DOCSLIB.ORG

Synthesis, Characterization and Properties of Coordination

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis, Characterization and Properties of Coordination SYNTHESIS, CHARACTERIZATION AND PROPERTIES OF COORDINATION- AND LOW BAND GAP POLYMERS FOR POTENTIAL CATALYTIC AND PHOTOVOLTAIC APPLICATIONS BY CHRISTOPHER M. MACNEILL A Dissertation Submitted to the Graduate Faculty of WAKE FOREST UNIVERSITY GRADUATE SCHOOL OF ARTS AND SCIENCES in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Chemistry May 2011 Winston-Salem, North Carolina Approved by: Ronald E. Noftle, Ph. D., Advisor David L. Carroll, Ph. D., Chair Christa L. Colyer, Ph.D. Stephen B. King, Ph. D. Abdessadek Lachgar, Ph. D. ACKNOWLEDGEMENTS I would first like to acknowledge and extend my warmest regards and thanks to my advisor, Dr. Ronald E. Noftle, who has supported and guided me through my research over the past five years. I would like to give a special thanks to Dr. Cynthia S. Day for her patience and kindness while collecting my crystal structure data for the coordination polymers project. I was not the best crystal grower, but with her skills and help, I didn’t have to be. I also want to thank my committee members Dr. David L. Carroll, Dr. Abdessadek Lachgar and Dr. S. Bruce King for excellent discussions in all phases of my research, especially Dr. David L. Carroll and Dr. Robert C. Coffin for their mentoring with the organic solar cell project. I’d like to thank my fellow group members at the Wake Forest Center for Nanotechnology and Molecular Materials, especially Eric Peterson, Wanyi Nie, Gregory Smith and Chanitpa Khantha. I would like to acknowledge my current and former group members, Melissa Donaldson, Amy Marts, Alex MacIntosh, Eric Tainsh and Kasha Patel. Dr. Jianjun Zhang, and Sergio A. Gamboa for help with the coordination polymers project. I would also like to thank my fellow graduate students in the department of chemistry for making the past five years fun and enjoyable. For my parents, Michael and Karen MacNeill, and my sisters, Kerri and Molly, for supporting me always in whatever I endeavor. Without them, I wouldn’t be the person I am today. The utmost thanks to my beautiful fiancée, Samantha Miller, who has stuck with me through thick and thin. She is the most generous and kind-hearted person I’ve had the chance to know and I love her with all my heart. ii TABLE OF CONTENTS Page Acknowledgements ii Table of Contents iii List of Figures ix List of Schemes xiii List of Equations xiii List of Tables xiv Abbreviations xv Abstract xvii Chapter 1. Introduction to 1 1.1. Coordination Polymers 1 1.1.1. Coordination Chemistry 1 1.1.2. Coordination Polymers 2 1.2. Tuning Pore Size and Functionality 3 1.3. Gas Adsorption Properties of Coordination Polymers 6 1.3.1. Carbon Dioxide Gas 6 1.3.2. Hydrogen Gas 7 1.4. Luminescent Properties of Coordination Polymers 8 1.4.1. Luminescence 8 1.4.2. Luminescence of Coordination Polymers 9 1.4.3. Luminescence of Lanthanide-based Coordination Polymers 9 iii 1.5. Catalytic Properties of Coordination Polymers 10 1.5.1. Zeolites vs. Coordination Polymers 10 1.5.2. Catalytic Sites in Coordination Polymers 11 1.5.3. Catalytic Reactions using Coordination Polymers 12 1.5.3.1. Cyanosilylation of Aldehydes 12 1.5.3.2. The Biginelli Reaction 14 1.5.3.3. Knoevenagel Condensation 15 1.6. Research Goal 17 2. Experimental 18 2.1. Materials 18 2.2. Methods 19 2.2.1. Analytical Methods 19 2.2.2. X-ray Diffraction Methods 19 2.3. Synthesis 20 2.3.1. Solvothermal Method 20 2.3.2. Reflux Method 22 2.3.3. Vapor Diffusion