solution as well as in air.

Chapter 3 RESULTS AND DISCUSSION

Graph-3.1

Graph-3.2

Chapter 3 RESULTS AND DISCUSSION

Graph-3.3

3.8.2 Stability determination of Ni-complex of 18-Crown-6

 λ max of Ni complex of 18-Crown-6 solution in H2O was determined while it was synthesized.

 The above solution was kept for five weeks and its λ max was periodically

noted as following and a graph of λ max was plotted against time. 1. After every 3 hours for first 24 hours. (Graph-3.4) 2. After 24 hours for first week. (Graph-3.5) 3. After 48 hours for rest of the 5 weeks. (Graph-3.6) No change was noted through out the experiment. Every time a fresh solution was also run for λ max to check its stability in solid crystalline form and there was also no change in λ max in the fresh solution. Hence, it was found that this complex is stable both in solution as well as in air.

Graph-3.4

Chapter 3 RESULTS AND DISCUSSION

Graph-3.5

Graph-3.6

Chapter 3 RESULTS AND DISCUSSION

3.8.3 Stability determination of Cu-complex of 18-Crown-6

From UV studies, it was concluded that the complex was pure and stable in solid as well as is solution form because the same λ max was achieved even after five weeks. From Figure-3.11, Figure-3.12 and Figure-3.13, it is clear that there is no any change in λ max even after five weeks.

 λ max of Cu complex of 18-Crown-6 solution in H2O was determined while it

was synthesized. (λ max =306 nm)

 The above solution was kept for five weeks and its λ max was periodically

noted as following and a graph of λ max was plotted against time. 1. After every 3 hours for first 24 hours. (Graph-3.7) 2. After 24 hours for first week. (Graph-3.8) 3. After 48 hours (2 days) for rest of the 5 weeks. (Graph-3.9)

No change was noted through out the experiment. Every time a fresh solution was also run for λ max to check its stability in solid crystalline form and there was also no change in λ max in the fresh solution. Hence, it was found that this complex is stable both in solution as well as in air.

λ max Vs Time

400

375

350

325

300

max λ λ 275

250

225

200 0 3 6 9 12 15 18 21 24 27 Time ( Hours )

Graph-3.7

Chapter 3 RESULTS AND DISCUSSION

λ max Vs Time

400

375

350

325

300

max λ λ 275

250

225

200 0 24 48 72 96 120 144 168 192 216 Time ( Hours )

Graph-3.8

λ max Vs Days

400

375

350

325

300 max

λ λ 275

250

225

200 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Days

Graph-3.9

Chapter 3 RESULTS AND DISCUSSION

3.8.4 Stability determination of Zn-complex of 18-Crown-6

 λ max of Zn complex of 18-Crown-6 solution in H2O was determined while it was synthesized.

 The above solution was kept for five weeks and its λ max was periodically

noted as following and a graph of λ max was plotted against time. 1. After every 3 hours for first 24 hours. (Graph 3.10) 2. After 24 hours for first week. (Graph 3.11) 3. After 48 hours for rest of the 5 weeks. (Graph 3.12)

No change was noted through out the experiment. Every time a fresh

solution was also run for λ max to check its stability in solid crystalline form and

there was also no change in λ max in the fresh solution. Hence, it was found that this complex is stable both in solution as well as in air.

Graph-3.10

Chapter 3 RESULTS AND DISCUSSION

Graph-3.11

Graph-3.12

Chapter 3 RESULTS AND DISCUSSION

3.9 TGA of Ni, Cu and Zn complexes with 18-Crown-6 It is defined in a way that the TG is a technique for measuring the changes in mass of the sample in heating (cooling) process. Change may be physical or chemical in nature e.g., change may be in colour, structure, composition, phase or weight etc. TGA is mostly concerned with change in weight e.g.

CuSO4.5H2O CuSO4.H2O + 4H2O CuSO4 CuO 150°C 1500°C Usually when compounds are heated the common change, generally occurs is loss of weight but sometimes by heating weight increases e.g. If Copper metal is heated it forms oxides. Hence weight increases by heating as well.

3.9.1 TGA of Ni-18-Crown-6 complex In TGA we observed the weight loss with respect to increase in temperature for the synthesized Nickel complexes of 18-Crown-6. Graph in Figure-3.17 shows that 1st loss in weight occurs at 140.1 OC to 178.3 OC and it is 15.62% loss. Second loss occurs at 178.3 OC to 188.9 OC and its value is 55.20% and third loss in weight occurs at 188.9 OC to 363.2 OC and it is 14.58 % loss and there is no loss in weight from 363.2 OC to 500 OC. Total loss in weight from 140.1 OC to 500 OC is 85.41 %. There is no peak in the range of melting point. Hence it is concluded that the metal complexes is stable, which is also supported by UV studies.

Graph-3.13 TGA graph of Ni-18-Crown-6 complex 68

Chapter 3 RESULTS AND DISCUSSION

3.9.2 TGA of Cu-18-crown-6 complex In TGA, we observed the weight loss with respect to increase in temperature for the synthesized Copper complexes of 18-Crown-6. Graph in Figure-3.18 shows that the 1st loss in weight occurs at 101.9 OC to 170 OC and this loss is 29.16 % and second loss in weight occurs at 170 OC to 280 OC and this loss is 28.12%. Total loss in weight from 101.9 OC to 496 OC is 57.29 %. There is no peak in melting point region. Hence it is concluded that the metal complex is stable, which is also supported by UV studies.

Graph-3.14 TGA Graph of Cu-18-Crown-6 Complex

3.9.3 TGA of Zn-18-Crown-6 complex In TGA we observed the weight loss with respect to increase in temperature for the synthesized Zinc complexes of 18-Crown-6. Graph in Figure-3.19 shows that the 1st loss in weight occurs at 135 OC to 318 OC and this loss is 29.16 % and loss in weight from 136.8 OC to 496 OC is 30.20 % and loss in weight from 318 OC to 496 OC is 1.041 % and total loss in weight at 135OC to 496OC is 30.20 %. There is no peak in melting point region.

Chapter 3 RESULTS AND DISCUSSION

Hence, it is concluded that the metal complex is stable, which is also supported by UV studies.

Graph-3.15 TGA graph of Zn-18-Crown-6 complex

Chapter 3 RESULTS AND DISCUSSION

3.10 Characterization of 2, 2-methylene-bis-[(6-hydroxymethyl)-4-tert- butylphenol] (H2mhtbp)

CH3 CH3 CH3

H C CH H3C CH3 H3C CH3 3 3 1. NaOH (10%), N2 8 days, 50 OC + 2HCHO 2. Acetic acid (50%)

OH OH OH OH OH

Melting Point: 145-147 0C

TLC Rf = 0.30 in chloroform:acetone 5:1 (V/V) 1 H NMR (d-CHCl3), [ppm]: 1.29(s, 18H, C(CH3)3), 3.9(s, 2H, CH2), 4.78(s, 4H,

CH2OH), 6.97(s, 2H, Ar), 7.29(s, 2H, Ar), 8.52 (s, 2H, ArOH)

EI-MS (relative intensity) and (peak assignment calc.): 395 (100%) [H3mhtbp + Na]+.

CHN Calc.: C 74.16%, H 8.66% for [C23H32O4] Found: C 74.14%, H 8.94% IR (KBr), ν [cm-1]: 2962 (s, OH); 1205 (s, ArOH);

In general, the synthesis of H2mhtbp was the most inconvenient and had the lowest overall yield 29.25%. The H2mhtbp was synthesized from 4-tert-butylphenol and formaldehyde following the literature procedure with slight modifications. 4-tert-butylphenol was ground before use and placed with formaldehyde under an atmosphere of N2. Then sodium hydroxide solution was added (Phenol: NaOH molar ratio 1:1) and the mixture was then heated at 50 °C in an atmosphere of N2 for 8 days. The resulting resinous precipitate was filtered off and dissolved in 50 mL of acetone. At this stage, another precipitate had formed which was removed by filtration. The acetone solution was then acidified using cold acetic acid. Because the expected oil separation did not take place, the acidic solution was diluted and extracted with diethyl ether and with ethylacetate. Both organic extracts were combined, washed with H2O and dried over anhydrous Na2SO4, and the solvents were removed to yield over 30 g of orange oily substance. This was dissolved in toluene and product was precipitated by light petroleum ether to produce H2mhtbp in 29.25% yield, greater than literature yield (20%).

Chapter 3 RESULTS AND DISCUSSION

The low literature yield of H2mhtbp[139] might suggest that the methylenediphenol is not the major species among several oligomeric phenol based products in the reaction mixture. Perhaps change of the experimental conditions such as a different reaction time or a base would result in the mixture where H2mhtbp will be a major compound. 1 The H NMR spectrum of H2mhtbp shows characteristic singlets at 3.83 ppm and

4.69 ppm, for CH2OH and CH2 in 2:1 ratio, which confirms the purity (Scan-3.1).

1 Scan-3.1 H NMR spectrum and proton assignments for H2mhtbp in CDCl3

3.11 Characterization of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol]

(H2mftbp)

CH CH 3 3 CH3 CH3 H C CH H C CH 3 3 3 3 H3C CH3 H3C CH3

MnO2, Chloroform

Stirring at room temperature

OH OH OH OH O OH OH O

Chapter 3 RESULTS AND DISCUSSION

Figure-3.1 X-ray crystal structure of (H2mftbp)

Figure-3.2 X-ray crystal structure of (H2mftbp)

Figure-3.3 X-ray crystal structure of (H2mftbp)

Melting Point: 182-185 OC

TLC Rf : 0.74 in chloroform 1 H NMR (d-CHCl3), [ppm]: 1.22(s, 18H, C(CH3)3), 3.96(s, 2H, CH2), 7.30(s, 2H, ArH), 7.58(s, 2H, ArH), 9.79(s, 2H, ArOH), 11.12 (s, 2H, CHO)

Chapter 3 RESULTS AND DISCUSSION

ESI-MS (relative intensity) and (peak assignment calc.): 391 (100%) [H2mftbp + Na]+.

CHN Calc.: C 74.97%, H 7.66% for [C23H28O4] Found: C 74.57%, H 7.72% IR (KBr), ν [cm-1]: 2967 (s, OH), 1660 (s, C=O), 1271 (s, ArOH)

Oxidation of H2mhtbp was very easy. H2mhtbp was just stirred in chloroform with MnO2 for 5 hours at ambient temperature and the reaction mixture was then filtered. The expected dialdehyde was produced after rotary evaporation of the chloroform washings. In addition, it was purified by recrystallization from EtOH to 1 give H2mftbp in 50% yield. Scan-3.2 shows the H NMR spectrum acquired in CDCl3 with proton assignments. NMR Spectroscopy confirmed the formation of aldehyde compound as, with the progress of the reaction, the peak due to the hydroxymethyl group at 4.66 [ppm] disappeared and the peak due to aldehyde appeared at 11 [ppm].

1 Scan-3.2 H NMR spectrum and proton assignments for H2mftbp in CDCl3

Chapter 3 RESULTS AND DISCUSSION

3.12 Characterization of macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1, 2-Bis-[2-aminoethoxy]ethane [L-1]

CH3 CH3

H3C CH3 H3C CH3

CH3 CH3 H C CH H C CH 3 3 3 3 N OH OH N

O O 2 - 4H2O 2 O O O O + H2N NH2

O OH OH O N OH OH N

H3C CH3 H3C CH3 CH3 CH3

Macrocyclic Ligand was prepared by the condensation reaction of 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane based on both templated and non-templated high dilution methods. This macrocyclic compound was prepared by stirring and refluxing equimolar quantities of ethanolic solution of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1,2-bis-[2- aminoethoxy]ethane overnight in a basic media. Shiff-base condensation reaction was involved in the synthesis of this macrocyclic ligand.

Elemental (CHN) analysis shows that the macrocycle (C58H80O8N4) contains 72.47% C, 8.39% H and 5.83% N.

3.12.1 H1 NMR Studies of macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1, 2-Bis-[2-aminoethoxy]ethane [L-1]

H1NMR study shows the peak at δ [ppm]: 8.1(s, 4H, N=CH) to ensure the Schiff- base condensation and confirms the formation of (-N=C-) imine bond. Proton signals at 13.48 ppm for the phenolic hydroxyl group, gives the indication about the presence of hydrogen bonds. Hydrogen bond is between phenolic hydrogen and nitrogen of the imine linkage of the same molecule.

1 H NMR (d-CHCl3), [ppm]: 1.27(s, 36H, C(CH3)3), 2.2(s, 4H, Ph-CH2-Ph), 3.22(t,

8H, -CH2-), 3.49(t, 8H, -CH2-), 3.53(t, 8H, -CH2-), 7.04(s, 4H, ArH), 7.4(s, 4H, ArH), 8.1(s, 4H, N=CH), 13.48(br, 4H, ArOH).

Chapter 3 RESULTS AND DISCUSSION

Scan-3.3 H1 NMR Spectrum of macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1,2-Bis-[2-aminoethoxy]ethane

3.12.2 ESI-MS Studies of macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1, 2-Bis-[2-aminoethoxy]ethane [L-1]

In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z 983.5847 indicates the presence of [(2+2)Na+1] macrocycle. Two molecules of 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2- aminoethoxy]ethane combine by Schiff-base condensation to make a (2+2) macrocycle with molecular formula C58H80O8N4.

Scan-3.4 MS-Scan of Synthesized macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1,2-Bis-[2-aminoethoxy]ethane

Chapter 3 RESULTS AND DISCUSSION

3.12.3 IR Studies of macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and 1, 2-Bis-[2-aminoethoxy]ethane [L-1]

IR (KBr-disc, cm-1) analysis reveals intense ν(-C=N-) bands and broad ν (O-H) bands at 1634.14cm-1 and 3401.12cm-1 respectively. Other peaks shown in the scan are at 2956.51cm-1, 2902.93cm-1, 2861.73cm-1, 1470.81cm-1, 1393.2cm-1, 1362.10cm- 1, 1344.38cm-1, 1278.25cm-1, 1223.19cm-1, 1128.44cm-1, 1018.58cm-1, 998.15cm-1, 936.54cm-1, 918.54cm-1, 875.35cm-1, 823.68cm-1, 790.33cm-1, 758.92cm-1, 743.23cm- 1, 701.46cm-1, 626.94cm-1, 591.35cm-1 and 509.4cm-1.

60 509.40cm-1

591.35cm-1 50

701.46cm-1 626.94cm-1 758.92cm-1 40 743.23cm-1

790.33cm-1 %T

30 998.15cm-1 1018.58cm-1 875.35cm-1 1393.20cm-1 936.94cm-1 1344.38cm-1 918.54cm-1 20 823.68cm-1

1362.10cm-1 10

1223.19cm-1 2902.93cm-1 1470.81cm-1 2861.73cm-1 1634.14cm-1 1278.25cm-1 2956.51cm-1 1128.44cm-1 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-5 Crystal Sample 001 By Analyst Date Wednesday, June 20 2012 Scan-3.5 IR-Scan of Synthesized macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1,2-Bis-[2-aminoethoxy]ethane

3.13 Characterization of macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and triethylene tetramine [L-5.1]

CH3 CH3

H3C CH3 H3C CH3

CH3 CH3 H C CH H C CH 3 3 3 3 N OH OH N

NH HN 2 - 4H2O 2 NH NH NH HN + H2N NH2

O OH OH O N OH OH N

H3C CH3 H3C CH3

CH3 CH3 77

Chapter 3 RESULTS AND DISCUSSION

3.13.1 H1 NMR Studies of a macrocyclic ligand based on 2,2-methylene-bis[(6- formyl)-4-tert-butylphenol] and triethylene tetramine [L-5.1]

H1NMR study shows the peak at δ [ppm]: 8.06(s, 4H, N=CH) to ensure the Schiff- base condensation and confirms the formation of -N=C-. Proton signals at 13.38 ppm for the phenolic hydroxyl group, provides indication about the presence of hydrogen bonds. Hydrogen bond is between phenolic hydrogen and nitrogen of the imine linkage of the same molecule.

1 H NMR (d-CHCl3), [ppm]: 1.95(s, 36H, C(CH3)3), 2.58(s, 4H, Ph-CH2-Ph),

3.59(t, 8H, -CH2-), 3.66(t, 8H, -CH2-), 3.99(t, 8H, -CH2-), 7.19(s, 4H, ArH), 7.27(s, 4H, ArH), 8.06(s, 4H, N=CH), 8.25(s,4H, N-H), 13.38(br, 4H, ArOH).

Scan-3.6 H1 NMR Spectrum of Synthesized macrocyclic ligand based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine

Elemental (CHN) analysis for C58H84O4N8.H2O shows that the macrocycle contains 71.42% C, 8.89% H and 11.49% N.

Chapter 3 RESULTS AND DISCUSSION

3.13.2 ESI-MS Studies of a macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and triethylene tetramine [L-5.1] In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z +1 1083.7871 indicates the presence of [(2+2)H2O+2(C2H5OH)+NH4 ] macrocycle. Two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of triethylene tetramine combine by Schiff-base condensation to make a

(2+2) macrocycle with molecular formula C58H84O4N8.

Scan-3.7 MS-Scan of Synthesized macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and triethylene tetramine

3.13.3 IR Studies of a macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)- 4-tert-butylphenol] and triethylene tetramine [L-5.1] IR (KBr-disc, cm-1) analysis reveals intense ν(-C=N-) bands and broad ν (O-H) bands at 1646cm-1 and 3187.50cm-1 respectively. Presence of (O-H) indicates the presence of hydrogen bond between phenolic hydrogen and nitrogen of imine bond (- N=C-). Other peaks found in IR scan are 2954.50cm-1, 1474.00cm-1, 1392.91cm-1, 1361.66cm-1, 1320.95cm-1, 1220.90cm-1, 1125.11cm-1, 1031.93cm-1, 875.68cm-1, 821.39cm-1, 753.49cm-1, 703.67cm-1, 618.18cm-1 and 600.69cm-1.

