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Syntheses of Enantiomerically Pure Chiral Hosts Using Amino Acid Derived Ligands with Fe(III), Ni(II) and Cu(II) Ions

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Syntheses of Enantiomerically Pure Chiral Hosts Using Amino Acid Derived Ligands with Fe(III), Ni(II) and Cu(II) Ions Syntheses of Enantiomerically Pure Chiral Hosts using Amino Acid Derived Ligands with Fe(III), Ni(II) and Cu(II) ions A Thesis Submitted In Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY By Md. Akhtarul Alam Department of Chemistry Indian Institute of Technology Guwahati Guwahati-781039 March, 2004 Dedicated to my parents TH-149_994501 i INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI Department of Chemistry STATEMENT I hereby declare that the matter embodied in this thesis is the result of investigations carried out by me in the Department of Chemistry, Indian Institute of Technology Guwahati, India under the supervision of Dr. Manabendra Ray Assistant Professor in Chemistry. In keeping with the general practice of reporting observations, due acknowledgements have been made wherever the work described is based on the findings of other investigators. I.I.T. Guwahati Md. Akhtarul Alam March, 2004 TH-149_994501 ii Dr. Manabendra Ray Assistant Professor INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI Department of Chemistry Tel. 91 361 2582310 E-mail: [email protected] Fax. 91 361 2690762 CERTIFICATE This is to certify that Mr. Md. Akhtarul Alam has been working under my supervision since August 2, 1999. I am forwarding his thesis entitled “Syntheses of Enantiomerically Pure Chiral Hosts using Amino Acid Derived Ligands with Fe(III), Ni(II) and Cu(II) ions” being submitted for the Ph.D. degree of this Institute. I certify that he has fulfilled all the requirements according to the rules of this Institute and regarding the investigations embodied in his thesis and work has not been submitted elsewhere for a degree. I.I.T. Guwahati Dr. Manabendra Ray March, 2004 Supervisor TH-149_994501 iii INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI Department of Chemistry COURSE CERTIFICATE This is to certify that Mr. Md. Akhtarul Alam has satisfactorily completed all the courses required for the Ph.D. degree programme. These courses include: CH 611 Bioinorganic Chemistry CH 631 Experimental Spectroscopy CH 620 Art in Organic Synthesis CH 630 A Fundamental Approach to Physical Chemistry Mr. Md. Akhtarul Alam has successfully completed his Ph. D. qualifying examination in February 2001. Dr. Jubaraj B. Baruah Dr. Anil Kumar Saikia Head Secretary Department of Chemistry Departmental Post Graduate Committee I.I.T. Guwahati Department of chemistry I.I.T. Guwahati TH-149_994501 iv INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI Department of Chemistry Ph.D. GRADE CARD Name: Md. Akhtarul Alam Department: Chemistry Roll No: 994501 Semester: July-November, 1999 Course Course Name Credit Grade CH 611 Bioinorganic Chemistry 6 AB CH 631 Experimental Spectroscopy 6 BB CH 620 Art in Organic Synthesis 6 AA CH 630 A Fundamental Approach to Physical Chemistry 6 BC Semester Performance Index (S.P.I): 8.50 Cumulative Performance Index (C.P.I): 8.50 I.I.T. Guwahati Assistant Registrar March, 2004 Academic TH-149_994501 Acknowledgements v Acknowledgements I convey my sincere sense of gratitude to my supervisor Dr. Manabendra Ray who has initiated me to the artistic science of inorganic chemistry and crystal engineering. His active leadership, priceless suggestions and invaluable support, revitalized my curiosity in the subject. His continuous imaginative initiatives and decisive insights assisted me to become skilled, both in the theoretical and practical aspects of my subject. As his first student, working with him was a great opportunity and delight for me. I express my sincere appreciation to Dr. M. Nethaji at Indian Institute of Science Bangalore, for his enormous help and tremendous patience in recording the data and solving the X-ray structure of all my crystals, without his help it would be impossible to proceed any further during my research work. I also thank to Prof. T. N. Guru Row, who first took the initiative for solving the crystal structure of my compounds. I would like to thank Prof. R. N. Mukherjee, who allowed me to perform the variable temperature magnetic susceptibility measurements and EPR studies reported in this thesis at his laboratory. His Ph. D. student V. Balamurugan was instrumental in recording the variable temperature magnetic susceptibility measurements at I.I.T. Kanpur. I wish to show my gratitude to Dr. P. K. Madhusudanan (CDRI, Lucknow) for 1H NMR, elemental analysis and optical rotation facilities made available to me. I am always indebted to Prof. Mihir K. Chaudhury for his tremendous input and encouragement throughout this tenure as the Head of my Doctoral Committee. My honest regards are due to all the faculty members of the department and fellow friends for their motivation and encouragement that guided me to this end. I convey my regards to Dr. Nikhil Gucchait for his encouragement. My parents and other family members were always behind me with their constant encouragement, inspiration and support. I specially thank to Rupa Sultana for her love, inspiration