Method 23 2.3.4. Catalytic Experiments 25 2.3.4.1. Heterogeneous Catalysts 25 2.3.4.2. Homogeneous Catalysts 27 3. Synthesis, Crystal Structure and Properties of Coordination Polymers 1-4 28 3.1. Synthesis of Coordination Polymers 1-4 29 iv 3.2. Single Crystal X-ray Diffraction 29 3.2.1. Crystal structure of La2(2,5-TDC)3(DMF)2H2O . DMF (1) 29 3.2.2. Crystal structure of Gd2(2,5-TDC)3(DMF)2H2O (2) 32 3.2.3. Crystal structure of Eu4(C6H2O4S)6(H2O)2(DMF)3 (H2O/n-prOH) (3) 35 3.2.4. Crystal structure of Y(2,5-TDC)(DMF)2(NO3) (4) 37 3.3. Thermogravimetric Analysis 38 3.4. Infrared Spectroscopy 39 3.5. Solid State Photoluminescence 42 3.6. Catalytic Properties 43 3.7. Conclusion 46 4. Synthesis, Crystal Structure and Properties of Coordination Polymers 5-9 48 4.1. Synthesis of Coordination Polymers 5-9 49 4.2. Single Crystal X-ray Diffraction 50 4.2.1. Crystal Structure of Tb2(F4BDC)3(DEF)2EtOH2 . 2(DEF) (5) 50 4.2.2. Crystal Structure of Gd2(F4BDC)3(DEF)2EtOH2 . 2(DEF) (6), Eu2(F4BDC)3-(DEF)2EtOH2 . 2(DEF) (7), La2(F4BDC)3-(DEF)2EtOH2 . 2(DEF) (8) and Nd2(F4BDC)3-(DEF)2EtOH2 . 2(DEF) (9) 53 4.3. Thermogravimetric Analysis 53 4.4. Infrared Spectroscopy 54 v 4.5. Solid State Photoluminescence 55 4.6. Catalytic Properties 57 4.7. Conclusion 59 5. Introduction to 61 5.1. The Environment 61 5.2. History of Photovoltaics 62 5.2.1. The Photoelectric Effect 62 5.2.2. Inorganic Photovoltaics 62 5.2.3. Organic Photovoltaics 64 5.3. Theory and Device Physics of Organic Solar Cells 65 5.3.1. Open Circuit Voltage 66 5.3.2. Short Circuit Current 67 5.3.3. Fill Factor 67 5.4. Device Architectures of Organic Solar Cells 69 5.5. Critical Parameters of Organic Solar Cells 70 5.6. Research Goal 73 6. Experimental 75 6.1 Materials 75 6.2. Methods 75 6.2.1. Analytical Methods 75 6.2.2. Electrochemical Methods 76 6.2.3. X-ray Diffraction Methods 76 6.2.4. Photovoltaic Methods 77 vi 6.3. Synthesis 78 7. Synthesis, Characterization and Photovoltaic Properties of P1-P3 87 7.1. Synthesis of Polymers P1-P3 88 7.2. Thermogravimetric Analysis of P1-P3 91 7.3. UV-Visible Spectroscopy of P1-P3 92 7.4. Electrochemistry of P1-P3 92 7.5. X-ray Powder Diffraction of P1-P3 94 7.6. Photovoltaic Properties of P1-P3 95 7.7. Conclusion 97 8. Synthesis, Characterization and Photovoltaic Properties of P4-P11 99 8.1. Synthesis of Polymers P4-P11 100 8.2. Thermogravimetric Analysis of P7-P11 103 8.3. UV-Visible Spectroscopy of P7-P11 104 8.4. Electrochemistry of P7-P11 105 8.5. X-ray Powder Diffraction of P7-P11 106 8.6. Photovoltaic Properties of P7-P11 108 8.7. Solvent Additive Processing of Polymer P11 110 8.8. Conclusion 113 9. Synthesis, Characterization and Photovoltaic Properties of P12-P14 115 9.1. Synthesis of Polymers P12-P14 116 9.2. Thermogravimetric Analysis of P12-P14 117 9.3. UV-Visible Spectroscopy of P12-P14 118 vii 9.4. Electrochemistry of P12-P14 119 9.5. X-ray Powder Diffraction of P12-P14 120 9.6. Photovoltaic Properties of P12-P13 122 9.7. Conclusion 124 Conclusions 126 Future Work 129 References 131 Appendix A 154 Appendix B 221 Publishing Permission and License 231 Scholastic Vitae 256 viii List of Figures Page Figure 1: Examples of coordination polymers with different dimensionalities. 2 Figure 2: The molecular building block (MBB) approach to coordination polymers. Adapted from James.51 4 Figure 3: Organic linkers based on geometry for use in the synthesis of coordination polymers. 5 Figure 4: Coordination environment around (a) La3+(1) and (b) La3+(2) ion. 30 Figure 5: (a) The La(1)-La(2) dimer formed by four bridging TDC2- linkages. (b) A chain formed through linking of dimers from coordination polymer 1 shown down the a-axis. The La environment is shown as teal polyhedra, O (red), C (grey), S (yellow). 