Chapter 3 RESULTS AND DISCUSSION

5 1031.93cm-1

875.68cm-1

4 %T

753.49cm-1 1125.11cm-1 703.67cm-1 2 618.18cm-1 600.69cm-1 1220.90cm-1 821.39cm-1

1646.00cm-1 1392.91cm-1 3187.50cm-1 2954.50cm-1 1474.00cm-1 1361.66cm-1 0 1320.95cm-1 -0 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description L-5.1_1 Sample 004 By Analyst Date Monday, September 24 2012 Scan-3.8 IR-Scan of macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and triethylene tetramine

3.14 Characterization of a macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and Bis-[2-aminoethyl]-amine [L-2]

CH3 CH3

H3C CH3 H3C CH3

CH3 CH3

H3C CH3 H3C CH3 N OH OH N

- 4H2O 2 2 N NH HN + NH H2N H 2 N OH OH N O OH OH O

H3C CH3 H3C CH3

CH3 CH3

3.14.1 H1 NMR Studies of a macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and Bis-[2-aminoethyl]-amine [L-2]

H1NMR study shows the peak at δ [ppm]: 8.31(s, 4H, N=CH) to ensure the Schiff- base condensation and confirms the formation of -N=C-. Proton signals at 13.20 ppm for the phenolic hydroxyl group, provides indication about the presence of hydrogen bonds. Hydrogen bond is between phenolic hydrogen and nitrogen of the imine linkage of the same molecule.

Chapter 3 RESULTS AND DISCUSSION

1 H NMR (d-CHCl3), [ppm]: 1.50(s, 36H, C(CH3)3), 2.16(s, 4H, Ph-CH2-Ph),

3.42(t, 8H, -CH2-), 3.67(t, 8H, -CH2-), 6.98(s, 4H, ArH), 7.19(s, 4H, ArH), 8.31(s, 4H, N=CH), 12.92(s,2H, N-H), 13.20(br, 4H, ArOH).

Scan-3.9 H1 NMR Spectrum of Synthesized macrocyclic ligand based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and Bis-[2-aminoethyl]-amine

Elemental analysis calculated for C54H74O24N6: C 67.94%; H 6.45%; Observed: C 64.18%; H 5.91%.

3.14.2 ESI-MS Studies of a macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and Bis-[2-aminoethyl]-amine [L-2] In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z 893.5642 (100%) indicates the presence of [(2+2)+Na+1] macrocycle. Two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of Bis-[2- aminoethyl]-amine combine by Schiff-base condensation to make a (2+2) macrocycle with molecular formula C54H74O4N6. A singly charged peak at m/z 1765.1425 shows

Chapter 3 RESULTS AND DISCUSSION the presence of [(4+4)Na+1] macrocycle. Four molecules of 2,2-methylene-bis[(6- formyl)-4-tert-butylphenol] and four molecules of Bis-[2-aminoethyl]-amine combine by Schiff-base condensation to make a (4+4) macrocycle with molecular formula

C108H148O8N12.

Scan-3.10 MS-Scan of Synthesized macrocyclic ligand based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and Bis-[2-aminoethyl]-amine

3.14.3 IR Studies of a macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)- 4-tert-butylphenol] and Bis-[2-aminoethyl]-amine [L-2] IR (KBr-disc, cm-1) analysis reveals intense ν(C=N) bands and broad ν (O-H) bands at 1633.36cm-1 and 3401.15cm-1 respectively. Formation of -C=N- bond ensures the cyclization by Schiff‘s base condensation reaction and presence of –OH group reveals the presence of hydrogen bond. Other peaks found in scan are at 2957.60cm-1, 1467.15cm-1, 1274.61cm-1, 1221.62cm-1, 1121.70cm-1, 1077.73cm-1, 870.76cm-1, 823.55cm-1 and 626.17cm-1.

Chapter 3 RESULTS AND DISCUSSION

1121.70cm-1 35 1077.73cm-1 823.55cm-1

30 1221.62cm-1

%T 626.17cm-1 25 1274.61cm-1 870.76cm-1

20 2957.60cm-1

3401.15cm-1 1633.36cm-1 10

5 1467.15cm-1

2 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-4 Sample 002 By Analyst Date Wednesday, June 13 2012 Scan-3.11 IR-Scan of Synthesized macrocyclic ligand based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and Bis-[2-aminoethyl]-amine

3.15 Characterization of a macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1,3-diamino-2-propanol [IR-2]

CH3 CH3

H3C CH3 H3C CH3

CH3 CH3

H3C CH3 H3C CH3 N OH OH N - 4H O NH 2 HO OH 2 + 2 H2N 2 OH N OH OH N O OH OH O

H3C CH3 H3C CH3

CH3 CH3

3.15.1 ESI-MS Studies of a macrocyclic ligand based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1,3-diamino-2-propanol [IR-2] In ESI-MS (m/z, rel. intensity, assignment), a duobly charged peak at m/z 423.2635 (100%) indicates the presence of [(2+2)]+2 macrocycle. Two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1,3-diamino-2-

Chapter 3 RESULTS AND DISCUSSION propanol combine by Schiff-base condensation to make a (2+2) macrocycle with molecular formula C52H68O6N4.

Scan-3.12 MS-Scan of Synthesized macrocyclic ligand based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol

Elemental analysis for C52H68O6N4 shows that macrocyclic ligand contains 73.27% C, 8.54% H and 6.94% N.

3.15.2 IR Studies of a macrocyclic ligand based on 2, 2-methylene-bis[(6-formyl)- 4-tert-butylphenol] and 1,3-diamino-2-propanol [IR-2] IR (KBr-disc, cm-1) scan gives the peaks at 3400.83 for ν (O-H) that indicates the presence of hydrogen bonding. Another peak at 1636.17 ν(-C=N-) ensure the Schiff- base condensation. Other peaks shown in scan are at 2959.21cm-1, 1536.09cm-1, 1463.34cm-1, 1391.88cm-1, 1362.10cm-1, 1267.13cm-1, 1218.87cm-1, 1096.32cm-1, 1024.33cm-1, 877.85cm-1, 827.82cm-1, 796.41cm-1, 743.02cm-1, 711.63cm-1, 633.5cm- 1 and 527.05cm-1.

Chapter 3 RESULTS AND DISCUSSION

71 70

40 527.05cm-1 633.50cm-1 %T 35 711.63cm-1 743.02cm-1 1096.32cm-1 30 1024.33cm-1 796.41cm-1 3400.83cm-1 1536.09cm-1 827.82cm-1 25 877.85cm-1

1267.13cm-1 20 1362.10cm-1 1218.87cm-1 15

10 1391.88cm-1 2959.21cm-1 1636.17cm-1 1463.34cm-1 4 4000 3000 2000 1000 250 cm-1 Name Description IR-2 Sample 005 By Analyst Date Thursday, October 20 2011 Scan-3.13 IR-Scan of Synthesized macrocyclic ligand based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1,3-diamino-2-propanol

3.16 ELECTROSPRAY IONIZATION MASS SPECTROMETERY STUDY OF METAL COMPLEXES Electrospray ionization mass spectrometry analysis was performed on Thermo Fisher Exactive Orbitrap mass spectrometer coupled to an Advion TriVersa Nanomate injection system at departmental mass spectrometry service at Loughborough University, UK. The instrument was used in positive ion mode and samples were delivered to ESI source using nanomate chip base system. Spray voltage was set to 1478V and the capillary voltage to 92.5V. Temperatures were set as 191 oC at capillary, 27 oC at analyser and 46 oC at ESI source. Nebulizer or sheet gas flows were not employed. Data was processed using Thermo Xcalibur software version 2.1.0.1139 provided by Thermo Scientific [4]. Isotope pattern calculations were carried on Thermo Xcalibur Qual Browser.

Chapter 3 RESULTS AND DISCUSSION

3.17 ESI-MS studies of Ni, Cu and Zn complexes of 18-crown-6 Table 3.7 Mass spectroscopic data for Ni, Cu and Zn complexes of 18-crown-6 No. of compd. Found (m/z) Assignment Calc. Mass +1 IHCNi 384 [MNi+NO3] 385 +1 IHCCu 389 [MCu+NO3] 389 359 [MZn+Na]+1 352 +2 IHCZn 828 [M5Zn5] 1648 +1 +1 1083 [M3Zn3(H2O)(NO3)(NH4) ] 1087 +1 +2 1358 [M8Zn8(NO3)(NH4) ] 2717

3.17.1 MS Studies of Nickel complex of 18-Crown-6 [IHCNi] ESI-MS (m/z, rel. intensity, assignment) shows a singly charged peak at m/z 287.1460 (100%) for crown ether ligand [M+Na+1]+1 and a singly charged peak at m/z +1 384.0793 confirms the formation of a complex [MNi+NO3] .

Scan-3.14 MS-Scan of Ni-18-crown-6 complex

Chapter 3 RESULTS AND DISCUSSION

3.17.2 MS studies of Copper complex of 18-Crown-6 [IHCCu] ESI-MS (m/z, rel. intensity, assignment) shows a singly charged peak at m/z 287.1460 (100%) for crown ether ligand [M+Na+1]+1and a singly charged peak at m/z +1 389.0736 indicates the formation of a complex [MCu+NO3] .

Scan-3.15 MS-Scan of Cu-18-crown-6 complex

3.17.3 MS Studies Zinc complex of 18-Crown-6 [IHCZn]

ESI-MS (m/z, rel. intensity, assignment) shows a singly charged peak at m/z 287.1461 (100%) for crown ether ligand [M+Na+1]+1, a singly charged peak at m/z 359.0674 for complex [MZn+Na]+1, a doubly charged peak at m/z 828.0656 indicates +2 the presence of a complex [M5Zn5] , a singly charged peak at m/z 1083.7889 +1 +1 confirms the presence of a complex [M3Zn3(H2O)(NO3)(NH4) ] and a doubly charged peak at m/z 1358.9647 shows the presence of complex +1 +2 [M8Zn8+NO3+NH4 ] .

Chapter 3 RESULTS AND DISCUSSION

Scan-3.16 MS-Scan of Zn-18-crown-6 complex

3.18 MS studies of metal complexes of macrocycles derived from 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol

Table 3.8 Mass spectroscopic data for metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol. No. of Found (m/z) Assignment Calc. Mass compd. +1 +1 IR-4/IR-2 959 [Ca2(2+2)(H2O)(NH4) ] 957 +1 +1 IR-5B 1051 [Zn2(2+2)(CH3COO)(NH4) ] 1051 +1 +2 CE-25 475 [Mn(2+2)(C2H5OH).4H ] 950 +1 +2 740 [MnBa(3+3)(H2O).2H ] 1480

Chapter 3 RESULTS AND DISCUSSION

3.18.1 MS Study of a homo-nuclear complex of calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2- propanol [IR-4/ IR-2] In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z 959.49 +1 +1 [Ca2(2+2)(H2O)(NH4) ] indicates the presence of calcium complex of [(2+2)] macrocycle with molecular formula C52H70O7N5Ca2. It means that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 3-diamino- 2-propanol make a (2+2) macrocycle to make dinulear complex with calcium and calcium behaves as a template to make macrocycle by Schiff-base condensation reaction rather than an oily product.

Scan-3.17 MS Scan of a homo-nuclear complex of Calcium based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol

3.18.2 MS Studies of a homo-nuclear complex of Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2- propanol [ IR-5B ]

[(2+2)Zn2.CH3COO] complex was prepared by reacting 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] (H2mftbp) in a round-bottomed flask containing

Ca(ClO4)2 in 60 ml ethanol. It was refluxed to dissolve H2mftbp completely. To this

Chapter 3 RESULTS AND DISCUSSION clear solution, 1, 3-diamino-2-propanol was added and refluxed for further 45 minutes and then to this refluxing solution, Et3N was added and refluxed it overnight. Sample was taken from the refluxing solution and submitted for MS. ESI-MS scan showed a +1 +1 singly charged peak at m/z 959.49 [Ca2(2+2)(H2O)(NH4) ] to confirm the formation of calcium complex [(2+2)Ca2] but when Zn(CH3COO)2.2H2O was added and refluxed for further 6 hrs. Zn replaced Ca metal and a new complex of Zn was formed as [Zn2(2+2)] complex. A yellow powder was filtered after cooling at room temperature. This powder was crystallized by vapour diffusion method using DMF and Diethyl Ether. In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z +1 +1 1051.7992 indicates the presence of [Zn2(2+2)(CH3COO)(NH4) ] . It means that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 3-diamino-2-propanol make a (2+2) macrocycle to make dinulear complex with Zinc and Zinc acts as a template to make macrocycle by Schiff-base condensation reaction rather than an oily product.

Scan-3.18 MS Scan of a homo-nuclear complex of Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol

Chapter 3 RESULTS AND DISCUSSION

3.18.3 MS Studies of a hetro-nuclear complex of Manganese and Barium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3- diamino-2-propanol [CE-25] In this reaction mixture of two different complexes was found. In ESI-MS (m/z, rel. intensity, assignment), a doubly charged peak at m/z 475.1782 (100%) indicates +2 the presence of [Mn(2+2)(C2H5OH)] . It means that two molecules of 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 3-diamino-2- propanol combine by Schiff base condensation reaction to make a (2+2) macrocycle and this macrocycle further makes acomple with Manganese. A singly charged peak +2 at m/z 740.3782 reveals the formation of a complex [MnBa(3+3)(H2O)] . It reveals that three molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and three molecules of 1, 3-diamino-2-propanol combine by Schiff base condensation reaction to make a (2+2) macrocycle and this macrocycle further makes acomple with Manganese and Barium.

Scan-3.19 MS-Scan of a hetro nuclear complex of manganese and barium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3- diamino-2-propanol

Chapter 3 RESULTS AND DISCUSSION

3.19 MS Studies of a homo-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 4- diaminobutane [CE-24]

In this reaction, a mixture of different complexes was synthesized. ESI-MS (m/z, rel. intensity, assignment) shows a doubly charged peak at m/z 815.5803 to confirm +1 +2 the presence of a complex [CaZn4(3+3)(C2H5OH)(Na) ] . It shows that three molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and three molecules of 1, 4-diaminobutane make a (3+3) macrocycle and this macrocycle further makes a hetro-nuclear complex with Calcium and Zinc. A singly charged peak at m/z 967.3845 reveals the formation of a complex [CaZn(2+2)(Na)+1]+1. It reveals that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 4-diaminobutane make a (2+2) macrocycle by Schiff base reaction and this macrocycle further makes a hetro-nuclear complex with Calcium and Zinc. A singly charged peak at m/z 1083.7889 tells about the presence of a complex +1 +1 [(2H)CaZn2(2+2)(C2H5OH)(Na) ] .

Scan-3.20 MS Scan of a hetro nuclear complex of calcium and zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 4-diaminobutane

Chapter 3 RESULTS AND DISCUSSION

3.20 ESI-MS studies of metal complexes of macrocycles derived from 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane Table 3.9 Mass spectroscopic data for metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane. No. of compd. Found (m/z) Assignment Calc. Mass +1 CE-1 1425 [Pb2(2+2)(C2H5OH)H4] 1425 +2 CE-3 640 [BaNi3(2+2)H4] 1274 +1 +2 887 [BaNi3(3+3)(NH4) ] 1773 +2 CE-7 647 [LaCu3(2+2)H4] 1294 +2 CE-9 613 [BaCu2(2+2)H] 1226 +1 +1 CE-13 1264 [BaZn2(2+2)(H2O)(NH4) ] 1265 +1 +2 CE-15 757 [La2Ni4(2+2)(H2O)(Na) ] 1514 +1 +1 CE-17 1087 [CaNi(2+2)(Na) (H)4] 1087 CE-19 1087 [CaZn(2+2)(Na)+1]+1 1089 +1 CE-20/27 1083 [Cu2(2+2)] 1084 +1 +2 641 [Cu4(2+2)(C2H5OH)(Na) ] 1284 +1 CE-26 640 [Ni4(2+2)(H2O)(C2H5OH)(Na) 1280 ]+2 +1 CE-5 1286 [Ca6(2+2)(H2O)(C2H5OH)(Na) 1288 ]+1

3.20.1 MS study of a hetro-nuclear complex of Lead and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-1] In ESI-MS scan (m/z, rel. intensity, assignment), a singly charged peak at m/z +1 1425.7706 confirms the formation of a complex [Pb2(2+2)(C2H5OH)H4] . It tells that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy]ethane make a macrocycle by Schiff base condensation reaction and this macrocycle further makes a complex with Lead. Copper was also introduced in the reaction mixture but ligand could not coordinate with copper. MS scan does not show the presence of hetro-nuclear complex with both metals. (Scan is given in Appendix-I, Scan-5.1)

Chapter 3 RESULTS AND DISCUSSION

3.20.2 MS Studies of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-3] Ms Study shows that mixture of hetro-nuclear complexes of (2+2) and (3+3) macrocycles has been obtained. In ESI-MS scan (m/z, rel. intensity, assignment), a doubly charged peak at m/z 640.2426 (80%) indicates the presence of a complex +2 [BaNi3(2+2)H4] . It means that two molecules of 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy]ethane make a macrocycle by Schiff base condensation reaction and this macrocycle further makes a complex with Barium and Nickel. Another doubly charged peak at m/z 887.2169 +1 +2 (80%) reveals the formation of [BaNi3(3+3)(NH4) ] . It tells that three molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and three molecules of 1, 2-bis-[2- aminoethoxy]ethane combine to make a macrocycle by Schiff base condensation reaction and this macrocycle further makes a complex with Barium and Nickel.

