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Design and Characterization of Metal-Thiocyanate Coordination Polymers

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Design and Characterization of Metal-Thiocyanate Coordination Polymers Design and characterization of metal-thiocyanate coordination polymers by Didier Savard M.Sc., University of Ottawa, 2010 Thesis Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in the Department of Chemistry Faculty of Science Didier Savard 2018 SIMON FRASER UNIVERSITY Spring 2018 Approval Name: Didier Savard Degree: Doctor of Philosophy Title: Design and characterization of metal-thiocyanate coordination polymers Examining Committee: Chair: Hua-Zhong Yu Professor Daniel B. Leznoff Senior Supervisor Professor Tim Storr Supervisor Associate Professor Zuo-Guang Ye Supervisor Professor Jeffrey J. Warren Internal Examiner Assistant Professor Prof. Mark M. Turnbull External Examiner Professor Carlson School of Chemistry Clark University Date Defended/Approved: January 12, 2018 ii Abstract This thesis focuses on exploring the synthesis and chemical reactivity of thiocyanate- y- based building blocks of the type [M(SCN)x] for the synthesis of coordination polymers. A series of potassium, ammonium, and tetraalkylammonium metal isothiocyanate salts of the type Qy[M(SCN)x] were synthesized and structurally characterized. Most of the salts were revealed to be isostructural and classic Werner complexes, but for (Et4N)3[Fe(NCS)6] and (n-Bu4N)3[Fe(NCS)6], a solid-state size-dependent change in colour from red to green was observed. This phenomenon was attributed to a Brillouin light scattering effect by analyzing the UV-Visible spectra of various samples with different sized crystals. Coordination polymers of the type [M(L)x][Pt(SCN)4] were prepared and structurally characterized using a variety of bi- or tri-dentate capping ligands (ethylenediamine, 2,2’- bipyridine, 2,2';6',2"-terpyridine, N,N,N′,N′-Tetramethylethane-1,2-diamine). Overall, structural correlations between the ligand, the metal centre, the coordinating mode of the 2- [Pt(SCN)4] building block and the topologies of the coordination polymers were established. Similar systems were synthesized using the ligands N,N’- bis(methylpyridine)ethane-1,2-diamine (bmpeda) and N,N’- bis(methylpyridine)cyclohexane-1,2-diamine (bmpchda) and were revealed to be multidimensional coordination polymers by structural analysis. Five complexes of the type [Cu2(μ-OH)2(L)2][A]x·yH2O (where L = 1,10-Phenanthroline, tmeda and 2,2’-bipyridine) were prepared and have been characterized by spectroscopic and crystallographic structural analyzes and by SQUID magnetometry. Two complexes were revealed to be dinuclear molecular units capped with the SCN- ligand. The - complexes involving the [Au(CN)4] anion were structurally characterized as double salts involving the dinuclear Cu(II) unit with a varying degree of hydration. The complex [Cu2(μ-OH)2(tmeda)2Pt(SCN)4] was revealed to be a 1D coordination polymer with trans- 2- bridging [Pt(SCN)4] units. The magnetic susceptibility versus temperature was measured and fitted for each system to obtain J-coupling values that were qualitatively compared to the previously published magnetostructural correlation for dinuclear hydroxide-bridged units. The birefringence and luminescent properties for four new complexes of the type [Pb(4’-R-terpy)(SCN)2] were measured. The complexes presented unique luminescence based on the presence of the SCN- unit, whereas the birefringence - of the complexes was compared to [Au(CN)2] analogues and was correlated to the structural properties of the system. iii Dedication For my grandfather, Gilles iv Acknowledgements I would first like to thank my supervisor, Prof. Daniel B. Leznoff for his teachings, his understanding and insights, his enthusiasm about this work and his support throughout the years. I would like to thank the members of my supervisory committee, Prof. Zuo-Guang Ye and Prof. Tim Storr for guiding me through my research, for encouraging me to persevere through the hardships and for providing wisdom over the years. I would like to specifically thank Prof. Tim Storr for teaching me about DFT calculations. I would like to thank Dr. Jeffrey J. Warren and Prof. Mark M. Turnbull for taking to the time carefully read my thesis and for their comments and corrections. I would also like to thank Prof. Ken Sakai from Kyushu University and Mr. Masayuki 2- Kobayashi for their previous work on [Pt(SCN)4] complexes, Prof. Vance E. Williams for his insight on Brillouin Light Scattering, Prof. Christian Réber for his advice and analysis on FTIR and Raman spectroscopic data, Dr. Michael J. Katz for his teachings on solving X-ray structures and for his work on birefringence, Mr. Frank Haftbaradaran and Mr. Paul Mulyk for their help with elemental analyses, Dr. Jeffrey S. Ovens for his insights on X-ray crystallography and birefringence, Dr. John K. Thompson for his teachings for birefringence measurements, Dr. Ryan J. Roberts for his help on luminescence and uv- visible spectroscopy, Dr. Cassandra Hayes for her insights on air-sensitive chemistry and for being a good friend and Mr. Ian Johnston for his hard work and a great summer work term. I would also like to thank the Natural Science and Engineering Council, the government of British Columbia, Simon Fraser University and Natural Resources of Canada (ARG) for research funding. I also thank Westgrid and Compute Canada. v Table of Contents Approval .......................................................................................................................... ii Abstract .......................................................................................................................... iii Dedication ...................................................................................................................... iv Acknowledgements ......................................................................................................... v Table of Contents ........................................................................................................... vi List of Tables .................................................................................................................. ix List of Figures................................................................................................................. xi List of Abbreviations ..................................................................................................... xvii Chapter 1. Introduction ............................................................................................. 1 1.1. Coordination polymers ............................................................................................ 1 - 1.2. The chemistry of the (iso)thiocyanate (SCN ) ligand ............................................... 6 1.3. Thiocyanates and their usage in CPs ..................................................................... 8 1.4. Research Objectives ............................................................................................ 11 1.5. Synthesis, characterization methods and optical properties .................................. 12 1.5.1. General synthetic approach to synthesis of CPs. ..................................... 12 1.5.2. X-ray crystallography ............................................................................... 13 1.5.3. Vibrational spectroscopy .......................................................................... 13 1.5.4. Luminescence ......................................................................................... 14 1.5.5. Birefringence ........................................................................................... 15 Chapter 2. Synthesis, structure and light scattering properties of metal isothiocyanate salts .............................................................................. 16 2.1. Introduction ........................................................................................................... 16 2.2. Syntheses ............................................................................................................. 19 2.3. Vibrational Spectroscopy ...................................................................................... 22 2.4. Structural Analyses ............................................................................................... 25 2.4.1. Chromium(III) salts .................................................................................. 25 2.4.2. Manganese(II) salts ................................................................................. 31 2.4.3. Iron(III) salts ............................................................................................ 36 2.4.4. Cobalt(II) salts ......................................................................................... 37 2.4.5. Nickel(II) salts .......................................................................................... 37 2.4.6. Lanthanide salts ...................................................................................... 38 2.4.7. Discussion of the crystallographic data .................................................... 40 + + + 2.5. Light Scattering of Q3[Fe(NCS)6] (Q = Me4N (2.11), Et4N (2.12), Bu4N (2.13)). .................................................................................................................. 41 2.6. Discussion ............................................................................................................ 45 2.6.1. Challenges in crystallization and purification ............................................ 45 2.7. Using first-row transition metal cations for the synthesis of coordination polymers
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