31 Figure 6: A perspective view of coordination polymer 1 along the a-axis with solvent molecules omitted for clarity. 32 Figure 7: The coordination environments around (a) Gd3+(1) and (b) Gd3+(2) ion. 33 Figure 8: (a) The Gd(1)-Gd(1) dimer formed by four bridging TDC2- linkages. b) The Gd(2)-Gd(2) dimer formed by four bridging TDC2- linkages. c) A chain formed through the linking of dimers 1 and 2 down the a-axis for coordination polymer 2. The Gd environment is shown as blue polyhedra. 34 Figure 9: The coordination environments around the (a) Eu3+(1) ion and (b) Eu3+(2) ion. 35 Figure 10: (a) The asymmetric unit of Eu(1) and Eu(2) (pink) linked by two TDC2- (bridging) linkages along with eight TDC2- linkages (all monodentate), two DMF molecules and one H2O molecule (bridging) forming Eu4(2,5-TDC)6(DMF)3(H2O)2(H2O/n-prOH) (3). (b) A chain formed through the linking of dimers in (a) of coordination polymer 3 down the a-axis. Carboxylates are shown in red. 36 ix Figure 11: (a) A representation of the environment around the yttrium ion in coordination polymer 4 along the crystallographic ab-plane. b) A view of coordination polymer 4 along the crystallographic a-axis. 37 Figure 12: The TGA curves of coordination polymers 1-4. 38 Figure 13: The infrared spectra of coordination polymer 1 at room temperature (RT) and after heating to 380oC (compound 1a). 40 Figure 14: X-ray powder diffraction spectra comparing the room temperature pattern to the patterns at 380oC and 900oC of coordination polymer 1. 41 Figure 15: (a) Excitation (inset) and emission spectra of coordination polymer 3 excited at 390 nm.
Load more

Recommended publications
  • Synthesis, X-Ray Structure and Properties of a Calcium(II) Coordination Polymer Showing Μ2-Η :Η and Μ3-Η :Η Coordination M
    Ms. Ref. No.: POLY-D-08-00248 (REVISED PAPER) Published in Polyhedron: 27(15); 2008; 3299-3305 Synthesis, X-ray structure and properties of a 1 1 calcium(II) coordination polymer showing µ2-η :η 2 1 and µ3-η :η coordination modes of 4-nitrobenzoate ∗ BIKSHANDARKOIL R SRINIVASAN , SANTOSH Y SHETGAONKAR, JYOTI V SAWANT, PALLEPOGU RAGHAVAIAH a Department of Chemistry, Goa University, Goa 403206 India email: [email protected] aPresent address: School of Chemistry, University of Hyderabad, Hyderabad, India 500 046 Abstract 1 2 The reaction of the monomeric compound [Ca(H 2O) 4(η -4-nba)( η -4-nba)] 1 (4-nba = 4-nitrobenzoate) with N-methylimidazole (N-MeIm) or imidazole (Im) at 100 oC results in the formation of the anhydrous mixed ligand complexes of composition [Ca(L)(4- nba) 2] (L=N-MeIm 2; L=Im 3). The compounds were characterized by elemental analysis, IR, UV-Vis and 1H NMR spectra, TG-DSC thermograms, weight loss studies and the structure of 2 was determined by single crystal X-ray crystallography. Compounds 2 and 3 can be transformed into 1 by heating with water. At elevated temperatures all compounds ( 1-3) are thermally decomposed to CaO. Compound 2 crystallizes in the centrosymmetric triclinic space group P ī with all atoms located in general positions. The structure reveals that 2 is a polymer and can be formulated as 1 1 2 1 catena -poly[[(N-methylimidazole)calcium(II)]( µ2-η :η -4-nitrobenzoato)( µ2-η :η -4- 1 1 2 1 nitrobenzoato)] . The structure of [[Ca(N-MeIm)]( µ2-η :η -4-nba)( µ3-η :η -4-nba)] n 2 2 consists of a central Ca(II) ion, a terminal N-MeIm ligand and two crystallographically independent 4-nba ligands.