Scan-3.21 MS-scan of Barium and Nickel complex with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

Chapter 3 RESULTS AND DISCUSSION

Scan-3.22 MS-scan of Barium and Nickel complex with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

3.20.3 MS study of a hetro-nuclear complex of Lanthanum and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy] ethane [CE-7] The product contains mixture of hetro-nuclear complexes with different number of metal ions. In ESI-MS scan (m/z, rel. intensity, assignment), a doubly charged peak +2 at m/z 647.7356 shows the formation of a complex [LaCu3(2+2)H4] . It means that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy] ethane make a macrocycle (2+2) by Schiff base reaction and this macrocycle further makes a complex with Lanthanum and +2 Copper as [LaCu3(2+2)H4] . (Scan is given in Appendix-I, Scan-5.2)

Chapter 3 RESULTS AND DISCUSSION

3.20.4 MS study of a hetro-nuclear complex of Barium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-9] ESI-MS (m/z, rel. intensity, assignment) shows a doubly charged peak at m/z +2 613.1374 and confirms the presence of a complex [BaCu2(2+2)H] . It means that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy] ethane make a macrocycle (2+2) by Schiff base condensation reaction and this macrocycle further makes a complex with Barium and +2 Copper as [BaCu2(2+2)H] . (Scan is given in Appendix-I, Scan-5.3)

3.20.5 MS study of a hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-13] In ESI-MS(m/z, rel. intensity, assignment), a singly charged peak at m/z +1 +1 1264.8138 indicates the formation of a complex [BaZn2(2+2)(H2O)(NH4) ] . It reveals that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy] ethane make a (2+2) macrocycle by Schiff base condensation reaction and this macrocycle further makes a complex with Barium +1 +1 and Zinc as [BaZn2(2+2)(H2O)(NH4) ] . (Scan is given in Appendix-I, Scan-5.4)

3.20.6 MS study of a hetro-nuclear complex of Lanthanum and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-15] In ESI-MS(m/z, rel. intensity, assignment), a doubly charged peak at m/z +1 +2 757.6931 confirms the formation of a complex [La2Ni4(2+2)(H2O)(Na) ] . It shows that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy] ethane make a (2+2) macrocycle by Schiff base condensation reaction and this macrocycle further makes a complex with +1 +2 Lanthanum and Nickel as [La2Ni4(2+2)(H2O)(Na) ] . (Scan is given in Appendix-I, Scan-5.5)

Chapter 3 RESULTS AND DISCUSSION

3.20.7 MS study of a hetro-nuclear complex of Calcium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-17] ESI-MS(m/z, rel. intensity, assignment) shows a singly charged peak at m/z +1 +1 1087.6501 and confirm the formation of a complex [CaNi(2+2)(Na) H4] . It tells that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy] ethane make a (2+2) macrocycle by Schiff base condensation reaction and this macrocycle further makes a complex with +1 +1 Calcium and Nickel as [CaNi(2+2)(Na) H4] . (Scan is given in Appendix-I, Scan- 5.6)

3.20.8 MS study of a hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-19] In ESI-MS(m/z, rel. intensity, assignment), a singly charged peak at m/z 1087.4251 shows the presence of a complex [CaZn(2+2)(Na)+1]+1. It means that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy] ethane make a (2+2) macrocycle by Schiff base condensation reaction and this macrocycle further makes a complex with Calcium and Zinc as [CaZn(2+2)(Na)+1]+1. (Scan is given in Appendix-I, Scan-5.7)

3.20.9 MS Studies of a homo-nuclear complex of Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-20/27] This complex was prepared by stirring 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] (H2mftbp) and Cu(CH3COO)2.H2O in a round-bottomed flask containing methanol. To this clear solution, 1, 2-bis-[2-aminoethoxy]ethane and a base was added and refluxed overnight. Yield of this reaction contains a mixture of complexes of different number of substrate ions. In ESI-MS scan (m/z, rel. intensity, assignment), a singly charged peak at m/z 1083.7891 (80%) indicates the presence of +1 [Cu2(2+2)] . Two molecules of 2,2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1,2-bis-[2-aminoethoxy]ethane make a macrocycle by Schiff-base condensation and ultimately a complex with copper metal. Another doubly charged +1 +2 peak at m/z 641 shows the formation of [Cu4(2+2)(C2H5OH)(Na) )] .

Chapter 3 RESULTS AND DISCUSSION

Scan-3.23 MS-Scan of Copper complex with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

3.20.10 MS Studies of a homo-nuclear complex of Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-26] This complex was prepared by refluxing 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] (H2mftbp) in a round-bottomed flask containing Ni(ClO4)2.6H2O in ethanol. To refluxing solution, 1, 2-bis-[2-aminoethoxy]ethane and a base was added and refluxed overnight. In ESI-MS Scan (m/z, rel. intensity, assignment), a doubly charged peak at m/z 640.2393 (90%) indicates the presence of +1 +2 [Ni4(2+2)(H2O)(C2H5OH)(Na) ] . Two molecules of 2, 2-methylene-bis[(6-formyl)- 4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy]ethane make a (2+2) macrocycle by Schiff-base condensation and ultimately this macrocycle makes a complex with nickel metal.

Chapter 3 RESULTS AND DISCUSSION

Scan-3.24 MS-Scan of Nickel complex with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

3.20.11 MS study of a heomo-nuclear complex of Calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-5] In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z +1 +1 1286.8033 tells the formation of a complex [Ca6(2+2)(H2O)(C2H5OH)(Na) ] . Two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of 1, 2-bis-[2-aminoethoxy]ethane make a (2+2) macrocycle by Schiff-base condensation and ultimately this macrocycle makes a complex with Calcium metal as +1 +1 [Ca6(2+2)(H2O)(C2H5OH)(Na) ] . (Scan is given in Appendix-I, Scan-5.8)

Chapter 3 RESULTS AND DISCUSSION

3.21 ESI-MS studies of metal complexes of macrocycles derived from 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine Table 3.10 Mass spectroscopic data for the metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine. No. of Found (m/z) Assignment Calc. Mass compd. +2 CE-22 864 [Ba4Ni3(2+2)(C2H5OH)] 1728 +1 +2 639 [CaCu4(2+2)(Na) ] 1274 +1 +2 CE-23 905 [Ca2Cu4(3+3)(H2O)(Na) ] 1811 1083 [CaCu(2+2)(Na)+1]+1 1083

3.21.1 MS study of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [CE-22] This complex was synthesized by adding 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] (H2mftbp) in a round-bottomed flask containing Ba(ClO4)2.3H2O and

Ni(ClO4)2.6H2O in ethanol. To this solution, triethylene tetramine and NaOH was added and refluxed overnight. ESI-MS(m/z, rel. intensity, assignment) shows a doubly charged peak at m/z 864.5517 and indicates the presence of a complex +2 [Ba4Ni3(2+2)(C2H5OH)] . It means that two molecules of 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and two molecules of triethylene tetramine make a (2+2) macrocycle by Schiff-base condensation reaction and ultimately this macrocycle +2 makes a complex with Barium and Nickel metal as [Ba4Ni3(2+2)(C2H5OH)] . (Scan is given in Appendix-I, Scan-5.9)

3.21.2 MS Studies of a hetro-nuclear complex of Calcium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [CE-23] In this reaction, a mixture of different sizes of macrocycles and its complexes with different combination were obtained. In ESI-MS scan (m/z, rel. intensity, assignment), a doubly charged peak at m/z 639.3590 indicates the presence of a +1 +2 complex [CaCu4(2+2)(Na) ] . Two molecules of 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and two molecules of triethylene tetramine combine together by

100

Chapter 3 RESULTS AND DISCUSSION

Schiff-base condensation reaction to make a (2+2) macrocycle and this macrocycle makes a complex with calcium and copper metal. A doubly charged peak at m/z +1 +2 905.5573 tells the formation of a complex [Ca2Cu4(3+3)(H2O)(Na) ] . Three molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and three molecules of triethylene tetramine combine together by Schiff-base condensation reaction to make a (3+3) macrocycle and this macrocycle makes a complex with calcium and copper metal. Another singly charged peak at m/z 1083.7827 confirms the presence of a complex [CaCu(2+2)(Na)+1]+1.

Scan-3.25 MS-Scan of a complex of Calcium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine

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Chapter 3 RESULTS AND DISCUSSION

3.22 ESI-MS studies of the metal complexes of macrocycles derived from 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

Table 3.11 Mass spectroscopic data for the metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine. No. of Compd. Found (m/z) Assignment Calc. Mass +1 CE-2 1125 [BaNi2(2+2)] 1125 +1 CE-4 1009 [Ca(2+2)(ClO4)] 1009 +1 +1 CE-8 965 [Cu(2+2)(H2O)(NH4) ] 970 +1 +3 768 [La2Zn4(4+4)(Na) ] 2304 +1 +2 CE-10 1182 [La2Zn4(4+4)(H2O)(C2H5OH)(NH4) ] 2363 +1 +1 1286 [LaZn4(2+2)(NH4) ] 1289 +1 CE-12 1204 [BaZn3(2+2)] 1204 +2 490 [CaZn(2+2)H4] 980 +1 +2 CE-18 832 [Ca2Zn4(3+3)(NH4) ] 1666 +1 +1 952 [Zn(2+2)(NH4) ] 952 +1 +2 1062 [Ca2Zn4(4+4)(H2O)(Na) ] 2125 +2 CE-29 928 [Ni2(4+4)] 1856 +1 +1 1083 [Ni3(2+2)(H2O)(NH4 )] 1083

3.22.1 MS study of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-2] In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z +1 1125.4247 indicates the formation of a complex [BaNi2(2+2)] . It means that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of diethylenetriamine make a (2+2) macrocycle by Schiff-base condensation reaction and ultimately this macrocycle makes a complex with Barium and Nickel metal as +1 [BaNi2(2+2)] . (Scan is given in Appendix-I, Scan-5.10)

102

Chapter 3 RESULTS AND DISCUSSION

3.22.2 MS study of a homo-nuclear complex of Calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-4] In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z +1 1009.4867 reveals the formation of a complex [Ca(2+2)(ClO4)] . Two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of diethylenetriamine make a (2+2) macrocycle by Schiff-base condensation reaction and ultimately this macrocycle makes a complex with Calcium metal as +1 [Ca(2+2)(ClO4)] . (Scan is given in Appendix-I, Scan-5.11)

3.22.3 MS study of a homo-nuclear complex of Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-8] ESI-MS(m/z, rel. intensity, assignment) shows a singly charged peak at m/z +1 +1 965.3802 and confirms the presence of a complex [Cu(2+2)(H2O)(NH4) ] . Two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of diethylenetriamine make a (2+2) macrocycle by Schiff-base condensation reaction +1 +1 and a complex with Copper metal as [Cu(2+2)(H2O)(NH4) ] . In fact, metal ion behaves as a template and it support to cyclisation of these (2+2) molecules to make a macrocycle. (Scan is given in Appendix-I, Scan-5.12)

3.22.4 MS Studies of a hetro-nuclear complex of Lanthanum and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-10] The product of this reaction had a mixture of different complexes. In ESI-MS scan (m/z, rel. intensity, assignment), a triply charged peak at m/z 768.9063 ensures +1 +3 the presence of a complex [La2Zn4(4+4)(Na) ] . Four molecules of 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and four molecules of diethylenetriamine makes a macrocycle by shiff-base condensation reaction and this macrocycle makes a complex with lanthanum and zinc. A doubly charged peak at m/z 1182.8661 confirms the +1 +2 formation of a complex [La2Zn4(4+4)(H2O)(C2H5OH)(NH4) ] . A singly charged +1 +1 peak at m/z 1286.4505 shows the preparation of a complex [LaZn4(2+2)(NH4) ] . It tells that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of diethylenetriamine makes a macrocycle by shiff-base condensation

103

Chapter 3 RESULTS AND DISCUSSION reaction and this macrocycle makes a complex with Lanthanum and Zinc. Lanthanum and Zinc metal ions behave as a template and support to make a macrocycle rather than an oily polymer.

Scan-3.26 MS-Scan of a complex of Lanthanum and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

3.22.5 MS study of a hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-12] In ESI-MS (m/z, rel. intensity, assignment), a singly charged peak at m/z +1 1204.4456 ensures the synthesis of a complex [BaZn3(2+2)] . It tells that two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of diethylenetriamine makes a macrocycle by shiff-base condensation reaction and this macrocycle makes a complex with Barium and Zinc. Barium and Zinc metal ions behave as a template and support to make a macrocycle rather than an oily polymer. (Scan is given in Appendix-I, Scan-5.13)

104

Chapter 3 RESULTS AND DISCUSSION

3.22.6 MS Studies of a hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-18] The synthesis of this complex involves the refluxing of 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] (H2mftbp) and diethylenetriamine in the presence of a base in a round-bottomed flask containing Ca(ClO4)2.6H2O and Zn(CH3COO)2.2H2O in ethanol. Variety of complexes obtained in this reaction. In ESI-MS scan (m/z, rel. intensity, assignment), a doubly charged peak at m/z 490.7199 ensures the presence of +2 a complex [CaZn(2+2)H4] . Two molecules of 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] and two molecules of diethylenetriamine makes a macrocycle by Schiff- base condensation reaction and this macrocycle makes a complex with calcium and zinc as template. A doubly charged peak at m/z 832.3402 confirms the formation of a +1 +2 complex [Ca2Zn4(3+3)(NH4) ] . Three molecules of 2, 2-methylene-bis[(6-formyl)- 4-tert-butylphenol] and three molecules of diethylenetriamine makes a macrocycle by Schiff-base condensation reaction and this macrocycle makes a complex with calcium and zinc as template. A singly charged peak at m/z 952.4007 shows the preparation of +1 +1 a complex [Zn(2+2)(NH4) ] and a doubly charged peak at m/z 1062.3389 informs +1 +2 the synthesis of a complex [Ca2Zn4(4+4)(H2O)(Na) ] .

Scan-3.27 MS-Scan of a complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

105

Chapter 3 RESULTS AND DISCUSSION

3.22.7 MS Studies of a homo-nuclear complex of Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-29] This complex was synthesized by refluxing 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] (H2mftbp) and diethylenetriamine in the presence of a base in a round- bottomed flask containing Ni(ClO4)2.6H2O in ethanol. ESI-MS scan (m/z, rel. intensity, assignment) shows a doubly charged peak at m/z 928.1787 and ensures the +2 presence of a complex [Ni2(4+4)] . Four molecules of 2, 2-methylene-bis[(6-formyl)- 4-tert-butylphenol] and four molecules of diethylenetriamine make a (4+4) macrocycle by Schiff-base condensation reaction and this macrocycle makes a complex with nickel as template. A singly charged peak at m/z 1083.7883 confirms +1 +1 the formation of a complex [Ni3(2+2)(H2O)(NH4) ] . Two molecules of 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and two molecules of diethylenetriamine make a (2+2) macrocycle by Schiff-base condensation reaction and this macrocycle makes a complex with nickel. Nickel acts a template and help to make a macrocycle rather than an oily polymer.

Scan-3.28 MS-Scan of a Nickel complex with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

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Chapter 3 RESULTS AND DISCUSSION

3.23 INFRA RED SPECTROSCOPIC STUDY

The characteristic response of ethers in the infrared is associated with the stretching vibration of the C-O-C system. Since the vibrational characteristics of this system would not be expected to differ greatly from the C-C-C system, it is not surprising to find the response C-O-C stretching in the same general region. However, since vibrations involving oxygen atoms result in greater dipole moment changes than those involving carbon atoms, more intense infrared bands are observed for ethers. The C-O-C stretching bands of ethers, as is the case with the C-O stretching band of alcohals, involve coupling with other vibrations within the molecule. In the spectra of aliphatic ethers, the most characteristic absorption is a strong band in the 1150-1085 cm-1 region because of asymmetrical C-O-C stretching;this band usually occurs near 1125 cm-1. The symmetrical stretching band is usually weak is more readly observed in the Raman spectrum. The C-O-C group in a 6-membered ring absorbs at the same frequency as in an acyclic ether. As the ring becomes smaller, the asymmetrical C-O-C stretching vibration moves progressively to lower wavenumbers (longer wavelength), whereas the symmetrical C-O-C stretching vibration moves to higher wavenumbers.

3.24 IR Spectroscopic studies of Ni, Cu and Zn complexes of 18-crown-6 Table 3.12 Infra Red spectroscopic data for Ni, Cu and Zn complexes of 18-crown-6 Bond 18-crown-6 Ni-Complex Cu-Complex Zn-Complex C-H Stretching 2921.7 2915.03 2853.70 3125.67 C-H Bending 1461.8 1634.76 1460.30 1470.45 C-O-C 1257.2 1396.59 1375.80 1352.98

3.24.1 IR Studies of Ni-complex of 18-Crown-6 [IHCNi] -1 +1 IR (KBr-disc, cm ) spectra of the complex [MNi+NO3] shows peaks at 2915.03 cm-1 confirming the presence of (C-H) stretching. Another peak at 1634.76 cm-1 indicates the presence of (C-H) bending. Similarly a peak at 1396.59 cm-1 confirms the formation of (C-O-C) bond. Other peaks are at 3379.34 cm-1, 2396.06 cm-1, 2066.22 cm-1, 1763.20 cm-1, 1253.41 cm-1, 1096.72 cm-1, 961.84 cm-1, 826.67 cm-1 and 688.82 cm-1. (Scan has been put in Appendix-II, Scan-6.1)

107

Chapter 3 RESULTS AND DISCUSSION

3.24.2 IR Studies of Cu-complex of 18-crown-6 IR scan of copper complex with 18-crown-6 in Figure-10 shows the peaks at 2853.70 cm-1 that reveals the presence of (C-H) stretching. A peak at 1460.30 cm-1 shows (C-H) bending. Another peak at 1375.8 cm-1 tell the formation of (C-O-C) bond. Other peaks are at 3786.0 cm-1, 3697.8 cm-1, 3658.2 cm-1, 3377.9 cm-1, 2922.3 cm-1, 1725.0 cm-1, 1586.7 cm-1, , 1101.6 cm-1, 957.4 cm-1, 835.6 cm-1, 794.7 cm-1 and 723.3 cm-1.

Scan-3.29 IR-Scan of Copper complex of 18-Crown-6

3.24.3 IR Studies of Zn-complex of 18-Crown-6

IR (KBr-disc, cm-1) spectra of the Zn-18-Crown-6 complex in Figure-10 shows the peak at 3125.67 cm-1 that reveals the presence of (C-H) stretching. A peak at 1470.45 cm-1 indicates the presence of (C-H) bending. Another peak at 1352.98 cm-1 tell the formation of (C-O-C) bond. Other peaks are at 3236.2 cm-1, 2236.72 cm-1, 1619.24 cm-1, 1083.5 cm-1, 983.61 cm-1, 960.82 cm-1, 755.92 cm-1. (Scan has been put in Appendix-II, Scan-6.2)

108

Chapter 3 RESULTS AND DISCUSSION

3.25 IR Spectroscopic studies of metal complexes of macrocycle derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol Table 3.13 IR spectroscopic data for metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol. No. of Found Assignment Calc. IR Spectra (cm- compd. (m/z) Mass 1) +1 +1 IR-4/IR-2 959 [Ca2(2+2)(H2O)(NH4) ] 957 3401.19(v, OH); 1636.21(s, C=N) +1 +1 IR-5B 1051 [Zn2(2+2)(CH3COO)(NH4) ] 1051 3435.89(v, OH); 1627.37(s, C=N) +1 +2 CE-25 475 [Mn(2+2)(C2H5OH).4H ] 950 3400.69(v, OH); +1 +2 740 [MnBa(3+3)(H2O).2H ] 1480 1621.73(s, C=N)

3.25.1 IR Studies of a homo-nuclear complex of calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2- propanol [IR-4/IR-2] In IR (KBr-disc, cm-1), the peaks at 3401.19cm-1 (v O-H) shows the presence of hydrogen bond and peeak at 1636.21 cm-1 (v C=N) confirms the Schiff-base condensation reaction. Other peaks are at 2957.41 cm-1, 1479.97 cm-1, 1362.89 cm-1, 1269.93 cm-1, 1218.75 cm-1, 1108.36 cm-1 and 875.35 cm-1.

