University of Missouri, St. Louis IRL @ UMSL Dissertations UMSL Graduate Works 7-21-2017 Cadmium Chloride Dimensionality Changes From Ortho-Substituted Anilines Stephanie Cernicek University of Missouri-St. Louis, [email protected] Follow this and additional works at: https://irl.umsl.edu/dissertation Part of the Inorganic Chemistry Commons Recommended Citation Cernicek, Stephanie, "Cadmium Chloride Dimensionality Changes From Ortho-Substituted Anilines" (2017). Dissertations. 668. https://irl.umsl.edu/dissertation/668 This Dissertation is brought to you for free and open access by the UMSL Graduate Works at IRL @ UMSL. It has been accepted for inclusion in Dissertations by an authorized administrator of IRL @ UMSL. For more information, please contact [email protected]. Cadmium Chloride Dimensionality Changes From Ortho-Substituted Anilines By Stephanie R. Cernicek B.S., Chemistry, University of Missouri Saint Louis M.S., Chemistry, University of Missouri Saint Louis A DISSERTATION Submitted to the Graduate School of the UNIVERSITY OF MISSOURI- ST. LOUIS In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY In CHEMISTRY With an Emphasis in Inorganic Chemistry August 2017 Advisory Committee Dr. Alicia M. Beatty Chairperson Dr. George Gokel Dr. Stephen Holmes Dr. Janet Braddock-Wilking Abstract Cadmium Chloride Dimensionality Changes From Ortho-Substituted Anilines (August 2017) Stephanie R. Cernicek B.S., Chemistry, University of Missouri Saint Louis M.S., Chemistry, University of Missouri Saint Louis Chair of Committee: Dr. Alicia M. Beatty Inorganic-organic hybrid metal halide materials have been of great interest recently due to the useful properties offered by such a combination. The inorganic 2- portions usually consisting of MX6 subunits, (M = Pb, Sn, Cd, Cu; X = Cl, Br, I) most often form 2-D perovskite layers where the metals are bridged by corner sharing halides. The organic portion, usually consisting of primary amines or anilines provides a template for the inorganic framework and in some cases, dictates the dimensionality (2-D, 1-D, 0- D) of the network. These materials have various applications in host-guest chemistry catalysis, and gas storage, or as superconductors or quantum dots. It has been established by the Beatty group that it is possible to alter the metal halide assembly by changing the size of the substituent ortho to an aniline/amine group. Cadmium chloride complexes can be transformed from 2-D to 0-D based on the size of the substituent ortho to the nitrogen on a dianilinium complex. When the substituent in the ortho position is small (H) a perovskite layer is formed (Cd-Cl distance 2.4-2.7 Å). If 2- the substituent is changed to a methyl group the [CdCl6] layer expands (Cd-Cl distance 3.14-3.87 Å). If the group is changed to a larger ethyl group, the steric bulkiness of the group causes the layer to collapse into a hexameric cluster with Cd-Cl distances that are slightly shorter than that of the expanded layer while still being longer than that of a normal perovskite layer (2.8-3.04 Å). To determine if this phenomenon occurs generally, we have used metal halides such as CdX2 and CuX2 (where X = Cl, Br, I) with a number of ortho-substituted anilines and dianilines (ortho = H, Cl, CH3, CH2CH3, CH(CH3)2, C(CH3)3, C6H5). i Dedication This dissertation is dedicated to my husband Scott, and my son Elias. Their love and support have pushed me to complete this degree. ii Acknowledgements I would like to acknowledge Dr. Alicia Beatty who served as my advisor during my undergraduate and graduate research. She has helped me on countless research projects and course work through out the years to ensure I got the most out of my time at UMSL. She has also provided funding and research projects during my undergraduate and graduate education. UMSL has also been indespensible in providing funding and a setting for me to complete my undergraduate and graduate research. I would also like to thank my committee members Dr. George Gokel, Dr. Janet Braddock-Wilking, and Dr. Stephen Holmes. Not only has every single committee member served as a teacher to me during my time here, they have each helped to increase my knowledge and understanding of chemistry. They have provided council to me during my graduate degree that I find invaluable. Dr. Nigam Rath is also quite deserving of my acknolwdgement. He allowed me to shadow him as a teaching assistant and gain a deep understanding of X-ray crystallography. He took the time to explain every aspect of crystallography and ensure that I understood it. Finally, I would like to acknowledge my family and the countless hours they’ve spent helping me though out my long journey at UMSL. iii Table of Contents Abstract………………………………………………………………………………........i Dedication……………………………………………………………………...