    [Show full text]
  • Sonochemical Synthesis of Cadmium(II) Coordination Polymer Nanospheres As Precursor for Cadmium Oxide Nanoparticles
    crystals Article Sonochemical Synthesis of Cadmium(II) Coordination Polymer Nanospheres as Precursor for Cadmium Oxide Nanoparticles Farhad Akbari Afkhami 1 , Ali Akbar Khandar 1, Ghodrat Mahmoudi 2,* , Reza Abdollahi 3, Atash V. Gurbanov 4,5 and Alexander M. Kirillov 5,6,* 1 Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, 51666-16471 Tabriz, Iran; [email protected] (F.A.A.); [email protected] (A.A.K.) 2 Department of Chemistry, Faculty of Science, University of Maragheh, 55181-83111 Maragheh, Iran 3 Department of Physical Chemistry, Faculty of Chemistry, University of Tabriz, 51666-16471 Tabriz, Iran; [email protected] 4 Department of Organic Chemistry, Baku State University, Z. Khalilov str. 23, AZ 1148 Baku, Azerbaijan; [email protected] 5 Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal 6 Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya st., Moscow 117198, Russia * Correspondence: [email protected] (G.M.); [email protected] (A.M.K.) Received: 15 March 2019; Accepted: 2 April 2019; Published: 9 April 2019 Abstract: Nanospheres of a new coordination polymer {[Cd2(µ-HL)(µ-L)(NO3)3(H2O)]·H2O}n (1) were easily prepared by a sonochemical method from cadmium(II) nitrate and HL (HL, pyridine-2-carboxaldehyde isonicotinoyl hydrazone) in ethanol. Single crystals of 1 were also obtained using a branched tube method. The crystal structure of 1 indicates that the µ-HL/µ-L− blocks act as linkers between the Cd(II) centers, assembling them into 1D tooth-shaped interdigitated chains, which are further interlinked into a complex 3D H-bonded network with a rare hms (3,5-conn) topology.
    [Show full text]
  • Porous Coordination Polymers with Ubiquitous and Biocompatible Metals and a Neutral Bridging Ligand
    ARTICLE Received 30 Apr 2014 | Accepted 14 Nov 2014 | Published 16 Jan 2015 DOI: 10.1038/ncomms6851 OPEN Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand Shin-ichiro Noro1,2,3,4, Junya Mizutani2, Yuh Hijikata5, Ryotaro Matsuda3,6, Hiroshi Sato6, Susumu Kitagawa6, Kunihisa Sugimoto7, Yasutaka Inubushi8,w, Kazuya Kubo1,2 & Takayoshi Nakamura1,2 The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs. 1 Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan. 2 Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan. 3 PRESTO, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi 332-0012, Japan. 4 Creative Research Institute (CRIS), Hokkaido University, Sapporo 001-0021, Japan.