55 875.35cm-1

50 %T 45 3401.19cm-1 1108.36cm-1

1362.89cm-1

1269.93cm-1 40 1218.75cm-1

35 2957.41cm-1

1479.97cm-1 30 1636.21cm-1

27 4000 3000 2000 1000 250 cm-1 Name Description IR-4 Sample 001 By Analyst Date Tuesday, January 31 2012 Scan-3.30 IR-Scan of a homo-nuclear complex of calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol

109

Chapter 3 RESULTS AND DISCUSSION

3.25.2 IR Studies of a homo-nuclear complex of Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol [ IR-5B ] IR Spectroscopy also confirmed the successful synthesis of macrocycle. A stretching band at 1627.37 cm-1 indicates the presence of (–N=C-) imine bond and ensures Schiff-base condensation reaction. Similarly a peak at 3435.89 cm-1 shows the presence of (-OH) and confirms the presence of hydrogenbond. Other peaks found in scan are 2955.92 cm-1, 2902.12 cm-1, 1563.55 cm-1, 1463.35 cm-1, 1400.92 cm-1, 1361.18 cm-1, 1322.73 cm-1, 1271.15 cm-1, 1212.93 cm-1, 1121.05 cm-1, 1019.69 cm-1, 875.50 cm-1, 828.40 cm-1, 802.78 cm-1, 748.94 cm-1, 661.87 cm-1 and 618.40 cm-1.

618.40cm-1 55 1121.05cm-1 875.50cm-1 802.78cm-1 50 748.94cm-1 1019.69cm-1 828.40cm-1 3435.89cm-1 661.87cm-1 45

40 %T 1322.73cm-1 1212.93cm-1 35 2902.12cm-1 1361.18cm-1

30 1271.15cm-1

2955.92cm-1 1400.92cm-1 20

15 1627.37cm-1 1463.35cm-1 10 1563.55cm-1 9 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description IR-5B Sample 001 By Analyst Date Wednesday, March 14 2012 Scan-3.31 IR-Scan of a homo-nuclear complex of Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propano

3.25.3 IR Studies of a hetro-nuclear complex of Manganese and Barium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3- diamino-2-propanol [CE-25] IR Spectroscopy confirmed the successful synthesis of macrocycle. A stretching band at 1621.73 cm-1 indicates the presence of (–N=C-) imine bond and ensures Schiff-base condensation reaction. Similarly a peak at 3400.69 cm-1 shows the presence of (-OH) and confirms the presence of hydrogenbond. Other peaks found in

110

Chapter 3 RESULTS AND DISCUSSION scan are at 2955.31 cm-1, 1549.63 cm-1, 1443.48 cm-1, 1393.94 cm-1, 1363.74 cm-1, 1314.08 cm-1, 1269.14 cm-1, 1245.95 cm-1, 1219.89 cm-1, 1142.74 cm-1, 1111.22 cm-1, 1087.05 cm-1, 940.96 cm-1, 856.68 cm-1, 836.09 cm-1 and 766.68 cm-1.

940.96cm-1 %T

836.09cm-1 15 856.68cm-1 766.68cm-1 1245.95cm-1 10 1219.89cm-1 1142.74cm-1 1314.08cm-1 5 1549.63cm-1 1269.14cm-1 626.35cm-1 3400.69cm-1 1621.73cm-1 1363.74cm-1 1111.22cm-1 535.22cm-1 1443.48cm-1 1087.05cm-1 2955.31cm-1 1393.94cm-1 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description Ce-25 Sample 002 By Analyst Date Monday, September 24 2012 Scan-3.32 IR-Scan of a hetro nuclear complex of manganese and barium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3- diamino-2-propanol

3.26 IR Studies of a homo-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 4- diaminobutane [CE-24] IR-Scan (KBr-disc, cm-1) tells the successful synthesis of macrocycle. A stretching band at 1609.60 cm-1 indicates the presence of (–N=C-) imine bond and confirms Schiff-base condensation reaction. Similarly a peak at 3435.78 cm-1 shows the presence of (-OH) and confirms the presence of hydrogenbond. Other peaks found in scan are at 3212.12 cm-1, 3118.98 cm-1, 2943.09 cm-1, 1561.35 cm-1, 1554.53 cm-1, 1536.19 cm-1, 1451.07 cm-1, 1270.31 cm-1, 1147.74 cm-1, 1137.92 cm-1, 1119.81 cm-1, 1113.33 cm-1, 1104.89 cm-1, 1090.5 cm-1, 1083.41 cm-1, 1077.01 cm-1, 968.38 cm-1, 946.27 cm-1, 876.66 cm-1, 674.64 cm-1, 660.28 cm-1 and 636.72 cm-1.

111

Chapter 3 RESULTS AND DISCUSSION

45 876.66cm-1

509.96cm-1 40 456.67cm-1

469.97cm-1 35 487.03cm-1 1270.31cm-1

30 946.27cm-1 %T

25 968.38cm-1

15 674.64cm-1 660.28cm-1 3435.78cm-1 2943.09cm-1 1137.92cm-1 10 1147.74cm-1 1119.81cm-1 1077.01cm-1 5 1104.89cm-1 3118.98cm-1 1609.60cm-11561.35cm-11451.07cm-1 1113.33cm-1 1536.19cm-1 1083.41cm-1 636.72cm-1 3212.12cm-1 1090.50cm-1 626.55cm-1 0 1554.53cm-1 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-24 Sample 002 By Analyst Date Friday, August 24 2012 Scan-3.33 IR Scan of a hetro nuclear complex of calcium and zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 4-diaminobutane

3.27 IR Spectroscopic studies of metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane Table 3.14 IR spectroscopic data for the metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane. No. of Found Calc. compd. (m/z) Assignment Mass IR Spectra (cm-1) +1 CE-1 1425 [Pb2(2+2)(EtOH)] 1421 3468.64(v, OH); 1621.81(s, C=N); +2 CE-3 640 [BaNi3(2+2)H4] 1274 3414.19(v, OH); +1 +2 887 [BaNi3(3+3)(NH4) ] 1773 1623.00(s C=N) +2 CE-7 647 [LaCu3(2+2)H4] 1294 3413.30(v, OH); +1 +1 1103 [LaCu2(2+2)(Na) ] 1620.24(s, C=N) +2 CE-9 613 [BaCu2(2+2)H] 1226 3435.85(v, OH); 1621.33(s, C=N) +1 +1 CE-13 1264 [BaZn2(2+2)(H2O)(NH4) ] 1265 3447.89(v, OH); 1619.33(s, C=N)

112

Chapter 3 RESULTS AND DISCUSSION

No. of Found Calc. compd. (m/z) Assignment Mass IR Spectra (cm-1) +1 +2 CE-15 757 [La2Ni4(2+2)(H2O)(Na) ] 1514 3435.90(v, OH); 1630.98(s, C=N) +1 +1 CE-17 1087 [CaNi(2+2)(Na) (H)4] 1087 3400.95(v, OH); 1628.28(s, C=N) CE-19 1087 [CaZn(2+2)(Na)+1]+1 1089 3420.04(v, OH); 1619.00(s, C=N) +1 CE-20/27 1083 [Cu2(2+2)] 1088 3435.87(v, OH); 1619.25(s, C=N) +1 +2 CE-26 640 [Ni4(2+2)(H2O)(EtOH)(Na) ] 1283 3435.64(v, OH); 1637.59(s, C=N) +1 +1 CE-5 1286 [Ca6(2+2)(H2O)(EtOH)(Na) ] 1288 3401.12(v, OH) 1465.73(s, C=N)

3.27.1 IR study of a hetro-nuclear complex of Lead and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-1] In IR-scan (KBr-disc, cm-1), peak at 3468.64 cm-1 (v, OH) indicates the presence of -OH group and hydrogen bond. A sharp peak at 1621.81 cm-1(v C=N) confirms formation of imine bond (-C=N-) by Schiff base condensation reaction. Other peaks in scan are at 2953.10 cm-1, 2903.67 cm-1, 2864.48 cm-1, 1542.24 cm-1, 1445.44 cm-1 (s, COO-), 1392.01 cm-1, 1362.18 cm-1, 1329.38 cm-1, 1268.9 cm-1, 1216.94 cm-1, 1124.24 cm-1, 936.05 cm-1, 871.69 cm-1, 833.97 cm-1, 771.87 cm-1, 708.61 cm-1 and 533.97 cm-1. (Scan has been put in Appendix-II, Scan-6.3)

3.27.2 IR Studies of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-3] In IR-scan (KBr-disc, cm-1), a peak at 3414.19 cm-1 (v, OH) indicates the presence of -OH group and hydrogen bond. Similarly a sharp peak at 1623 cm-1 (v, C=N) confirms formation of imine bond (-C=N-) by Schiff base condensation reaction. Other peaks in scan are at 2954.51 cm-1, 2866.67 cm-1, 1546.88 cm-1,

113

Chapter 3 RESULTS AND DISCUSSION

1453.49 cm-1, 1393.34 cm-1, 1362.63 cm-1, 1270.19 cm-1, 1218.71 cm-1, 1109.3 cm-1, 832.01 cm-1, 770.36 cm-1 and 625.03 cm-1.

68 65

770.36cm-1

40 832.01cm-1 %T 35 625.03cm-1

30 1218.71cm-1 1546.88cm-1 2866.67cm-1 25 3414.19cm-1 1362.63cm-1

20 1270.19cm-1 1393.34cm-1

2954.51cm-1 1109.30cm-1 15 1453.49cm-1 1623.00cm-1 10 9 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-3 Sample 001 By Analyst Date Wednesday, June 13 2012 Scan-3.34 IR-scan of Barium and Nickel complex with a macrocycle based on 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

3.27.3 IR study of a hetro-nuclear complex of Lanthanum and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy] ethane [CE-7] IR-scan also (KBr-disc, cm-1) shows a peak at 1620.24 cm-1 (v C=N) to indicate the formation of imine bond. A broad peak at 3413.30 cm-1 (v, OH) reveals the presence of hydrogen bond. Other peaks in scan are at 2954.49 cm-1, 1541.68 cm-1, 1444.12 cm-1, 1384.65 cm-1, 1268.76 cm-1, 1216.87 cm-1, 1121.46 cm-1, 834.63 cm-1 and 478.29 cm-1. (Scan has been put in Appendix-II, Scan-6.4)

3.27.4 IR study of a hetro-nuclear complex of Barium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-9] IR-scan (KBr-disc, cm-1) shows a peak at 1621.33 cm-1 (v C=N) to indicate the formation of imine bond. A broad peak at 3435.85 cm-1 (v, OH) reveals the presence of hydrogen bond. Other peaks in scan are at 2953.71 cm-1, 1542.03 cm-1, 1445.65 cm-1, 1361.74 cm-1, 1330.33 cm-1, 1268.01 cm-1, 1216.86 cm-1, 1120.88 cm-1 and 834.35 cm-1. (Scan has been put in Appendix-II, Scan-6.5)

114

Chapter 3 RESULTS AND DISCUSSION

3.27.5 IR study of a hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-13] IR-scan (KBr-disc, cm-1) shows a peak at 1619.33 cm-1 (v, C=N) to indicate the formation of imine bond. A broad peak at 3447.89 cm-1 (v, OH) reveals the presence of hydrogen bond. Other peaks in scan are at 2957.4 cm-1, 2866.96 cm-1, 1750.51 cm- 1, 1546.78 cm-1, 1446.87 cm-1, 1362.16 cm-1, 1316.81 cm-1, 1265.48 cm-1, 1212.27 cm-1, 1107.78 cm-1, 926.58 cm-1, 857.36 cm-1, 829.63 cm-1, 803.37 cm-1, 771.98 cm-1, 755.06 cm-1, 693.56 cm-1, 624.65 cm-1 and 534.9 cm-1. (Scan has been put in Appendix-II, Scan-6.6)

3.27.6 IR study of a hetro-nuclear complex of Lanthanum and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-15] IR-scan (KBr-disc, cm-1) tells a peak at 1630.98 cm-1 (v, C=N) to indicate the formation of imine bond and confirms the Schiff base condensation reaction. A broad peak at 3435.90 cm-1 (v, OH) reveals the presence of hydrogen bond. Other peaks in scan are at 2955.09 cm-1, 2868.61 cm-1, 1458.8 cm-1, 1387 cm-1, 1269.19 cm-1, 1243.88 cm-1, 1220.07 cm-1, 1089.83 cm-1, 920.65 cm-1, 831.49 cm-1, 799.49 cm-1, 769.17 cm-1, 749.84 cm-1, 625.48 cm-1 and 531.35 cm-1. (Scan has been put in Appendix-II, Scan-6.7)

3.27.7 IR study of a hetro-nuclear complex of Calcium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-17] IR-scan (KBr-disc, cm-1) indicates a peak at 1628.28 cm-1 (v, C=N) to confirms the formation of imine bond and ensures the Schiff base condensation reaction. A broad peak at 3400.95 cm-1 (v, OH) reveals the presence of hydrogen bond. Other peaks in scan are at 2955.35 cm-1, 1458.88 cm-1, 1269.75 cm-1, 1216.58 cm-1, 1145.24 cm-1, 1114.76 cm-1, 1087.42 cm-1, 866.13 cm-1, 830.28 cm-1 and 626.65 cm-1. (Scan has been put in Appendix-II, Scan-6.8)

115

Chapter 3 RESULTS AND DISCUSSION

3.27.8 IR study of a hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2- bis-[2-aminoethoxy]ethane [CE-19] IR-scan (KBr-disc, cm-1) shows a peak at 1619.00 cm-1 (v, C=N) to ensures the formation of imine bond and confirms the Schiff base condensation reaction. A broad peak at 3420.04 cm-1 (v, OH) reveals the presence of hydrogen bond. Other peaks in scan are at 3662.39 cm-1, 2957.03 cm-1, 2866.62 cm-1, 1546.7 cm-1, 1448.35 cm-1, 1393.46 cm-1, 1362.19 cm-1, 1317.03 cm-1, 1265.48 cm-1, 1235.56 cm-1, 1211.54 cm-1, 1107.38 cm-1, 927.43 cm-1, 903.31 cm-1, 875.99 cm-1, 829.94 cm-1, 803.00 cm-1, 772.13 cm-1, 754.99 cm-1, 703.05 cm-1, 624.67 cm-1, 534.61 cm-1, 506.31 cm-1 and 472.64 cm-1. (Scan has been put in Appendix-II, Scan-6.9)

3.27.9 IR Studies of a homo-nuclear complex of Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-20/27] In IR scan (KBr-disc, cm-1), broad peak at 3435.87 cm-1 indicates the presence of –OH group. The –OH group ensures the presence of hydrogen bond. Similarly another sharp peak at 1619.25 cm-1 confirms the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 2953.31 cm-1, 2903.39 cm-1, 2864.52 cm-1, 1542.5 cm-1, 1445.11 cm-1, 1392.01 cm-1, 1362.27 cm-1, 1329.81 cm-1, 1268.95 cm-1, 1216.85 cm-1, 1122.61 cm-1, 936.82 cm-1, 871.68 cm-1, 834.05 cm-1, 807.77 cm-1, 771.82 cm-1, 709.51 cm-1, 533.46 cm-1 and 482.61 cm-1.

56 55

40 807.77cm-1

35 709.51cm-1

936.82cm-1 482.61cm-1 871.68cm-1 30 533.46cm-1 771.82cm-1 %T 25

3435.87cm-1 20 834.05cm-1

10 1216.85cm-1 1392.01cm-1 1122.61cm-1 2864.52cm-1 1362.27cm-1 5 2903.39cm-1 1329.81cm-1 1542.50cm-1 1268.95cm-1 2953.31cm-1 1619.25cm-1 0 1445.11cm-1 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-20 Sample 007 By Analyst Date Friday, August 24 2012 Scan-3.35 IR-Scan of Copper complex with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane 116

Chapter 3 RESULTS AND DISCUSSION

3.27.10 IR Studies of a homo-nuclear complex of Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-26] In IR scan (KBr-disc, cm-1), broad peak at 3435.64 cm-1 indicates the presence of – OH group. The presence of –OH group ensure the presence of hydrogen bond. Similarly another sharp peak at 1637.59 cm-1 confirms the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 3468.38 cm-1, 3349.56 cm-1, 2953.36 cm-1, 2023.00 cm-1, 1555.04 cm-1, 1455.68 cm-1, 1395.12 cm-1, 1361.78 cm-1, 1303.92 cm-1, 1271.34 cm-1, 1243.23 cm-1, 1220.63 cm-1, 1070.00 cm-1, 1022.82 cm-1, 986.00 cm-1, 913.35 cm-1, 810.47 cm-1, 772.71 cm-1, 636.26 cm-1, 624.46 cm-1, 540.68 cm-1, 474.87 cm-1.