and support. I also thank my friend Tridib and Deepa di. The financial support from Council of Scientific and Industrial Research (CSIR), New Delhi [No. 9/731(28)/2003] is duly acknowledged. I thank Indian Institute of Technology, Guwahati for all the facilities that were made available to me and for the initial financial support. Md. Akhtarul Alam TH-149_994501 Abstract vi Abstract This thesis represents our attempt to synthesize enantiopure chiral cavities, with our exploration of the coordination chemistry of the amino acid derived chiral tetradentate ligands and three first row transition metal ions namely Fe(III), Ni(II) and Cu(II). In the process we have been successful in the synthesis and characterization of three chiral cavities of different size and shape, one porous 1D helical network and two structural models for metalloenzyme active sites. The thesis has been divided into seven chapters. Chapter wise summary of the work is presented below. Chapter I Introduction In this chapter we present the importance of research works and recent developments related to the technologically potent area involving the synthesis of enantiomerically pure chiral host and their applications. Recognition of chiral molecule by a host is an important area of research having applications in chiral separation, enantiopure drug synthesis, stereospecific synthesis of organic molecules and in the domain of chiral sensors. A diverse set of approaches in the design and functioning of hosts have been reported in the recent literature ranging from rigid and bulky organic molecules changing color with one enantiomer having preferred binding of the enantiomer inside chiral nanoporous channels to chirally modified polymers changing frequency of a coated crystal with one enantiomer. Recognition of a molecule, chiral or achiral, inside a molecular cavity working as a host has been pursued intensely in the last three decades. Within the last few years witnessed synthesis of several synthetically challenging, architecturally beautiful molecular cup, bowl, and capsule shaped guest molecules. Literature survey showed that a majority of these have been synthesized in multi-step processes and most of them are achiral and thus a major requirement for chiral recognition is missing. TH-149_994501 Abstract vii The objective of this thesis has been set to synthesize multinuclear enantiopure transition metal complexes with available binding sites inside a cavity. The advantage of using a metal complex stems from the fact that the metal ion gives the conformational rigidity to the otherwise flexible organic ligand. Chapter II Ligand Synthesis In this chapter we present the experimental conditions for the synthesis of polydentate ligands with potential to form enantiomerically pure chiral complexes. We have chosen the relatively less explored amino acid derived reduced Schiff base ligands. The reason is that the natural amino acids are available in pure enantiomeric form rather cheaply. In addition, the ligand was designed to have several possible H-bond formation sites to assist in assembling multinuclear assembly through H-bonding. Figure 1. The histidine-derived ligand (S-H2Salhis) Chapter III Synthesis and solution properties of a self-assembled molecular capsule with copper (II) complex This chapter contains the synthesis and characterization of an octameric Cu(II) complex with the formula [Cu8(S-Salhis)8Py10].Py.3MeOH.(C2H5)2O. The crystal structure showed that eight CuL units form a capsular cavity that traps four pyridine molecules. In this capsular cavity top to bottom distance was about 13.6 Å and across the TH-149_994501 Abstract viii Figure 2. Capsular structure of the octameric Cu(II) complex cavity was about 10.0 Å. To understand the stability of the capsule in different chemical environments, we further studied the characteristics of the complex using a combination of spectroscopic methods and recrystallization techniques in various solvents. We observed the assembly and disassembly of the capsule in different solvent medium and using external ligands. These experimental results suggest that the capsular complex synthesized has potential for use as storage (holding a guest inside the capsule) and delivery agent (either solvent or imidazole mediated) for trapped guest molecules. Chapter IV Synthesis and characterization of a 1D chiral microporous channels with a Fe(III) complex and insertion of iodine inside the channels This chapter contains the synthesis and characterization of a dinuclear iron(III) complex [Fe 2(ì-OH)(ì-OAc)(S-Salhis)2].4H2O. Crystal structure of the complex showed the formation of one-dimensional (1D) helical channels with diameter of 7-9 Å in the crystal lattice. The channels are filled with water molecules. These water molecules are H-bonded with the bridging hydroxo group and the ligand carboxylate oxygen. The usability of the channels as hosts has been ascertained by removing water from the channel thermally and filled the evacuated channels with iodine. Structural characterization of the empty crystals and the iodine filled channels showed that the iodine molecules inside the channels were organized in a helical array similar to those of water molecules inside the channels.
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