    [Show full text]
  • A Cd(II) Coordination Polymer Based on Mixed Ligands: Synthesis, Crystal Structure, and Properties
    crystals Article A Cd(II) Coordination Polymer Based on Mixed Ligands: Synthesis, Crystal Structure, and Properties Shuai-Shuai Han, Zi-Wei He, Lei Li and Shui-Sheng Chen * College of Chemistry and Chemical Engineering, Fuyang Normal University, Fuyang 236041, China; [email protected] (S.-S.H.); [email protected] (Z.-W.H.); [email protected] (L.L.) * Correspondence: [email protected] Received: 11 November 2019; Accepted: 25 November 2019; Published: 27 November 2019 Abstract: A new coordination polymer, namely, [Cd(L)(frda)(H O)] 0.5L H O(1) was synthesized 2 · · 2 by hydrothermal reaction based on mixed multi-N donor 1-(4-(1H-imidazol-5-yl) phenyl)-1H- 1,2,4-triazole (L) and O-donor 2,5-furandicarboxylic acid ligands (H frda) with CdCl 2.5H O. 2 2· 2 Compound 1 was characterized by single-crystal x-ray diffraction, elemental analysis, and IR 2 spectroscopy. In 1, both the multi-N donor and O-donor frda − ligands act as linear two-connectors to bridge Cd(II) atoms, forming a two-dimensional (2D) layer. Interestingly, the parallel 2D layers stack in an AAA mode, and the infinite one-dimensional (1D) channels formed along the a-axis ··· direction, where the uncoordinated L molecules were embedded in the void. Furthermore, the weak interactions including the rich hydrogen bonding and π π stacking interactions progress the 2D − structure into a three-dimensional (3D) supramolecular polymer. Diffuse reflectance spectra and the luminescent property were also investigated. Keywords: coordination polymer; characterization; optical property 1. Introduction Coordination polymers (CPs) consisting of organic ligands and metal ions have attracted an upsurge in research during the past decades, due to their charming structures and their possibly applied domain of luminescence [1–4], gas adsorption/separation [5,6], proton conductivity [7], chemical separations [8], catalysis [9], and so on.
    [Show full text]
  • Crown Ethers and Their Alkali Metal Ion Complexes As Assembler Groups in Uranyl–Organic Coordination Polymers With
    Crown Ethers and Their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis -1,3-, cis -1,2-, and trans -1,2-Cyclohexanedicarboxylates Pierre Thuéry, Youssef Atoini, Jack Harrowfield To cite this version: Pierre Thuéry, Youssef Atoini, Jack Harrowfield. Crown Ethers and Their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis -1,3-, cis -1,2-, and trans - 1,2-Cyclohexanedicarboxylates. Crystal Growth & Design, American Chemical Society, In press, 18 (5), pp.3167-3177. 10.1021/acs.cgd.8b00266. cea-01759418 HAL Id: cea-01759418 https://hal-cea.archives-ouvertes.fr/cea-01759418 Submitted on 6 Apr 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Crown Ethers and their Alkali Metal Ion Complexes as Assembler Groups in Uranyl–Organic Coordination Polymers with cis -1,3-, cis -1,2- and trans -1,2-Cyclohexanedicarboxylates Pierre Thuéry* ,† Youssef Atoini ‡ and Jack Harrowfield*,‡ †NIMBE, CEA, CNRS, Université Paris-Saclay, CEA Saclay, 91191 Gif-sur-Yvette, France ‡ISIS, Université de Strasbourg, 8 allée Gaspard Monge, 67083 Strasbourg, France ABSTRACT: Alkali metal cations (Na +, K +) and crown ether molecules (12C4, 15C5, 18C6) were used as additional reactants during the hydrothermal synthesis of uranyl ion complexes with cis /trans -1,3-, cis -1,2- and trans -1,2- cyclohexanedicarboxylic acids ( c/t-1,3-chdcH2, c-1,2-chdcH2 and t-1,2-chdcH2, respectively, the latter as racemic or pure (1 R,2 R) enantiomer).
    [Show full text]
  • Coordination Polymers, Metal-Organic Frameworks and the Need for Terminology Guidelines
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE Accepted manuscript: CrystEngComm, 2012,14, 3001-3004 provided by Chalmers Publication Library DOI: 10.1039/C2CE06488J, http://pubs.rsc.org/en/content/articlelanding/2012/ce/c2ce06488j Coordination Polymers, Metal-Organic Frameworks and the Need for Terminology Guidelines Stuart R. Battena, Neil R. Champnessb, Xiao-Ming Chenc, Javier Garcia-Martinezd, Susumu Kitagawae, Lars Öhrströmf*, Michael O’Keeffeg, Myunghyun Paik Suhh and Jan Reedijki,j Coordination Polymers (CP) and Metal-Organic Frameworks (MOF) are among the most prolific research areas of inorganic chemistry and crystal engineering in the last 15 years, and yet it still 5 seems that consensus is lacking about what they really are, or are not. Background Nomenclature and terminology should always create added value. They are tools to incorporate new results into the greater weave of science and enable us to go from the specific to the general. New terminology should also help us to constructively discuss new compounds, 10 materials and phenomena without having to proceed through endless preambles of definitions. When two or more sub-disciplines of science find themselves preparing and analysing similar kinds of new materials, an ad hoc terminology often develops from different viewpoints and may not naturally converge into a self-consistent and logical result. This dual situation occurs for Coordination Polymers (CP)1 and Metal-Organic Frameworks 2 15 (MOF) , compounds generated in interdisciplinary research fields with their origins in solid state, inorganic and coordination chemistry that have expanded rapidly during the last 15 years. The diversity in both focus and scientific basis of the researchers involved has lead to numerous terminology suggestions and practices for this class of compounds and of several subgroups within them;3 additionally, a disquieting number of acronyms are also in use for these materials.