61 60

2023.00cm-1 40

30 %T

15 1555.04cm-1 1395.12cm-1 10

3435.64cm-1 1243.23cm-1 913.35cm-1 540.68cm-1 5 1220.63cm-1 3468.38cm-1 1455.68cm-1 772.71cm-1 474.87cm-1 3349.56cm-1 1361.78cm-1 1022.82cm-1 810.47cm-1 636.26cm-1 624.46cm-1 1271.34cm-1 1070.00cm-1 0 2953.36cm-1 1637.59cm-1 1303.92cm-1 986.00cm-1 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-26 Sample 001 By Analyst Date Monday, September 24 2012 Scan-3.36 IR-Scan of Nickel complex with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

3.27.11 IR study of a homo-nuclear complex of Calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane [CE-5] In IR scan (KBr-disc, cm-1), broad peak at 3401.12 cm-1 indicates the presence of –OH group. The presence of –OH group ensure the presence of hydrogen bond. Similarly another sharp peak at 1465.73 cm-1 confirms the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 2958.99 cm-1, 1119.74 cm-1, 1083.37 cm-1, 870.30 cm-1, 849.80 cm-1, 702.30 cm-1 and 628.55 cm-1. (Scan has been put in Appendix-II, Scan- 6.10)

117

Chapter 3 RESULTS AND DISCUSSION

3.28 IR Spectroscopic studies of the metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine

Table 3.15 Selected data for the metal complexes of macrocycles derived from 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine. No. of Found Calc. compd. (m/z) Assignment Mass IR Spectra (cm-1) +2 CE-22 864 [Ba4Ni3(2+2)(C2H5OH)] 1728 3400.78(v, OH); 1574.63(s, C=N) +1 +2 639 [CaCu4(2+2)(Na) ] 1274 3389.05(v, OH); +1 +2 CE-23 905 [Ca2Cu4(3+3)(H2O)(Na) ] 1811 1508.36(s, C=N) 1083 [CaCu(2+2) (Na)+1]+1 1083

3.28.1 IR study of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [CE-22] In IR scan (KBr-disc, cm-1), broad peak at 3400.78 cm-1 indicates the presence of –OH group. The presence of –OH group ensures the presence of hydrogen bond. Similarly another sharp peak at 1574.63 cm-1 confirms the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 1427.17 cm-1, 1115.38 cm-1, 1086.05 cm-1, 858.2 cm-1, 814.53 cm-1, 693.26 cm-1 and 626.22 cm-1. (Scan has been put in Appendix-II, Scan- 6.11)

3.28.2 IR Studies of a hetro-nuclear complex of Calcium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine [CE-23] In IR scan (KBr-disc, cm-1), broad peak at 3389.05 cm-1 indicates the presence of –OH group. The presence of –OH group ensure the presence of hydrogen bond. Similarly another sharp peak at 1508.36 cm-1 confirms the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 1418.02 cm-1, 1144.94 cm-1, 1114.00 cm-1, 1086.75 cm-1, 865.13 cm-1, 813.48 cm-1 and 626.32 cm-1.

118

Chapter 3 RESULTS AND DISCUSSION

12 %T 10

4 813.73cm-1

865.29cm-1 626.39cm-1 3389.02cm-1 1144.98cm-1 2 1508.36cm-1 1114.04cm-1 1086.78cm-1 1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-23_1 Sample 001 By Analyst Date Monday, September 24 2012 Scan-3.37 IR-Scan of a complex of Calcium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine

3.29 IR Spectroscopic studies of the metal complexes of macrocycles derived from 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

Table 3.16 Selected data for the metal complexes of macrocycles derived from 2, 2- methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine. No. of Found Calc. compd. (m/z) Assignment Mass IR Spectra (cm-1) +1 CE-2 1125 [BaNi2(2+2)] 1125 3435.91(v, OH); 1625.20(s, C=N) +1 CE-4 1009 [Ca(2+2)(ClO4)] 1009 3401.15(v, OH); 1633.36(s, C=N) +1 +1 CE-8 965 [Cu(2+2)(H2O)(NH4) ] 970 3435.63(v, OH); 1620.08(s, C=N) +1 +3 768 [La2Zn4 (4+4)(Na) ] 2304 3436.13(v, OH); + +2 CE-10 1182 [La2Zn4(4+4)(H2O)(EtOH)(NH4) ] 2363 1635.38(s, C=N) +1 +1 1286 [LaZn4(2+2)(NH4 ] 1289

119

Chapter 3 RESULTS AND DISCUSSION

+1 CE-12 1204 [BaZn3(2+2)] 1204 3401.15(v, OH); 1634.37(s, C=N) +2 490 [CaZn(2+2)H4] 980 3325.35(v, OH); +1 +2 CE-18 832 [Ca2Zn4(3+3)(NH4) ] 1666 1637.75(s, C=N) +1 +1 952 [Zn(2+2)(NH4) ] 952 +1 +2 1062 [Ca2Zn4(4+4)(H2O)(Na) ] 2125 +2 CE-29 928 [Ni2(4+4)] 1856 3344.95(v, OH); +1 +1 1083 [Ni3(2+2)(H2O)(NH4 )] 1083 1587.59(s, C=N)

3.29.1 IR study of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-2] In IR scan (KBr-disc, cm-1), broad peak at 3435.91 cm-1 indicates the presence of –OH group. The presence of –OH group ensure the presence of hydrogen bond. Similarly another sharp peak at 1625.20 cm-1 confirms the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 2958.66 cm-1, 1454.92 cm-1, 1267.7 cm-1, 1213.55 cm-1, 1147.05 cm-1, 1119.66 cm-1, 1086.81 cm-1, 856.83 cm-1 and 626.19 cm-1. (Scan has been put in Appendix-II, Scan-6.12)

3.29.2 IR study of a homo-nuclear complex of Calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-4] In IR scan (KBr-disc, cm-1), a broad peak at 3401.15 cm-1 shows the presence of –OH group. The presence of –OH group confirms the presence of hydrogen bond. Similarly another sharp peak at 1633.36 cm-1 indicates the presence of the imine bond (v C=N). The presence of imine bond acknowledges the Schiff-base condensation reaction. Other peaks in the scan are 2957.6 cm-1, 1467.15 cm-1, 1274.61 cm-1, 1221.62 cm-1, 1121.70 cm-1, 1077.73 cm-1, 870.76 cm-1, 823.55 cm-1 and 626.17 cm-1. (Scan has been put in Appendix-II, Scan-6.13)

120

Chapter 3 RESULTS AND DISCUSSION

3.29.3 IR study of a homo-nuclear complex of Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-8] In IR scan (KBr-disc, cm-1), a broad peak at 3435.63 cm-1 shows the presence of –OH group. The presence of –OH group confirms the presence of hydrogen bond. Similarly another sharp peak at 1620.08 cm-1 indicates the presence of imine bond (v C=N). The presence of imine bond acknowledges Schiff-base condensation reaction. Other peaks in the scan are 2957.47 cm-1, 1417.81 cm-1, 1267.12 cm-1, 1114.84 cm-1, 1089.23 cm-1 and 626.75 cm-1. (Scan has been put in Appendix-II, Scan-6.14)

3.29.4 IR Studies of a hetro-nuclear complex of Lanthanum and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-10] In IR scan (KBr-disc, cm-1), broad peak at 3436.13 cm-1 shows the presence of – OH group. The presence of –OH group ensure the presence of hydrogen bond. Similarly another sharp peak at 1635.38 cm-1 confirms the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 2955.03 cm-1, 1569.84 cm-1, 1385.41 cm-1, 1268.8 cm-1, 1215.79 cm-1, 1079.05 cm-1, 1050.4 cm-1, 1019.9 cm-1, 937.66 cm-1, 856.41 cm-1, 828.16 cm-1, 772.11 cm-1, 668.05 cm-1, 620.17 cm-1 and 527.78 cm-1.

31 30

20 937.66cm-1 18 856.41cm-1 772.11cm-1 16 1050.40cm-1 1079.05cm-1 828.16cm-1 1019.90cm-1 %T 14 527.78cm-1

12 620.17cm-1 1215.79cm-1

10 668.05cm-1

1268.80cm-1 6

2 1635.38cm-1 3436.13cm-1 2955.03cm-1 1569.84cm-1 1385.41cm-1 0 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-10 Sample 002 By Analyst Date Friday, July 20 2012 Scan-3.38 IR-Scan of a complex of Lanthanum and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

121

Chapter 3 RESULTS AND DISCUSSION

3.29.5 IR study of a hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-12] In IR scan (KBr-disc, cm-1), broad peak at 3401.15 cm-1 shows the presence of – OH group. The presence of –OH group ensures the presence of hydrogen bond. Similarly another sharp peak at 1634.37 cm-1 confirms the presence of imine bond (v, C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 2955.24 cm-1, 2450.99 cm-1, 1751.04 cm-1, 1570.81 cm-1, 1463.5 cm-1, 1442.00 cm-1, 1429.00 cm-1, 1088.04 cm-1, 857.45 cm-1, 693.38 cm-1, 625.28 cm-1 and 517.62 cm-1. (Scan has been put in Appendix-II, Scan-6.15)

3.29.6 IR Studies of a hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-18] In IR scan (KBr-disc, cm-1), broad peak at 3325.35 cm-1 shows the presence of – OH group. The presence of –OH group ensures the presence of hydrogen bond. Similarly another sharp peak at 1637.75 cm-1 confirms the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 2954.44 cm-1, 1487.32 cm-1, 1268.71 cm-1, 1215.69 cm-1, 1087.23 cm-1, 930.74 cm-1, 875.64 cm-1, 830.77 cm-1, 771.19 cm-1, 746.57 cm-1 and 624.67 cm-1.

35 930.74cm-1

771.19cm-1 30 830.77cm-1

%T 746.57cm-1 25 1215.69cm-1

20 624.67cm-1

15 1268.71cm-1 2954.44cm-1 10 3325.35cm-1 1087.23cm-1 5 1637.75cm-1 875.64cm-1 1487.32cm-1 0 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-18 Sample 002 By Analyst Date Friday, July 20 2012 Scan-3.39 IR-Scan of a complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine 122

Chapter 3 RESULTS AND DISCUSSION

3.29.7 IR Studies of a homo-nuclear complex of Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine [CE-29] In IR scan (KBr-disc, cm-1), broad peak at 3468.03 cm-1 shows the presence of – OH group. The presence of –OH group ensures the presence of hydrogen bond. Similarly another sharp peak at 1587.59 cm-1 indicates the presence of the imine bond (v C=N). The presence of imine bond ensures the Schiff-base condensation reaction. Other peaks in the scan are 3344.95 cm-1, 3271.8 cm-1, 3187.41 cm-1, 2939.33 cm-1, 2880.93 cm-1, 2027.5 cm-1, 1477.43 cm-1, 1449.9 cm-1, 1386.66 cm-1, 1326.48 cm-1, 1284.07 cm-1, 1254.69 cm-1, 1155.65 cm-1, 1135.22 cm-1, 1103.77 cm-1, 1083.34 cm-1, 1071.75 cm-1, 1014.02 cm-1, 975.20 cm-1, 941.17 cm-1, 910.24 cm-1, 888.84 cm-1, 864.61 cm-1, 830.76 cm-1, 629.81 cm-1 and 519.72 cm-1.

58 55

2027.50cm-1 35

30 %T 25 830.76cm-1 864.61cm-1 1284.07cm-1 20 910.24cm-1 1386.66cm-1 1254.69cm-1 15 1326.48cm-1 941.17cm-1 10

3187.41cm-1 1477.43cm-1 975.20cm-1 1449.90cm-1 5 3344.95cm-1 1014.02cm-1 3468.03cm-1 3271.80cm-1 2880.93cm-1 1587.59cm-1 1155.65cm-1 888.84cm-1 629.81cm-1 2939.33cm-1 1135.22cm-11103.77cm-11083.34cm-11071.75cm-1 519.72cm-1 0 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-29 Sample 003 By Analyst Date Monday, September 24 2012 Scan-3.40 IR-Scan of a Nickel complex with a macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

123

Chapter 3 RESULTS AND DISCUSSION

3.30 SINGLE CRYSTAL X-RAY ANALYSIS Single crystal X-ray diffraction data were collected at 150K on Bruker Apex II CCD [194] diffractometer using graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) at Loughborough University, Loughborough, UK. The structures were solved by direct methods and refined by full-matrix squares on F2. The Bruker SHELXTL [200] software was used for structure solution and refinement. All non- hydrogen atoms were refined anisotropically and hydrogen atoms were inserted at calculated positions using a riding model, unless otherwise stated. The crystallography graphics were done using XP [195] Mercury 2.4 [196] and Ortep 3 for Windows [197] and were rendered in POV-Ray software [198].

3.30.1 Single crystal X-ray of Cu-18-Crown-6 complex Copper complex of 18-Crown-6 has been synthesized by stirring equimolar quantity of methanolic solution of Copper Nitrate and 18-crown-6 under reflux overnight. Blue Crystals of 1:1 copper complex were obtained by slow evaporation of the solvent. The crystals of copper complex with 18-crown-6 grows in monoclinic space group P 2 1/n, with unit cell parameters a = 10.0228(7) Å , b = 12.9341(9) Å , c = 16.7351(12)Å , α = 90.00, β = 92.089(1), γ= 90.00, Z = 4, V= 2168.0(3) Å3. Figure- 4 shows that Unit cell has Z value equal to 4. It means unit cell contains four molecules of the complex. Single Crystal of copper complex of 18-crown-6 make a network in three dimensions as shown in Figure-3.66. In this complex, copper has coordination number 5 and it is bounded by coordination bond with three molecules of water and two molecules of nitrate. In one dimension, these three water molecules are further attached through hydrogenbonding with oxygen atoms of 18-crown-6 while oxygen atoms of Nitrate makes hydrogen bonding with hydrogen atoms attached with carbon atoms of the crown ether in other two dimensions. As we already know that sodium and potassium occupy the centre of the 18-crown-6 but in case of copper metal, copper metal does not occupy the centre of the 18-crown-6 because the size of the sodium or potassium is bigger than copper and copper does not exactly fit into the cavity of the 18-crown-6. The geometry around copper atom is trigonal bipyramidal. In fact copper does not make any direct contact with 18-crown-6 but oxygen atom of three molecules of water and two molecule of nitrate coordinated with copper, further

124

Chapter 3 RESULTS AND DISCUSSION make hydrogen bonding with oxygen and carbon atoms of 18-crown-6. Each coordination sphere is sandwiched between two molecules of 18-crown-6. O7 of water molecule coordinated with copper, makes hydrogen bonding with O6 of one molecule of 18-crown-6 and O3 of other molecule of 18-crown-6. Similarly, O8 and O9 are coordinated with copper at 180O with each other. O8 makes hydrogen bonding with O2 and O4 of one molecule of 18-crown-6 and O9 of the other coordination sphere. Similarly, O9 makes hydrogen bonding with O1, O5 and O6 of the other molecule of 18-crown-6. There are also hydrogenbonds between oxygen atoms of the nitrate and carbon atoms of the 18-crown-6 but these interactions are in other two dimensions e.i. C3 makes hydrogenbond with O10 and O11 of nitrate, C6 makes hydrogenbond with O12, C9 makes hydrogenbond with O10ii and O11iii, C10 makes hydrogenbond with O11iii and C12 makes hydrogenbond with O12ii and O12iv,. Symmetry transformations used to generate equivalent atoms are (i) -x+3/2, y+1/2, - z+3/2; (ii) -x+3/2, y-1/2, -z+3/2; (iii) x+1/2, -y+1/2, z-1/2; (iv) x-1/2, -y+1/2, z-1/2.

Figure-3.4

Figure-3.5 125

Chapter 3 RESULTS AND DISCUSSION

Figure-3.6

Figure-3.7 Three dimensional x-ray crystal structure of Copper complex of 18- crown-6

126

Chapter 3 RESULTS AND DISCUSSION

Table-3.17 Crystal data

C12H27CuN2O15 Z = 4

Mr = 502.89 F(000) = 1048 -3 Monoclinic, P21/n Dx = 1.541 Mg m a = 10.0228 (7) Å Mo K radiation,  = 0.71073 Å b = 12.9341 (9) Å  = 1.08 mm-1 c = 16.7351 (12) Å T = 150 K  = 92.089 (1)° 0.35 × 0.14 × 0.10 mm V = 2168.0 (3) Å3

Table-3.18 Data collection

Absorption correction: multi-scan Rint = 0.040 multi-scan

Tmin = 0.703, Tmax = 0.904 max = 28.4°, min = 2.0° 22015 measured reflections h = -1313 5422 independent reflections k = -1717 3811 reflections with I > 2 (I) l = -2122

Table-3.19 Refinement Refinement on F2 0 restraints Least-squares matrix: full Hydrogen site location: inferred from neighbouring sites R[F2 > 2 (F2)] = 0.036 H-atom parameters constrained

2 2 2 2 wR(F ) = 0.098 w = 1/[ (Fo ) + (0.0452P) + 0.8353P] 2 2 where P = (Fo + 2Fc )/3

S = 1.04 (/)max = 0.009 -3 5422 reflections max = 0.73 e Å -3 274 parameters min = -0.35 e Å

127

Chapter 3 RESULTS AND DISCUSSION

Table-3.20 Geometric parameters (Å, º)

Cu1—O8 1.9602 (15) O3—C7 1.425 (3)

Cu1—O9 1.9616 (15) O3—C6 1.426 (3)

Cu1—O13 1.9672 (15) O4—C8 1.429 (3)

Cu1—O10 1.9905 (15) O4—C9 1.435 (3)

Cu1—O7 2.2480 (15) O5—C11 1.426 (3)

N1—O11 1.226 (2) O5—C10 1.431 (3)

N1—O12 1.241 (3) O6—C12 1.426 (3)

N1—O10 1.300 (2) O6—C1 1.429 (3)

N2—O14 1.227 (3) C1—C2 1.493 (4)

N2—O15 1.232 (3) C3—C4 1.492 (4)

N2—O13 1.297 (2) C5—C6 1.493 (4)

O1—C2 1.424 (3) C7—C8 1.496 (3)

O1—C3 1.430 (3) C9—C10 1.496 (4)

O2—C5 1.425 (3) C11—C12 1.499 (4)

O2—C4 1.436 (3)

O8—Cu1—O9 174.45 (6) C7—O3—C6 113.05 (18)

O8—Cu1—O13 92.52 (6) C8—O4—C9 111.67 (18)

O9—Cu1—O13 91.47 (7) C11—O5—C10 110.98 (19)

O8—Cu1—O10 87.13 (6) C12—O6—C1 112.6 (2)

O9—Cu1—O10 88.92 (6) N1—O10—Cu1 106.98 (12)