………....ii Acknowledgements…………….………………………………………………………..iii Table of Contents………………………………………………………………......……iv Table of Figures…………………………………………………………………...….....vi Table of Schemes………………………………………………………………...……….x Table of Tables………………………………………………………………....……......xi Chapter 1: Introduction…………………………………………………………..……..1 1.1 Overview of Research Goals…………………………………………………...…2 1.2 Supramolecular Chemistry…………………………………………….…………..3 1.3 Crystal Engineering……………………………………………...………………..5 1.4 Overview of Steric Effects…………………………………….…………………..7 1.5 Steric Effects in Organic Chemistry………………………………………………8 1.6 Steric Effects in Organometallic Chemistry………………………………………9 1.7 Steric Effects in Inorganic Chemistry…………………………….……………...11 1.8 Perovskite Structures……………………………………………….……………11 1.9 Conclusions…………………………………………………………..…………..13 1.10 References…………………………………………………………..……………14 Chapter 2: Monoanilinium Complexes……………..…………………..……………..17 2. 1 Introduction ………………………………………………..………………….….…18 2.2 Experimental…………………………………………………………………………33 2.2.1 Synthesis …………………………………………………………..………33 2.2.2 X-Ray Crystallography ……………………………………………………35 2.3 Results……………………………………………………………………...………...38 2.4 Discussion……………………………………………………..…………………..…61 2.4.1 Known Cadmium Halide Structures…………………...……………..........61 2.4.2 Crystal Structure Motifs and Metal:Halide:Nitrogen Ratio………………..70 2.4.3 Hydrophobic-to-Total Volume Ratio………………………………………77 2.4.4 Cone Angles………………………………………………………………..79 2.5 Conclusion…………………………………………………………….……………..82 2.6 References……………………………………………………………………………84 Chapter 3: Dianilnium Complexes……….…………………………………..………..88 3.1 Introduction ……………………………………………………………..…….……..89 iv 3.2 Experimental………………………………………………………..………………..91 3.2.1 Synthesis ……………………………………………….......….…………..91 3.2.2 X-Ray Crystallography …………………………………………..………..94 3.3 Results…………………………………………………………………...……….......95 3.4 Discussion……………………………………………………..……………..………99 3.4.1 Known Cadmium Halide Structures …………………...………………….99 3.4.2 Crystal Structure Motifs and Metal:Halide:Nitrogen Ratio ……………...104 3.4.3 Hydrophobic-to-Total Volume Ratio…………………………...………...107 3.4.4 Bond Distances and Cone Angles ……………………………………..…108 3.5 Conclusion………………………………………………………………...………..111 3.6 References……..……………………………………………………………………113 Chapter 4: Bromination of Starting Materials….………………………………..…115 4.1 Introduction ……………………………………………………………….….…….116 4.2 Experimental…………………………………………………………………… ..…118 4.2.1 X-Ray Crystallography ……………………………..…………………....118 4.3 Results……………………………………………………………...……………….1 25 4.4 Discussion……………………………………………………..……..…………..…133 4.5 Conclusion…………………………………………………………..….………..…134 4.6 References………………………………………………………………………..…136 Chapter 5: Chloride and Bromide Anilinium Salts…………………………………139 5.1 Introduction …………………………………………………………………...……140 5.2 Experimental……………………………………………………………………..…141 5.3 Results………………………………………………………...………………….....148 5.4 Discussion……………………………………………..………..………………..…159 5.5 Conclusion…………………………………………………………………….……160 5.6 References……………………………………………………………………..……161 Chapter 6: Conclusion………………………………………..…………………….…164 6.1 Conclusion ………………………………………………………..………….….…165 Appendix I: Crystal Structure Data……………………………………...…. ………..A1 Appendix II: CSD Data….….….….……….……………………………............…..A145 Appendix III: Calculations….….…….….….….....…………………………….…...A151 Appendix IV: Nuclear Magnetic Resonance Data….….…..….….….….…...….…A157 Appendix V: Mass Spectrometry Data….….….....….….….….….….…………….A167 v Table of Figures + 1.2.1. Plot of repeating [Ni(L)4(H2O)2]2 unit at 120 K ….……………....………………5 1.6.1 Common ligands and their binding preferences…………………………..….……10 1.6.2 A) Ni(II) square planer complex with ortho-methyl groups blocking in the z direction B) Ni(II) square planer complex which is vulnerable to attack in the z direction………………………………………………………………………………….11 1.8. Model of a 3-D AMX3 type perovskite unit cell……………………….…………....12 2.1.1 Drawings of the following topologies: spherical (s), columnar, (c), lamellar, (l), perforated layers (pl), and cubic bicontinuous (bi). ……...……….......…...19 2.1.2 Phase diagram for polystyrene(PS)-polyisoprene diblock copolymer as a function of PS-to-total volume ratio. ………………………………..……..…………....21 2.1.3 Crystal structures and hydrophobic-to-total volume ratios of the following CSD structures a )ORCPHA, b) LESKAV, c) NUFQUI, d) TEJHIZ.………….……………..23 2.1.4 Crystal structures and hydrophobic-to-total volume ratios of silver salts……..…..25 2.1.5. Model of a 2-D layer type perovskite structure. The left figure shows a + monoammonium (RNH3 ) cation while the right figure shows a diammonium + + ( NH3RNH3 ) cation……………………………………………………………………..26 2.1.6 A) bridging halide hydrogen bonding scheme B) terminal halide