    [Show full text]
  • One Dimensional Coordination Polymers Based on Bridging N,N Donor Ligands
    One Dimensional Coordination Polymers Based on Bridging N,N Donor Ligands Der Naturwissenschaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg zur Erlangung des Doktorgrades Dr. rer. nat. vorgelegt von Nico Fritsch aus Forchheim Als Dissertation genehmigt von der Naturwissen- schaftlichen Fakultät der Friedrich-Alexander-Universität Erlangen-Nürnberg Tag der mündlichen Prüfung: 13. Juni 2014 Vorsitzender des Promotionsorgans: Prof. Dr. Johannes Barth Gutachter: Prof. Dr. Nicolai Burzlaff Prof. Dr. Julien Bachmann Die vorliegende Arbeit entstand in der Zeit von Juni 2011 bis März 2014 im Department für Chemie und Pharmazie (Lehrstuhl für Anorganische und Metallorganische Chemie) der Friedrich-Alexander-Universität Erlangen-Nürnberg unter der Anleitung von Prof. Dr. Nicolai Burzlaff. Teile dieser Dissertation wurden bereits veröffentlicht: “trans-1,2-Bis(N-methylimidazol-2-yl)ethylene: Towards Building Blocks of 2D Fabrics and MML-Type 2D Molecular Strands”, N.V. Fischer, M. S. Alam, I. Jum´h, M. Stocker, N. Fritsch, V. Dremov, F.W. Heinemann, N. Burzlaff, P. Müller, Chem. – Eur. J., 2011, 17, 9293-9297. “Battlement-shaped 1D coordination polymer based on bis(N-methylimidazole-2yl)butadiyne ligand”, T. Waidmann, N. Fritsch, J. Tucher, M. Rudolf, F. Glaser, D.M. Guldi, N. Burzlaff, CrystEngComm, 2013, 10157-10160. – Reproduced by permission of The Royal Society of Chemistry. You can´t always get what you want. But if you try sometimes you might find, You get what you need. (Sir Mick Jagger) Table of contents 1! GENERAL INTRODUCTION ............................................................................................ 1! 1.1! From metal organic frameworks to 1D coordination polymers ........................................... 2! 1.2! Different concepts of molecular wires .................................................................................... 5! 1.2.1! Organic based molecular wires ..........................................................................................
    [Show full text]
  • A Supramolecular Coordination Polymer Derived Electrocatalyst for Oxygen Evolution Reaction
    A Supramolecular Coordination Polymer Derived Electrocatalyst for Oxygen Evolution Reaction Chi Zhang,a Chen Zhang,b Yunchao Xie,a Xiaoqing He,c Tommi White,c d Derek Demaree,e Mark H. Griep,e Jerry L Atwood*b and Jian Lin*a a. Department of Mechanical & Aerospace Engineering, University of Missouri, Columbia, Missouri 65211, United States. E- mail: [email protected] b. Department of Chemistry, University of Missouri, Columbia, Missouri 65211, United States. E-mail: [email protected] c. Electron Microscopy Core Facility, University of Missouri, Columbia, MO 65211, United States d. Department of Biochemistry, University of Missouri, Columbia, MO 65211, United States e. U.S. Army Research Laboratory, 4600 Deer Creek Loop, Aberdeen Proving Groun, Maryland 21005, United States An iron oxide decorated nickel iron alloy nanoparticle/porous graphene hybrid exhibits high electrocatalytic activity and excellent durability toward oxygen evolution reaction (OER). It displays a LOW overpotential of 274 mV at 10 mA/cm2, and low Tafel slope of 37 mV/dec, showing a superior performance to the state-of-the-art RuO2 OER electrcatalyts. Scanning electron microscopy (SEM) was performed to characterize the morphology and structure. Fig. 1b shows that the nanoparticles are well dispersed on the surface of the LIG sheets. The corresponding elemental mapping confirms the existence of the C, O, Fe, and Ni elements and their uniform dispersion. High-resolution TEM (HRTEM) was further performed to investigate the nanostructures in more details. The HRTEM image (Fig. 1d) reveals well-resolved lattice fringes with interplanar distances of 0.205 nm, 0.290 nm and 0.364 nm, of Fe3O4 and (002) plane of graphene, respectively.