O13—Cu1—O10 179.28 (6) N2—O13—Cu1 114.79 (13)

O8—Cu1—O7 94.00 (6) O6—C1—C2 108.9 (2)

O9—Cu1—O7 90.05 (6) O1—C2—C1 108.6 (2)

128

Chapter 3 RESULTS AND DISCUSSION

O13—Cu1—O7 87.04 (6) O1—C3—C4 110.2 (2)

O10—Cu1—O7 92.35 (6) O2—C4—C3 110.0 (2)

O11—N1—O12 124.0 (2) O2—C5—C6 109.75 (19)

O11—N1—O10 118.8 (2) O3—C6—C5 109.0 (2)

O12—N1—O10 117.25 (17) O3—C7—C8 108.97 (19)

O14—N2—O15 123.5 (2) O4—C8—C7 108.52 (19)

O14—N2—O13 118.90 (18) O4—C9—C10 109.79 (19)

O15—N2—O13 117.6 (2) O5—C10—C9 110.6 (2)

C2—O1—C3 112.1 (2) O5—C11—C12 109.5 (2)

C5—O2—C4 110.46 (19) O6—C12—C11 109.1 (2)

O11—N1—O10— 179.98 (17) C7—O3—C6—C5 176.11 (19) Cu1

O12—N1—O10— -0.2 (2) O2—C5—C6—O3 -68.9 (2) Cu1

O14—N2—O13— 1.3 (3) C6—O3—C7—C8 -164.89 (19) Cu1

O15—N2—O13— -178.97 (17) C9—O4—C8—C7 178.15 (19) Cu1

C12—O6—C1— 165.2 (2) O3—C7—C8—O4 72.9 (2) C2

C3—O1—C2—C1 -178.4 (2) C8—O4—C9— 173.28 (19) C10

O6—C1—C2—O1 -71.5 (3) C11—O5—C10— -169.0 (2) C9

C2—O1—C3—C4 -170.4 (2) O4—C9—C10— -69.3 (3) O5

129

Chapter 3 RESULTS AND DISCUSSION

C5—O2—C4—C3 167.4 (2) C10—O5—C11— -174.6 (2) C12

O1—C3—C4—O2 70.6 (3) C1—O6—C12— -179.2 (2) C11

C4—O2—C5—C6 174.7 (2) O5—C11—C12— 67.0 (3) O6

Table-3.21 Hydrogen-bond geometry (Å, º) D—H···A D—H H···A D···A D—H···A O7—H7···O6 0.84 1.99 2.803 (2) 162 O8—H8···O2 0.84 2.10 2.925 (2) 169 O9—H9···O5i 0.84 2.02 2.849 (2) 168 O9—H9···O6i 0.84 2.62 3.028 (2) 111 C3—H3B···O10 0.99 2.55 3.360 (3) 139 C3—H3B···O11 0.99 2.62 3.453 (3) 141 C6—H6A···O12 0.99 2.54 3.452 (3) 152 C9—H9A···O10ii 0.99 2.47 3.300 (3) 141 C12— 0.99 2.50 3.387 (3) 150 H12B···O12ii C9—H9B···O11iii 0.99 2.50 3.191 (3) 126 C10— 0.99 2.53 3.133 (3) 119 H10B···O11iii C12— 0.99 2.30 3.212 (3) 154 H12A···O12iv

Symmetry transformations used to generate equivalent atoms: (i) -x+3/2, y+1/2, - z+3/2; (ii) -x+3/2, y-1/2, -z+3/2; (iii) x+1/2, -y+1/2, z-1/2; (iv) x-1/2, -y+1/2, z-1/2.

130

Chapter 3 RESULTS AND DISCUSSION

3.30.2 Single crystal X-ray of a macrocyclic ligand based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 2-Bis-[2-aminoethoxy]ethane

This macrocyclic ligand was obtained in a yellow crystalline solid form. The ligand crystallizes in the monoclinic space group P 2(1)/c, with unit cell dimensions, a = 21.2761(17) Å, b = 26.038(2) Å , c = 10.0873(8) Å , α = 90°, β = 93.7090(10)°, γ= 90°, Z = 8, V= 5576.6(8) Å3. Unit cell has Z=8, i.e. unit cell contains 8 molecules of macrocyclic ligand.

Figure-3.8

Figure-3.9

131

Chapter 3 RESULTS AND DISCUSSION

Figure-3.10

Intramolecular hydrogen bonding is present between phenolic hydrogen and nitrogen as shown in Figure-3.70, Figure-3.71, 3.72 and Figure-3.73.

Figure-3.11

132

Chapter 3 RESULTS AND DISCUSSION

Figure-3.12

Figure-3.13 133

Chapter 3 RESULTS AND DISCUSSION

Figure-3.14

Table-3.22 Crystal data and structure refinement for Synthesized Macrocyclic ligand Identification code ce5 Empirical formula C29H40N2O4 Formula weight 480.63 Temperature 150(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/c Unit cell dimensions a = 21.2761(17) Å = 90° b = 26.038(2) Å = 93.70(10) ° c = 10.0873(8) Å = 90°

Volume 5576.6(8) Å3 Z 8 Density (calculated) 1.145 Mg/m3 Absorption coefficient 0.076 mm-1

134

Chapter 3 RESULTS AND DISCUSSION

F(000) 2080 Crystal size 0.27 x 0.19 x 0.10 mm3 Crystal description yellow block Theta range for data collection 1.56 to 26.43°. Index ranges -26<=h<=26, -32<=k<=32, -12<=l<=12 Reflections collected 49624 Independent reflections 11456 [R(int) = 0.0702] Completeness to theta = 26.43° 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9925 and 0.9799 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 11456 / 0 / 659 Goodness-of-fit on F2 1.014 Final R indices [I>2sigma(I)] R1 = 0.0581, wR2 = 0.1353 R indices (all data) R1 = 0.1181, wR2 = 0.1629 Largest diff. peak and hole 0.408 and -0.228 e.Å-3

Table-3.23 Bond lengths [Å] and angles [°] for Synthesized Macrocyclic ligand ______N(1)-C(1) 1.275(3) C(4)-C(9) 1.400(3) N(1)-C(24) 1.470(3) C(4)-C(5) 1.536(3) N(2)-C(23) 1.274(3) C(5)-C(6) 1.524(4) N(2)-C(27) 1.459(3) C(5)-C(8) 1.530(3) O(1)-C(11) 1.352(3) C(5)-C(7) 1.536(4) O(2)-C(22) 1.357(3) C(11)-C(10) 1.407(3) O(3)-C(25) 1.418(3) C(10)-C(9) 1.379(3) O(3)-C(26) 1.430(3) C(10)-C(12) 1.515(3) O(4)-C(28) 1.402(3) C(12)-C(13) 1.519(3) O(4)-C(29) 1.425(3) C(13)-C(14) 1.391(3) C(1)-C(2) 1.457(3) C(13)-C(22) 1.395(3) C(2)-C(3) 1.401(3) C(14)-C(15) 1.398(3) C(2)-C(11) 1.405(3) C(15)-C(20) 1.387(3) C(3)-C(4) 1.382(3) C(15)-C(16) 1.536(3)

135

Chapter 3 RESULTS AND DISCUSSION

C(16)-C(18) 1.523(4) C(4A)-C(14A) 1.409(3) C(16)-C(17) 1.528(4) C(4A)-C(5A) 1.531(3) C(16)-C(19) 1.529(4) C(5A)-C(6A) 1.529(4) C(20)-C(21) 1.393(3) C(5A)-C(7A) 1.540(4) C(21)-C(22) 1.410(3) C(5A)-C(8A) 1.551(4) C(21)-C(23) 1.460(3) C(9A)-C(13A) 1.388(3) C(24)-C(25) 1.506(4) C(9A)-C(15A) 1.415(4) C(26)-C(29)#1 1.485(4) C(10A)-C(14A) 1.389(3) C(27)-C(28) 1.504(4) C(10A)-C(11A) 1.401(3) C(29)-C(26)#1 1.485(4) C(10A)-C(12A) 1.519(3) N(1A)-C(1A) 1.278(3) C(12A)-C(13A) 1.510(3) N(1A)-C(24A) 1.454(3) C(13A)-C(22A) 1.403(3) N(2A)-C(23A) 1.273(3) C(15A)-C(20A) 1.381(3) N(2A)-C(27A) 1.445(3) C(15A)-C(16A) 1.537(4) O(1A)-C(11A) 1.354(3) C(16A)-C(19A) 1.523(4) O(2A)-C(22A) 1.356(3) C(16A)-C(18A) 1.534(4) O(3A)-C(25A) 1.414(3) C(16A)-C(17A) 1.537(4) O(3A)-C(26A) 1.429(3) C(20A)-C(21A) 1.403(3) O(4A)-C(28A) 1.420(3) C(21A)-C(22A) 1.411(3) O(4A)-C(29A) 1.428(3) C(21A)-C(23A) 1.457(3) C(1A)-C(2A) 1.458(3) C(24A)-C(25A) 1.505(4) C(2A)-C(3A) 1.403(3) C(26A)-C(29A)#2 1.502(4) C(2A)-C(11A) 1.404(3) C(27A)-C(28A) 1.507(4) C(3A)-C(4A) 1.383(3) C(29A)-C(26A)#2 1.502(4)

C(1)-N(1)-C(24) 117.1(3) C(4)-C(3)-C(2) 122.1(2) C(23)-N(2)-C(27) 119.1(2) C(3)-C(4)-C(9) 116.8(2) C(25)-O(3)-C(26) 114.6(2) C(3)-C(4)-C(5) 122.9(2) C(28)-O(4)-C(29) 113.0(2) C(9)-C(4)-C(5) 120.3(2) N(1)-C(1)-C(2) 123.0(3) C(6)-C(5)-C(8) 108.0(2) C(3)-C(2)-C(11) 119.3(2) C(6)-C(5)-C(4) 112.2(2) C(3)-C(2)-C(1) 119.7(2) C(8)-C(5)-C(4) 110.0(2) C(11)-C(2)-C(1) 121.1(2) C(6)-C(5)-C(7) 108.7(2)

136

Chapter 3 RESULTS AND DISCUSSION

C(8)-C(5)-C(7) 108.7(2) O(2)-C(22)-C(13) 118.6(2) C(4)-C(5)-C(7) 109.2(2) O(2)-C(22)-C(21) 121.7(2) O(1)-C(11)-C(2) 121.2(2) C(13)-C(22)-C(21) 119.7(2) O(1)-C(11)-C(10) 119.0(2) N(2)-C(23)-C(21) 122.4(2) C(2)-C(11)-C(10) 119.8(2) N(1)-C(24)-C(25) 111.2(2) C(9)-C(10)-C(11) 118.2(2) O(3)-C(25)-C(24) 108.0(2) C(9)-C(10)-C(12) 121.6(2) O(3)-C(26)-C(29)#1 114.6(2) C(11)-C(10)-C(12) 120.2(2) N(2)-C(27)-C(28) 112.7(2) C(10)-C(9)-C(4) 123.7(2) O(4)-C(28)-C(27) 109.5(2) C(10)-C(12)-C(13) 112.67(19) O(4)-C(29)-C(26)#1 109.6(2) C(14)-C(13)-C(22) 119.0(2) C(1A)-N(1A)-C(24A) 117.2(2) C(14)-C(13)-C(12) 121.1(2) C(23A)-N(2A)-C(27A) 118.9(2) C(22)-C(13)-C(12) 119.9(2) C(25A)-O(3A)-C(26A) 114.2(2) C(13)-C(14)-C(15) 123.1(2) C(28A)-O(4A)-C(29A) 113.28(19) C(20)-C(15)-C(14) 116.3(2) N(1A)-C(1A)-C(2A) 122.7(2) C(20)-C(15)-C(16) 120.9(2) C(3A)-C(2A)-C(11A) 119.6(2) C(14)-C(15)-C(16) 122.7(2) C(3A)-C(2A)-C(1A) 119.8(2) C(18)-C(16)-C(17) 107.9(2) C(11A)-C(2A)-C(1A) 120.6(2) C(18)-C(16)-C(19) 108.7(2) C(4A)-C(3A)-C(2A) 122.0(2) C(17)-C(16)-C(19) 109.2(2) C(3A)-C(4A)-C(14A) 116.7(2) C(18)-C(16)-C(15) 112.1(2) C(3A)-C(4A)-C(5A) 123.0(2) C(17)-C(16)-C(15) 110.0(2) C(14A)-C(4A)-C(5A) 120.2(2) C(19)-C(16)-C(15) 109.0(2) C(6A)-C(5A)-C(4A) 112.3(2) C(15)-C(20)-C(21) 123.0(2) C(6A)-C(5A)-C(7A) 108.2(2) C(20)-C(21)-C(22) 118.9(2) C(4A)-C(5A)-C(7A) 109.4(2) C(20)-C(21)-C(23) 120.9(2) C(6A)-C(5A)-C(8A) 109.0(2) C(22)-C(21)-C(23) 120.3(2) C(4A)-C(5A)-C(8A) 108.4(2) C(7A)-C(5A)-C(8A) 109.5(2) O(1A)-C(11A)-C(2A) 121.1(2) C(13A)-C(9A)-C(15A) 123.6(2) C(10A)-C(11A)-C(2A) 119.9(2) C(14A)-C(10A)-C(11A) 118.5(2) C(13A)-C(12A)-C(10A) 111.25(19) C(14A)-C(10A)-C(12A) 121.7(2) C(9A)-C(13A)-C(22A) 118.0(2) C(11A)-C(10A)-C(12A) 119.8(2) C(9A)-C(13A)-C(12A) 122.6(2) O(1A)-C(11A)-C(10A) 119.0(2) C(22A)-C(13A)-C(12A) 119.3(2)

137

Chapter 3 RESULTS AND DISCUSSION

C(10A)-C(14A)-C(4A) 123.2(2) C(20A)-C(21A)-C(23A) 120.6(2) C(20A)-C(15A)-C(9A) 116.4(2) C(22A)-C(21A)-C(23A) 120.4(2) C(20A)-C(15A)-C(16A) 120.2(3) O(2A)-C(22A)-C(13A) 118.8(2) C(9A)-C(15A)-C(16A) 123.3(2) O(2A)-C(22A)-C(21A) 120.9(2) C(19A)-C(16A)-C(18A) 108.0(3) C(13A)-C(22A)-C(21A) 120.3(2) C(19A)-C(16A)-C(17A) 109.0(3) N(2A)-C(23A)-C(21A) 122.7(2) C(18A)-C(16A)-C(17A) 108.8(3) N(1A)-C(24A)-C(25A) 112.9(2) C(19A)-C(16A)-C(15A) 112.2(3) O(3A)-C(25A)-C(24A) 109.5(2) C(18A)-C(16A)-C(15A) 109.8(2) O(3A)-C(26A)-C(29A)#2 113.1(2) C(17A)-C(16A)-C(15A) 109.0(2) N(2A)-C(27A)-C(28A) 110.4(2) C(15A)-C(20A)-C(21A) 122.6(2) O(4A)-C(28A)-C(27A) 107.9(2) C(20A)-C(21A)-C(22A) 118.9(2) O(4A)-C(29A)-C(26A)#2 109.5(2) ______Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y+1,-z+1 #2 -x,-y+1,-z+1

Table-3.24 Hydrogen bonds for Synthesized Macrocyclic ligand [Å and °] ______D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ______O(1)-H(1)...N(1) 0.86(3) 1.81(4) 2.610(3) 153(3) O(2)-H(2)...N(2) 0.90(3) 1.74(3) 2.590(3) 156(3) O(1A)-H(2A)...N(1A) 1.04(3) 1.64(3) 2.593(3) 151(3) O(2A)-H(1A)...N(2A) 1.04(3) 1.60(3) 2.579(3) 154(3) ______Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y+1,-z+1 #2 -x,-y+1,-z+1

138

Chapter 3 RESULTS AND DISCUSSION

3.30.3 Single crystal X-ray of a Dizinc(II) complex of a Pseudocalixarene macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3- diamino-2-propanol

[(2+2)Zn2.CH3COO] complex was prepared by refluxing 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] (H2mftbp) and 1, 3-diamino-2-propanol in a round- bottomed flask containing Ca(ClO4)2 in ethanol in the presence of a base. Sample was taken from the refluxing solution and submitted for MS. ESI-MS showed the peak at m/z 923.5670 to confirm the formation of calcium complex [(2+2)Ca] but when

Zn(CH3COO)2.2H2O was added and refluxed for further 6 hrs. Zn replaced Ca metal and a new complex of Zn was formed as [Zn2(2+2)] complex. A yellow powder was filtered after cooling at room temperature. The powder was crystallized by vapour diffusion method using DMF and Diethyl Ether. The complex crystallizes in the monoclinic crystal system with space group P2(1)/n. Unit cell parameters are; a = 13.6595(7) Å, b = 18.5216(9) Å, c = 25.0723(12) Å, α = 90°, β = 95.7020(10)°, γ = 90°, Z = 8, and V= 6311.8(5) Å3. Unit cell has Z value 8, i.e. unit cell contains 8 molecules of dinuclear complex of zinc. Dinuclear complex of zinc is shown in Figure-3.74, Figure-3.75 and Figure-3.76. Each Zinc ion is coordinated to two imine groups, two phenol oxygen atoms and a bridging acetate ion. Geometry around each metal cation is square pyramidal with acetate oxygen at apical. Two hydrogen bond linkages are present between adjacent phenol oxygen atoms as shown in Figure-3.74. Presence of hydrogen bonds indicates that one proton is lost from each pair of phenols. Alcohol groups are not involved in bonding to zinc ions. The macrocycle adopts a saddle conformation with adjacent phenolic rings inclined at 68.5(1)° and 68.7(1)° as shown in Figure-3.75.

CH CH3 3

H3C CH3 H3C CH3

CH N O 3 O N

O HO Zn O Zn OH

N O O N

H3C CH3 H3C CH3

CH3 CH3 Dinuclear Complex of Zn with H2mftbp

139

Chapter 3 RESULTS AND DISCUSSION

Figure-3.15

Figure-3.16

140

Chapter 3 RESULTS AND DISCUSSION

Figure-3.17

Table-3.25 Crystal data and structure refinement for synthesized dizinc complex Identification code sad-sr Empirical formula C28.50 H37 Cl0.50 N2.50 O6.50 Zn Formula weight 601.70 Temperature 150(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P2(1)/n Unit cell dimensions a = 13.6595(7) Å = 90° b = 18.5216(9) Å = 95.70(10) ° c = 25.0723(12) Å = 90°

Volume 6311.8(5) Å3 Z 8 Density (calculated) 1.266 Mg/m3 Absorption coefficient 0.863 mm-1 F(000) 2528 Crystal size 0.39 x 0.23 x 0.20 mm3

141

Chapter 3 RESULTS AND DISCUSSION

Theta range for data collection 1.37 to 28.34° Index ranges -18<=h<=18, -24<=k<=24, -33<=l<=33 Reflections collected 64708 Independent reflections 15724 [R(int) = 0.0403] Completeness to theta = 28.34° 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.8463 and 0.7295 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 15724 / 0 / 720 Goodness-of-fit on F2 1.091 Final R indices [I>2sigma(I)] R1 = 0.0610, wR2 = 0.1808 R indices (all data) R1 = 0.0789, wR2 = 0.1915 Largest diff. peak and hole 2.617 and -0.732 e.Å-3

Table-3.26 Bond lengths [Å] and angles [°] for synthesized dizinc complex ______Zn(1)-O(5) 2.006(2) N(1)-C(52) 1.465(4) Zn(1)-N(1) 2.050(3) N(2)-C(23) 1.288(4) Zn(1)-O(7) 2.085(2) N(2)-C(24) 1.467(4) Zn(1)-N(4) 2.103(3) N(3)-C(27) 1.276(4) Zn(1)-O(1) 2.108(2) N(3)-C(26) 1.477(4) Zn(1)-O(9) 2.361(3) N(4)-C(49) 1.273(4) Zn(2)-O(8) 1.992(2) N(4)-C(50) 1.470(4) Zn(2)-O(2) 2.0354(19) N(5)-C(55) 1.329(6) Zn(2)-N(2) 2.074(3) N(5)-C(57) 1.426(6) Zn(2)-N(3) 2.090(3) N(5)-C(56) 1.444(5) Zn(2)-O(4) 2.104(2) O(1)-C(7) 1.362(3) Cl(1)-O(12) 1.360(5) O(2)-C(18) 1.332(3) Cl(1)-O(11) 1.381(4) O(3)-C(25) 1.399(5) Cl(1)-O(10) 1.401(5) O(4)-C(33) 1.367(3) Cl(1)-O(13) 1.402(7) O(5)-C(44) 1.342(3) N(1)-C(1) 1.285(4) O(6)-C(51) 1.385(4)

142

Chapter 3 RESULTS AND DISCUSSION

O(7)-C(53) 1.240(4) C(25)-C(26) 1.516(5) O(8)-C(53) 1.251(4) C(27)-C(28) 1.459(4) O(9)-C(55) 1.219(5) C(28)-C(29) 1.402(4) C(1)-C(2) 1.462(4) C(28)-C(33) 1.407(4) C(2)-C(7) 1.398(4) C(29)-C(30) 1.390(4) C(2)-C(3) 1.415(4) C(30)-C(31) 1.400(4) C(3)-C(4) 1.381(4) C(30)-C(34) 1.537(4) C(4)-C(5) 1.403(4) C(31)-C(32) 1.385(4) C(4)-C(8) 1.538(4) C(32)-C(33) 1.395(4) C(5)-C(6) 1.392(4) C(32)-C(38) 1.515(4) C(6)-C(7) 1.396(4) C(34)-C(35) 1.439(7) C(6)-C(12) 1.516(4) C(34)-C(37) 1.484(8) C(8)-C(10) 1.531(5) C(34)-C(36) 1.528(6) C(8)-C(11) 1.533(5) C(38)-C(39) 1.515(4) C(8)-C(9) 1.539(4) C(39)-C(40) 1.392(4) C(12)-C(13) 1.524(4) C(39)-C(44) 1.405(4) C(13)-C(14) 1.391(4) C(40)-C(41) 1.396(4) C(13)-C(18) 1.409(4) C(41)-C(42) 1.394(4) C(14)-C(15) 1.402(4) C(41)-C(45) 1.533(4) C(15)-C(16) 1.386(5) C(42)-C(43) 1.402(4) C(15)-C(19) 1.535(4) C(43)-C(44) 1.410(4) C(16)-C(17) 1.412(4) C(43)-C(49) 1.461(4) C(17)-C(18) 1.415(4) C(45)-C(46) 1.519(4) C(17)-C(23) 1.439(4) C(45)-C(47) 1.534(5) C(19)-C(21) 1.498(6) C(45)-C(48) 1.549(5) C(19)-C(22) 1.528(6) C(50)-C(51) 1.524(5) C(19)-C(20) 1.547(6) C(51)-C(52) 1.531(5) C(24)-C(25) 1.535(5) C(53)-C(54) 1.495(6)

O(5)-Zn(1)-N(1) 173.34(9) N(1)-Zn(1)-N(4) 94.45(10) O(5)-Zn(1)-O(7) 87.98(10) O(7)-Zn(1)-N(4) 100.16(11) N(1)-Zn(1)-O(7) 98.23(10) O(5)-Zn(1)-O(1) 93.34(8) O(5)-Zn(1)-N(4) 86.76(9) N(1)-Zn(1)-O(1) 84.79(9)

143

Chapter 3 RESULTS AND DISCUSSION

O(7)-Zn(1)-O(1) 85.72(10) C(49)-N(4)-Zn(1) 122.2(2) N(4)-Zn(1)-O(1) 174.11(10) C(50)-N(4)-Zn(1) 120.0(2) O(5)-Zn(1)-O(9) 85.99(10) C(55)-N(5)-C(57) 122.6(4) N(1)-Zn(1)-O(9) 87.43(10) C(55)-N(5)-C(56) 119.0(4) O(7)-Zn(1)-O(9) 166.84(13) C(57)-N(5)-C(56) 118.4(4) N(4)-Zn(1)-O(9) 91.18(12) C(7)-O(1)-Zn(1) 122.89(17) O(1)-Zn(1)-O(9) 82.96(11) C(18)-O(2)-Zn(2) 127.90(18) O(8)-Zn(2)-O(2) 120.96(10) C(33)-O(4)-Zn(2) 128.61(17) O(8)-Zn(2)-N(2) 102.63(11) C(44)-O(5)-Zn(1) 120.60(17) O(2)-Zn(2)-N(2) 86.84(9) C(53)-O(7)-Zn(1) 145.9(2) O(8)-Zn(2)-N(3) 94.53(11) C(53)-O(8)-Zn(2) 124.4(2) O(2)-Zn(2)-N(3) 144.22(10) C(55)-O(9)-Zn(1) 140.1(3) N(2)-Zn(2)-N(3) 89.79(10) N(1)-C(1)-C(2) 126.7(3) O(8)-Zn(2)-O(4) 97.54(10) C(7)-C(2)-C(3) 119.3(3) O(2)-Zn(2)-O(4) 85.46(8) C(7)-C(2)-C(1) 123.9(3) N(2)-Zn(2)-O(4) 159.58(10) C(3)-C(2)-C(1) 116.8(3) N(3)-Zn(2)-O(4) 85.49(9) C(4)-C(3)-C(2) 122.2(3) O(12)-Cl(1)-O(11) 119.2(4) C(3)-C(4)-C(5) 116.6(3) O(12)-Cl(1)-O(10) 112.2(5) C(3)-C(4)-C(8) 123.6(3) O(11)-Cl(1)-O(10) 109.8(3) C(5)-C(4)-C(8) 119.8(3) O(12)-Cl(1)-O(13) 102.4(6) C(6)-C(5)-C(4) 123.1(3) O(11)-Cl(1)-O(13) 107.9(4) C(5)-C(6)-C(7) 119.0(3) O(10)-Cl(1)-O(13) 103.7(5) C(5)-C(6)-C(12) 120.3(3) C(1)-N(1)-C(52) 117.1(3) C(7)-C(6)-C(12) 120.7(2) C(1)-N(1)-Zn(1) 124.9(2) O(1)-C(7)-C(6) 120.4(2) C(52)-N(1)-Zn(1) 117.98(19) O(1)-C(7)-C(2) 119.9(2) C(23)-N(2)-C(24) 116.5(3) C(6)-C(7)-C(2) 119.7(2) C(23)-N(2)-Zn(2) 125.6(2) C(10)-C(8)-C(11) 109.3(3) C(24)-N(2)-Zn(2) 117.3(2) C(10)-C(8)-C(4) 112.0(3) C(27)-N(3)-C(26) 115.9(3) C(11)-C(8)-C(4) 109.1(3) C(27)-N(3)-Zn(2) 127.0(2) C(10)-C(8)-C(9) 107.6(3) C(26)-N(3)-Zn(2) 116.9(2) C(11)-C(8)-C(9) 109.0(3) C(49)-N(4)-C(50) 117.4(3) C(4)-C(8)-C(9) 109.8(2)

144

Chapter 3 RESULTS AND DISCUSSION

C(6)-C(12)-C(13) 113.4(2) C(29)-C(30)-C(34) 121.6(3) C(14)-C(13)-C(18) 119.9(3) C(31)-C(30)-C(34) 122.2(3) C(14)-C(13)-C(12) 119.6(3) C(32)-C(31)-C(30) 123.2(3) C(18)-C(13)-C(12) 120.5(2) C(31)-C(32)-C(33) 119.5(3) C(13)-C(14)-C(15) 123.4(3) C(31)-C(32)-C(38) 118.8(3) C(16)-C(15)-C(14) 116.1(3) C(33)-C(32)-C(38) 121.7(3) C(16)-C(15)-C(19) 123.3(3) O(4)-C(33)-C(32) 120.8(2) C(14)-C(15)-C(19) 120.6(3) O(4)-C(33)-C(28) 119.9(3) C(15)-C(16)-C(17) 122.8(3) C(32)-C(33)-C(28) 119.3(3) C(16)-C(17)-C(18) 119.7(3) C(35)-C(34)-C(37) 113.3(7) C(16)-C(17)-C(23) 116.2(3) C(35)-C(34)-C(36) 110.4(6) C(18)-C(17)-C(23) 124.1(3) C(37)-C(34)-C(36) 101.9(6) O(2)-C(18)-C(13) 119.9(3) C(35)-C(34)-C(30) 110.1(3) O(2)-C(18)-C(17) 122.0(3) C(37)-C(34)-C(30) 111.2(4) C(13)-C(18)-C(17) 118.1(3) C(36)-C(34)-C(30) 109.6(3) C(21)-C(19)-C(22) 110.1(4) C(39)-C(38)-C(32) 113.5(2) C(21)-C(19)-C(15) 112.8(3) C(40)-C(39)-C(44) 119.6(3) C(22)-C(19)-C(15) 109.2(3) C(40)-C(39)-C(38) 120.4(3) C(21)-C(19)-C(20) 108.0(4) C(44)-C(39)-C(38) 119.9(2) C(22)-C(19)-C(20) 108.2(4) C(39)-C(40)-C(41) 122.9(3) C(15)-C(19)-C(20) 108.4(3) C(42)-C(41)-C(40) 116.7(3) N(2)-C(23)-C(17) 127.0(3) C(42)-C(41)-C(45) 120.0(3) N(2)-C(24)-C(25) 111.1(3) C(40)-C(41)-C(45) 123.3(3) O(3)-C(25)-C(26) 113.4(3) C(41)-C(42)-C(43) 122.3(3) O(3)-C(25)-C(24) 108.1(3) C(42)-C(43)-C(44) 119.7(3) C(26)-C(25)-C(24) 113.0(3) C(42)-C(43)-C(49) 116.8(3) N(3)-C(26)-C(25) 115.2(3) C(44)-C(43)-C(49) 123.4(3) N(3)-C(27)-C(28) 127.6(3) O(5)-C(44)-C(39) 119.8(3) C(29)-C(28)-C(33) 119.1(3) O(5)-C(44)-C(43) 121.5(3) C(29)-C(28)-C(27) 115.8(3) C(39)-C(44)-C(43) 118.7(3) C(33)-C(28)-C(27) 125.1(3) C(46)-C(45)-C(41) 109.5(3) C(30)-C(29)-C(28) 122.7(3) C(46)-C(45)-C(47) 108.7(3) C(29)-C(30)-C(31) 116.2(3) C(41)-C(45)-C(47) 110.0(3)

145

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C(46)-C(45)-C(48) 109.2(3) C(50)-C(51)-C(52) 114.9(3) C(41)-C(45)-C(48) 111.4(3) N(1)-C(52)-C(51) 113.1(3) C(47)-C(45)-C(48) 108.0(3) O(7)-C(53)-O(8) 124.5(3) N(4)-C(49)-C(43) 126.3(3) O(7)-C(53)-C(54) 117.9(4) N(4)-C(50)-C(51) 112.6(3) O(8)-C(53)-C(54) 117.6(3) O(6)-C(51)-C(50) 111.3(3) O(9)-C(55)-N(5) 124.6(5) O(6)-C(51)-C(52) 111.3(3)

Table-3.27 Hydrogen bonds for synthesized dizinc complex [Å and °] ______D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ______O(3)-H(3)...O(11) 0.84 2.16 2.992(6) 170.6 ______

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3.31 Conclusions Ligand, which was synthesized in this research work, is 1, 4, 7, 10, 13, 16- Hexaoxacyclooctadecane commonly called as 18-Crown-6 ether. This ligand was synthesized by the reaction of Triethylene glycol and 1, 2-bis (2-chloroethoxy) ethane and was purified by making acetonitrile complex. This ligand was used to make complexes with Ni(II), Cu(II) and Zn(II). My research also contains the synthesis of macrocycle based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol](H2mftbp) and 1, 3-diamino-2-propanol, a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) and 1, 4-diaminobutane, a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol](H2mftbp) and 1, 2-bis-[2-aminoethoxy]ethane, a macrocycle based on 2,

2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol](H2mftbp) was prepared by the oxidation of 2,2–methylene-bis-[(6-hydroxymethyl)-4-tert-butylphenol](H2mhtbp).

UV studies of 18-Crown-6 ether and its copper complex showed that λ max of ligand increases after making complex with metal ions. In IR studies, C-H, C-O, C-C, peaks appeared in their respective regions. So the presence of these bonds is confirmed. The qualitative and quantitative estimation of metals present in complexes was done by Atomic Absorption Spectroscopy. Stability of 18-Crown-6 ether and its complex with Copper was studied by using UV and TGA techniques and found stable in solid as well as in solution form over the whole period. Single X-Ray spectroscopic study was done of various synthesized novel ligands and complexes. 1 In H NMR of synthesized macrocyclic ligands, the peak [ppm] = 11.12

147

Chapter 3 RESULTS AND DISCUSSION disappears and a new peaks at [ppm]= 8.1 to 8.3 confirm the formation of imine bond by Schiff-base condensation reaction. In IR spectra, peak at ν [cm-1]= 1660 (s, C=O) disappears and new peak at ν [cm- 1] = 1600 to 1630 appears to ensure the formation of imine bond (-C=N-).

Double template effects in condensation of H2mftbp and diamines with metals was found to be not effected by changing dialdehydes, metal counter ions, base and diamines. For all the metal combinations investigated in this research are needed to distinguish between (4+4) and sandwich (2+2) species. Chemical kinetics of macrocyclic ligands for complex formation with metal ion depends on the following major factors;  Chelate effect  Macrocyclic effect  Coordination template effect  Effect of donor atoms on coordination bond formation  Soft and hard acid and base theory (SHAB)  Effect of guest cation on coordination bond formation  Template synthesis and transmetallation reactions

148

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3.32 Further Work Achieving a good quality crystals of complexes would allow examination of bond lengths to investigate possible delocalization of electrons in macrocyclic ligands which might be redox non-innocent. Also electrochemical methods could be employed to investigate the oxidation state of Cu(II) ions and lingand in complex. In case of good coordinating ligand such as chloride, copper produces only dinuclear complex. So CuCl2 should be investigated in condensation between H2mftbp and diamines in stoichiometries promoting synthesis of tri- and tetracopper(II) complexes to see if the chloride ions will prevent their formation. A minor change of diamines showed that a [MM*(4+4)]+2 complex could be achieved via [MM*(mftbp)]+2 in double template process. However, experiments with two metal system and diamines of different lengths should be investigated. This could result in a wider range of heteropolynuclear complexes and also would establish broader application of the mechanis. Finally, toxicity issues must be studied for each type of complex if they are to be used as pharmaceutical ingredients. The stability of the complexes must also be studied in different conditions (acidic, basic, aqueous etc.).