    [Show full text]
  • Synthesis and Crystal Structure of a New Calcium-Containing Trimesate Coordination Polymer: [Ca3(Btc)2(H2O)12]∞
    Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]1. Magatte Camara, Carole Daiguebonne, Olivier Guillou, Albert Manga Badiane, Insa Badiane, Saïbatou Yague, Florence Le Dret To cite this version: Magatte Camara, Carole Daiguebonne, Olivier Guillou, Albert Manga Badiane, Insa Badiane, et al.. Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]1.. Journal de la Société Ouest-Africaine de Chimie, Société Ouest-Africaine de Chimie, 2013, 035, pp.57-63. hal-01074624 HAL Id: hal-01074624 https://hal.archives-ouvertes.fr/hal-01074624 Submitted on 15 Oct 2014 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Journal de la Société Ouest-Africaine de Chimie J. Soc. Ouest-Afr. Chim. Code Chemical Abstracts : JSOCF2 Cote INIST (CNRS France) : <27680> ISSN 0796-6687 18èmeAnnée, Juin 2013, N° 035 Site Web: http://www.soachim.org J. Soc. Ouest-Afr. Chim. (2013) 035 ; 57 - 63 Synthesis and crystal structure of a new calcium-containing trimesate coordination polymer: [Ca3(btc)2(H2O)12]∞. Magatte Camaraa*, Carole Daiguebonneb,c, Olivier Guilloub,c, Albert Manga Badianea, Insa Badianea, Saïbatou Yaguea, Florence Le Dretb,c.
    [Show full text]
  • Mossbauer Spectroscopic Studies of Complexes of Fe(III) with Nitrogen Containing Polymers
    Polymer Journal, Vol. 23, No. 4, pp 339~342 (1991) NOTES Mossbauer Spectroscopic Studies of Complexes of Fe(III) with Nitrogen Containing Polymers E. A. BEKTUROV, S. E. KUDAIBERGENOV, G. S. KANAPYANOVA, S. S. SALTYBAEVA, A. I. SKUSHNIKOVA, A. L. PAVLOVA, and E. S. DoMNINA * Institute of Chemical Science, Kazakh SSR Academy of Sciences, Alma-Ata 480100, Krasin Str. 106, USSR * Institute of Organic Chemistry Siberian Branch of Academy of Sciences of the USSR, Irkutsk, USSR (Received July 30, I 990) KEY WORDS Nitrogen Containing Polymers / Complex Formation / Mossbauer Spectroscopy / Coordination polymer compounds have EXPERIMENT AL been successfully used in various catalytic processes such as hydrogenation, oxidation, P2VPy, P2M5VPy, and P4VPy were synthe­ hydroformylation, polymerization, isomeriza­ sized by the radical polymerization of mono­ tion, etc. 1 Nitrogen containing polymers are mers in methanol at 333 K in presence of interesting polymer ligands that function as azobisisobutyronitrile (AIBN) as initiator. 8 supports in catalysis. Copolymers based on VI and VP were Complex formation ability of nitrogen synthesized by radical copolymerization in containing polymers in relation to the transi­ ethanol at 333 Kin the presence of AIBN. All tion metal ions is due to the presence of polymers and copolymers were purified by primary, secondary and tertiary aminogroups fractional precipitation. The compositions of which are able to form donor-acceptor copolymers were determined by IR spectros­ bonds. 2 - 7 The structures of coordination copy9 and by elemental analysis. PVI with compounds influence on the catalytic activity molecular weight 16 x l 03 and commercial of polymer-metal complexes. sample of PVP with molecular weight 5.6 x 10 5 In the present paper the results of an were used.
    [Show full text]
  • A New Calcium(II) Coordination Polymer Based on a Μ2-Bridging Tridentate 4-Nitrobenzoate
    Indian Journal of Chemistry Vol. 51A, March 2012, pp. 435-443 A new calcium(II) coordination polymer based on a µ2-bridging tridentate 4-nitrobenzoate Bikshandarkoil R Srinivasana, *, Santosh Y Shetgaonkara, Manav Saxenab & Christian Nätherc aDepartment of Chemistry, Goa University, Goa 403 206, India Email: [email protected] bDepartment of Chemistry, Indian Institute of Technology, Kanpur, 208 016 India cInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth Strasse 2, D-24118 Kiel, Germany Received 17 September 2011; revised and accepted 16 January 2012 Reaction of a heptacoordinated Ca(II) compound [Ca(H2O)4(4-nba)2] (4-nba = 4-nitrobenzoate) with 3,5-dimethyl- pyrazole (dmp) leads to the formation of an eight coordinated Ca(II) compound, [[Ca(H2O)2(4-nba)2]·2dmp]n, containing two coordinated water molecules, two unique 4-nba ligands and two free dmp molecules in the lattice. The µ2-bridging tridentate binding mode of the unique 4-nba ligands results in the formation of a one-dimensional (1-D) coordination polymer. The title compound exhibits enhanced fluorescence emission. An analysis of the six different bridging binding modes of the 4-nba ligand in twenty two different structurally characterized 4-nitrobenzoate compounds is described. Keywords: Coordination chemistry, Calcium, 4-Nitrobenzoates, 3,5-Dimethylpyrazole, Coordination polymers, Metal organic frameworks Coordination polymers (CPs) also known as metal differing dimensionalities can be constructed. For the organic frameworks (MOFs) have attracted much oxophilic s-block metals, carboxylic acids are useful attention because of their topology and applications in linkers for the construction of coordination polymers catalysis, adsorption (gas storage), separation and as the metals can be linked into an extended chain luminescence1-3.
    [Show full text]
  • Synthesis and Characterization of a New Strontium(II) Coordination Polymer Based on a Μ2-Tridentate Bridging Zwitterionic Glyci
    Published in: Journal of Coordination Chemistry: 64(13); 2011; 2274-2283. Synthesis and characterization of a new strontium(II) coordination polymer based on a µ2-tridentate bridging zwitterionic glycine aS. Natarajan *, aJ. Kalyana Sundar, bS. Athimoolam, cBikshandarkoil R. Srinivasan a *School of Physics, Madurai Kamaraj University, Madurai 625 021, India b Department of Physics, University College of Engineering Nagercoil, Anna University of Technology Tirunelveli, Nagercoil 629 004, India c Department of Chemistry, Goa University, Goa 403206, India Abstract The synthesis and characterization of a new Sr(II) coordination polymer [Sr(H 2O)(H- gly)2Cl2]n 1 (H-gly = glycine) is described. Compound 1 crystallizes in the centrosymmetric orthorhombic space group Pcnb and its structure consists of a central Sr(II) ion, a terminal water, a unique zwitterionic glycine and a chloride ion. The central metal is nine coordinated and is bonded to six oxygen atoms from four different bridging H-gly ligands, two symmetry related chloride ions and a terminal water. The µ2-tridentate bridging nature of the zwitterionic glycine results in the formation of a one dimensional coordination polymer with a Sr···Sr separation of 4.560 Å across the chain. The chloride, H-gly and the coordinated water are involved in five varieties of H-bonding interactions. A comparative study of the structural chemistry of several alkaline-earth glycine compounds is described. Keywords: Coordination polymer; strontium; glycine; zwitterion. 1 REVISED MANUSCRIPT GCOO-2011-0182 1. Introduction Coordination polymers (CPs) also known as metal organic frameworks (MOFs) have attracted much attention because of their topology and applications in catalysis, adsorption (gas storage), separation, luminescence [1-3].
    [Show full text]