149

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179 D. H. Cook, D. E. Fenton, M. G. B. Drew, A. Rodgers, M. McCann, S. M. Nelson, J. Chem. Soc., Dalton Trans., 414-419 (1979) 180 S. M. Nelson, C. V. Knox, M. McCann, M. G. B. Drew, J. Chem. Soc., Dalton Trans., 1669-1677 (1981)

181 M. G. B. Drew, A. Rodgers, M. McCann, S. M. Nelson, J. Chem. Soc., Chem. Commun., 415-416 (1978)

182 V. McKee, J. Smith, J. Chem. Soc., Chem. Commun., 1465-1467 (1983) 183 G. W. Liesegang and E. M. Eyring in ― Synthetic multi-dentate compounds‖, R. M. Izatt, J. J. Christensen, Eds., Chap, 5, Academic Press, New York, (1978) 184 R. M. Izatt, J. S. Bradshaw, S. A. N. Elsen, J. D. Lamb, J. J. Christensen, Chem. Rev., 85, 271 (1985) 185 E. Shchori, J. Jagur-Grodzinski, M. Shporer, J. Am. Chem. Soc., 95, 3842 (1973) 186 M. shporer, Z. Luz, J. Am. Chem. Soc., 97, 665 (1975) 187 E. Schmidt, A. I. Popov, J. Am. Chem. Soc., 105, 1873 (1982) 188 B. O. Strasser, K. Hallenga, A. I. Popov, J. Am. Chem. Soc., 107, 789 (1985) 189 G. W. Liesegang, M. M. Farrow, N. Purdie, E. M. Eyring, J. Am. Chem. Soc., 98, 6905 (1976) 190 C. C. Chen, S. Petrucci, J. Phys. Chem., 86, 2601 (1982) 191 C. C. Chen, W. Wallace, E. M. Eyring, S. Petrucci J. Phys. Chem., 88, 2541 (1984) 192 W. Wallace, E. M. Eyring, S. Petrucci J. Phys. Chem., 88, 6353 (1984) 159

Chapter 4 REFERENCES

193 K. J. Maynard, D. E. Irish, E. M. Eyring, S. Petrucci J. Phys. Chem., 88, 729 (1984) 194 L. J. Rodriguez, G. W. Liesegang, M. M. Farrow, N. Purdie, E. M. Eyring, J. Phys. Chem., 82, 647 (1978) 195 Bruker, 1998, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA

196 G. M. Sheldrick, Acta Cryst., A64, 112-122 (2008)

197 I. J. Bruno, J. C. Cole, P. R. Edgington, M. Kessler, C. F. Macrae, P. McCabe, J. Pearson, R. Taylor, Acta Cryst., B58, 389-397 (2002)

198 L.J. Farrugia, J. Appl. Cryst., 30, 565-566 (1997)

199 Persistence of Vision Pty. Ltd. 2004, Persistence of Vision (TM) Raytracer, Persistence of Vision Pty. Ltd., Williamstown, Victoria, Australia, http://www.povray.org/

160

Appendix -I

(ESI-MS Spectra)

161

APPENDIX-I ESI-MS SPECTRA

Scan-5.1 MS-Scan of Lead complex based on 2, 2-methylene-bis[(6-formyl)-4-tert- butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

Scan-5.2 MS-Scan of Lanthanum and Copper complex based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

162

APPENDIX-I ESI-MS SPECTRA

Scan-5.3 MS-Scan of Barium and Copper complex based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

Scan-5.4 MS-Scan of Barium and Zinc complex based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane 163

APPENDIX-I ESI-MS SPECTRA

Scan-5.5 MS-Scan of Lanthanum and Nickel complex based on 2, 2-methylene- bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

Scan-5.6 MS-Scan of Calcium and Nickel complex based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

164

APPENDIX-I ESI-MS SPECTRA

Scan-5.7 MS-Scan of Calcium and Zinc complex based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

Scan-5.8 MS-Scan of Calcium complex based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and 1, 2-bis-[2-aminoethoxy]ethane

165

APPENDIX-I ESI-MS SPECTRA

Scan-5.9 MS-Scan of Barium and Nickel complex based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and triethylene tetramine

Scan-5.10 MS-Scan of Barium and Nickel complex based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and diethylenetriamine 166

APPENDIX-I ESI-MS SPECTRA

Scan-5.11 MS-Scan of Calcium complex based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and diethylenetriamine

Scan-5.12 MS-Scan of Copper complex based on 2, 2-methylene-bis[(6-formyl)-4- tert-butylphenol] and diethylenetriamine

167

APPENDIX-I ESI-MS SPECTRA

Scan-5.13 MS-Scan of Barium and Zinc complex based on 2, 2-methylene-bis[(6- formyl)-4-tert-butylphenol] and diethylenetriamine

168

Appendix -II

( -Spectra) IR

169

APPENDIX-II IR SPECTRA

7.7 7.5

582.56cm-1 7.0 555.79cm-1

6.5 564.62cm-1 547.16cm-1

6.0 590.97cm-1

467.11cm-1 5.5 688.82cm-1

5.0 662.20cm-1 608.93cm-1

4.5 2066.22cm-1 617.86cm-1

600.02cm-1 %T 4.0 2396.06cm-1 653.20cm-1 3.5 635.45cm-1 626.65cm-1

3.0 644.42cm-1

529.11cm-1 2.5 1763.20cm-1 475.98cm-1

2.0 1634.76cm-1 826.67cm-1 511.05cm-1 2915.03cm-1 1396.59cm-1 538.18cm-1

1.5 3379.34cm-1 1096.72cm-1961.84cm-1 520.00cm-1502.40cm-1493.57cm-1484.90cm-1 573.78cm-1458.66cm-1 1253.41cm-1 1.0 0.9 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description 18-C-Ni Sample 002 By Analyst Date Monday, September 24 2012 Scan-6.1 IR-Scan of Ni-18-crown-6 complex

3.1 3.0

2.8

2.6

2.4

2.2

2.0 960.82cm-1 1.8 2236.72cm-1

1.6

%T 1.4

1.2 1470.45cm-1 1.0 1352.98cm-1 0.8

0.6

0.4 983.61cm-1 499.30cm-1 457.93cm-1 629.00cm-1 0.2 1083.50cm-1 1619.24cm-1 755.92cm-1 540.74cm-1 3236.20cm-1 568.27cm-1 0.0 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description 18-C-Zn Sample 003 By Analyst Date Monday, September 24 2012 Scan-6.2 IR-Scan of Zn-18-crown-6 complex

170

APPENDIX-II IR SPECTRA

63 60

708.61cm-1 45 936.05cm-1 871.69cm-1

40 771.87cm-1 533.97cm-1 35

833.97cm-1

%T 30

3468.64cm-1 20 1362.18cm-1 1124.24cm-1 1392.01cm-1 15 1216.94cm-1 2864.48cm-1 1329.38cm-1 2903.67cm-1 1268.90cm-1 10 1542.24cm-1

2953.10cm-1 5 1445.44cm-1 1621.81cm-1

1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-1 Sample 007 By Analyst Date Wednesday, June 13 2012 Scan-6.3 IR Scan of a hetro-nuclear complex of Lead and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane

834.63cm-1 %T 35 1121.46cm-1 1216.87cm-1 478.29cm-1 30 1268.76cm-1

20 2954.49cm-1 1541.68cm-1

15 1444.12cm-1

3413.30cm-1 1620.24cm-1 1384.65cm-1 10 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-7 Sample 001 By Analyst Date Wednesday, June 13 2012 Scan-6.4 IR scan of a hetro-nuclear complex of Lanthanum and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis- [2-aminoethoxy] ethane

171

APPENDIX-II IR SPECTRA

55 834.35cm-1

45 1216.86cm-1

1361.74cm-1 1268.01cm-1 %T 40 1330.33cm-1 1120.88cm-1 1542.03cm-1 35 2953.71cm-1

1445.65cm-1

25 3435.85cm-1

1621.33cm-1 15 14 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-9 Sample 001 By Analyst Date Wednesday, June 13 2012 Scan-6.5 IR scan of a hetro-nuclear complex of Barium and Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis- [2-aminoethoxy]ethane

60 1750.51cm-1

803.37cm-1 50 755.06cm-1

926.58cm-1 771.98cm-1

40 829.63cm-1 534.90cm-1 624.65cm-1

693.56cm-1 %T

30 3447.89cm-1

2866.96cm-1 1212.27cm-1 20 1316.81cm-1 1362.16cm-1

1265.48cm-1 857.36cm-1 2957.40cm-1 1546.78cm-1 10 1107.78cm-1

1619.33cm-1 1446.87cm-1 0 -2 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-13 Sample 002 By Analyst Date Friday, July 20 2012 Scan-6.6 IR Scan of a hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane

172

APPENDIX-II IR SPECTRA

25 %T

10 920.65cm-1

1220.07cm-1 799.49cm-1 5 2868.61cm-1 1630.98cm-1 1269.19cm-1 749.84cm-1 531.35cm-1 3435.90cm-1 1458.80cm-1 1089.83cm-1 769.17cm-1 1387.00cm-1 831.49cm-1 0 2955.09cm-1 1243.88cm-1 625.48cm-1 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-15 Sample 002 By Analyst Date Friday, July 20 2012 Scan-6.7 IR Scan of a hetro-nuclear complex of Lanthanum and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis- [2-aminoethoxy]ethane

63 60

830.28cm-1 %T 30 1216.58cm-1

25 866.13cm-1 1269.75cm-1

2955.35cm-1 10 626.65cm-1 1145.24cm-1 1628.28cm-1 5 3400.95cm-1 1458.88cm-1 1114.76cm-1 1087.42cm-1 1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-17 Sample 002 By Analyst Date Friday, July 20 2012 Scan-6.8 IR Scan of a hetro-nuclear complex of Calcium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis- [2-aminoethoxy]ethane 173

APPENDIX-II IR SPECTRA

35 803.00cm-1 903.31cm-1 703.05cm-1 30 927.43cm-1 3662.39cm-1 754.99cm-1 %T 875.99cm-1 25 772.13cm-1 1235.56cm-1 20 829.94cm-1 534.61cm-1 506.31cm-1 624.67cm-1 472.64cm-1 15

3420.04cm-1 2866.62cm-1 10 1362.19cm-1 1211.54cm-1 1317.03cm-1 5 1546.70cm-1 2957.03cm-1 1448.35cm-1 1619.00cm-1 1265.48cm-1 0 1393.46cm-1 1107.38cm-1 -1 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-19 Sample 002 By Analyst Date Friday, July 20 2012 Scan-6.9 IR Scan of a hetro-nuclear complex of Calcium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane

42 40

849.80cm-1

20 702.30cm-1 %T

2958.88cm-1

15 1119.75cm-1 1083.41cm-1 628.57cm-1 10 870.31cm-1

5 3401.07cm-1

1465.75cm-1

-0 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-5_1 Sample 001 By Analyst Date Wednesday, June 13 2012 Scan-6.10 IR Scan of a heomo-nuclear complex of Calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 2-bis-[2- aminoethoxy]ethane

174

APPENDIX-II IR SPECTRA

68 65

814.53cm-1 35 693.26cm-1

858.20cm-1 %T

30 626.22cm-1

25 1115.38cm-1 1086.05cm-1 20

3400.78cm-1 10

1574.63cm-1 5 1427.17cm-1

0 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-22 Sample 002 By Analyst Date Friday, August 24 2012 Scan-6.11 IR Scan of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and triethylene tetramine

50 1213.55cm-1 1267.70cm-1 856.83cm-1 45 1147.05cm-1

40 %T

1086.81cm-1 35 1119.66cm-1 626.19cm-1

30 2958.66cm-1

25 1625.20cm-1

15 3435.91cm-1 1454.92cm-1 12 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-2 Sample 001 By Analyst Date Wednesday, June 13 2012 Scan-6.12 IR Scan study of a hetro-nuclear complex of Barium and Nickel with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine 175

APPENDIX-II IR SPECTRA

1121.70cm-1 35 1077.73cm-1 823.55cm-1

30 1221.62cm-1

%T 626.17cm-1 25 1274.61cm-1 870.76cm-1

20 2957.60cm-1

3401.15cm-1 1633.36cm-1 10

5 1467.15cm-1

2 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-4 Sample 002 By Analyst Date Wednesday, June 13 2012 Scan-6.13 IR Scan of a homo-nuclear complex of Calcium with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

62 60

35 1267.12cm-1 %T

30 1114.84cm-1 626.75cm-1 1089.23cm-1 25 2957.47cm-1

1417.81cm-1 15

10 1620.08cm-1 3435.63cm-1

5 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-8 Sample 001 By Analyst Date Wednesday, June 13 2012 Scan-6.14 IR Scan of a homo-nuclear complex of Copper with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

176

APPENDIX-II IR SPECTRA

67 65

50 2450.99cm-1

35 1751.04cm-1

%T 30

25 625.28cm-1

2955.24cm-1 15 1088.04cm-1 693.38cm-1 517.62cm-1

10 3401.15cm-1

5 1463.50cm-1 1634.37cm-1 1429.00cm-1 1442.00cm-1 857.45cm-1 0 1570.81cm-1 -2 4000 3500 3000 2500 2000 1500 1000 500450 cm-1 Name Description CE-12 Sample 002 By Analyst Date Friday, July 20 2012 Scan-6.15 IR Scan of a hetro-nuclear complex of Barium and Zinc with a macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and diethylenetriamine

177

Appendix -III

(Conferences and Publications)

178

APPENDIX-III CONFERENCES AND PUBLICATIONS

LIST OF CONFERENCES ATTENDED 1. RSC Dalton 2012 Meeting, University of Warwick, UK, 3-5April 2012 2. Chemistry Research Day, Department of Chemistry, Loughborough University, Loughborough, UK, 25 April 2012 3. A Celebration of Inorganic Chemistry, School of Chemistry, University of Nottingham, UK, 01 June 2012 4. 40th International Conference on Coordination Chemistry, Conference Centre in Valencia, Spain, 09-13 Sept 2012

LIST OF PUBLICATIONS 1 IMDAD HUSSAIN, RUBINA GILLANI, ZILLE HUMA, MUHAMMET KOSE, HABIB HUSSAIN, ZULFIQAR ALI; Templated Self-Assembly and Crystal Structure of Methyl Pamoate and its Polynuclear Clusters With Nickel(II) and Barium(II); Asian Journal of Chemistry (Submitted 2015)

2 IMDAD HUSSAIN, RUBINA GILLANI, VICKIE MCKEE, MUHAMMET KOSE, ZULFIQAR ALI, HABIB HUSSAIN; Synthesis, Characterization and X-Ray Crystal Structure of DiZinc(II) complex of Pseudocalixarene macrocycle based on 2, 2-methylene-bis[(6-formyl)-4-tert-butylphenol] and 1, 3-diamino-2-propanol; Asian Journal of Chemistry; Vol. 27, No. 7 (2015), 2630-2634

3 IMDAD HUSSAIN, RUBINA GILLANI, VICKIE MCKEE, HABIB HUSSAIN and ZULFIQAR ALI; Synthesis, Characterization and X-Ray Crystal Structure of Macrocyclic Ligand Based on 2,2-Methylene-bis[(6- formyl)-4-tert-butylphenol] and 1,2-bis-(2-aminoethoxy)ethane; Asian Journal of Chemistry; Vol. 26, No. 18 (2014), 6202-6206

4 IMDAD HUSSAIN, RUBINA GILLANI, VICKIE MCKEE, HABIB HUSSAIN and ZULFIQAR ALI; Synthesis, Characterization and X-Ray Crystal Structure of Copper Complex with 18-Crown-6; Asian Journal of Chemistry; Vol. 26, No. 13 (2014), 3953-3957

5 HABIB HUSSAIN, SYEDA RUBINA GILANI, FARKHANDA JABEEN, ZULFIQAR ALI, HAJIRA REHMAN and IMDAD HUSSAIN; Synthesis

179

APPENDIX-III CONFERENCES AND PUBLICATIONS

and Antibacterial Activity of Zn(II) Schiff Base Complexes derived from 3- acetyl-2H-chromen-2-one; Asian Journal of Chemistry; Vol. 27, No. 9 (2015), 3440-3444

6 HABIB HUSSAIN, SYEDA RUBINA GILANI, ZULFIQAR ALI, HAJIRA REHMAN and IMDAD HUSSAIN; Synthesis and Characterization of Novel (E)-1-(Hexa-3,5-dien-1-yl)-4-methoxybenzene via Boronate Complex; Asian Journal of Chemistry; Vol. 26, No. 21 (2014), 7401-7403

7 HABIB HUSSAIN, SYEDA RUBINA GILANI, ZULFIQAR ALI and IMDAD HUSSAIN; Asymmetric Synthesis, Characterization and Stereoselectivity of Novel 1-{2-[(1R,2S)-2- (Chloromethyl)cyclopropyl]ethyl}-4-methoxybenzene via Boronate Complex; Asian Journal of Chemistry; Vol. 26, No. 8 (2014), 2437-2442

8 HABIB HUSSAIN, SYEDA RUBINA GILANI, ZULFIQAR ALI and IMDAD HUSSAIN; Effect of Increase in Steric Bulk of Aryl lithium on Stereoselectivity of Boronate Complexes; Asian Journal of Chemistry; Vol. 25, No. 17 (2013), 9965-9969

9 H. HUSSAIN, S. R. GILANI, Z. ALI and I. HUSSAIN; Synthesis and Characterization of Novel (E)-tert-butyl 7-(4-methoxyphenyl)-5-(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)hept-2-enoate and (E)-diethyl (6-(4- methoxyphenyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hex-1-en-1- yl)phosphonate; Application of Olefin Cross Metathesis; Pak. J. Chem. 3(4): 1-9, 2013

10 HABIB HUSSAIN, SYEDA RUBINA GILANI, ZULFIQAR ALI, HAJIRA REHMAN and IMDAD HUSSAIN; Syntheses of Imines, their Ni (II) Complexes and Study of Antibacterial Activity against various Bacterial Strains; Asian Journal of Chemistry; (Submitted)

11 ZULFIQAR ALI, SYEDA RUBINA GILANI, HABIB HUSSAIN, HAJIRA REHMAN and IMDAD HUSSAIN; Synthesis, characterization and study of antibacterial activity of bis [3-acetyl-2H-chromene-2-one] silver (IV); Asian Journal of Chemistry; (Submitted)

180

APPENDIX-III CONFERENCES AND PUBLICATIONS

12 ZULFIQAR ALI, MIRZA NAMAN KHALID, SYEDA RUBINA GILANI, HABIB HUSSAIN, HAJIRA REHMAN, IMDAD HUSSAIN AND AYESHA SADIQA; Synthesis and Antibacterial Activity of Coumarin and its Derivatives; Asian Journal of Chemistry; Vol. 27, No. 9 (2015), 3321-3324

13 ZULFIQAR ALI, SYEDA RUBINA GILANI, FARKHANDA JABEEN, HABIB HUSSAIN, HAJIRA REHMAN and IMDAD HUSSAIN; Investigation of Antibacterial Activity of Alanine and Phenylalanine Derived Weinreb Amides Against Different Bacterial Strains; Asian Journal of Chemistry; Vol. 26, No. 20 (2014), 7067-7068

14 ZULFIQAR ALI, SYEDA RUBINA GILANI, HABIB HUSSAIN and IMDAD HUSSAIN; Conversion of Alanine and Phenylalanine into Weinreb Amides by Using Different Protecting Groups; Asian Journal of Chemistry; Vol. 26, No. 20 (2014), 6733-6736

15 ZULFIQAR ALI, RUBINA GILANI, HABIB HUSSAIN, IMDAD HUSSAIN; Quantitative Determination of Deltamethrin in Milk, Blood and Urine of Domestic Animals; IOSR Journal of Applied Chemistry; Volume 5, Issue 1 (Jul. – Aug. 2013), PP 51-56

181