University of Kentucky UKnowledge Theses and Dissertations--Chemistry Chemistry 2017 INTERACTIONS OF COMPOUNDS CONTAINING GROUP 12 AND 16 ELEMENTS Daniel Burriss University of Kentucky, [email protected] Author ORCID Identifier: https://orcid.org/0000-0003-1579-204X Digital Object Identifier: https://doi.org/10.13023/ETD.2017.457 Right click to open a feedback form in a new tab to let us know how this document benefits ou.y Recommended Citation Burriss, Daniel, "INTERACTIONS OF COMPOUNDS CONTAINING GROUP 12 AND 16 ELEMENTS" (2017). Theses and Dissertations--Chemistry. 89. https://uknowledge.uky.edu/chemistry_etds/89 This Doctoral Dissertation is brought to you for free and open access by the Chemistry at UKnowledge. It has been accepted for inclusion in Theses and Dissertations--Chemistry by an authorized administrator of UKnowledge. For more information, please contact [email protected]. STUDENT AGREEMENT: I represent that my thesis or dissertation and abstract are my original work. 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Daniel Burriss, Student Dr. David Atwood, Major Professor Dr. Mark Lovell, Director of Graduate Studies INTERACTIONS OF COMPOUNDS CONTAINING GROUP 12 AND 16 ELEMENTS _____________________________ DISSERTATION _____________________________ A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the College of Arts and Sciences at the University of Kentucky By Daniel Burriss Lexington, Kentucky Director: Dr. David Atwood, Professor of Chemistry Lexington, Kentucky 2017 Copyright © Daniel Burriss 2017 ABSTRACT OF DISSERTATION INTERACTIONS OF COMPOUNDS CONTAINING GROUP 12 AND 16 ELEMENTS The focus of this dissertation is on the interactions of compounds containing group 12 and 16 elements. This work is presented in three major parts. First, the interaction of the synthetic dithiol N,N’-bis(2-mercaptoethyl)isophthalamide), abbreviated BDTH2, with selenite. Second, the interaction of cysteine with Cd(II) and the biologically relevant Cd-Cysteine crystal structure. Third, the green synthesis of CdSe quantum dots (QDs). The interaction of BDTH2 with selenite is different from the interactions with other metals and metalloids previously studied. Under ambient conditions, BDTH2 is oxidized to the disulfide, BDT(S-S), while selenite is reduced to elemental selenium. However, under carefully controlled conditions, the reaction of BDTH2 with selenite produces a mixture of BDT(S-S) and the covalently bound Se(II) species, BDT(S-Se-S). While the mixture could not be separated, experimental 77Se NMR combined with computational analysis confirmed the presence of BDT(S-Se-S). The interaction of the amino acid cysteine with Cd(II) was studied as a means to sequester, and potentially recycle, Cd(II) from bulk CdS waste. Single crystals of Cd(Cys)Cl·H2O were grown, and the crystal structure determined. Surprisingly, this is only the second structure to be determined by X-ray crystallography of a compound containing the Cd-Cysteine unit. Not only does this structure have biological relevance, but it also corrects a structure proposed in 1965. Using the knowledge gained from studying the interaction of BDTH2 with selenite, a green synthesis of water-soluble CdSe QDs by the reaction of selenite with Cd(Cys)Cl·H2O in water at room temperature was developed. This green method for the synthesis of CdSe QDs was extended to ZnSe and HgSe QDs. The mechanism of CdSe formation was investigated using Cd(II) combined with various thiols. KEYWORDS: Thiols, Selenium, Cadmium, Quantum Dots, X-ray Crystallography Daniel Burriss Date: 11/28/17 INTERACTIONS OF COMPOUNDS CONTAINING GROUP 12 AND 16 ELEMENTS By Daniel Burriss Dr. David Atwood Director of Dissertation Dr. Mark Lovell Director of Graduate Studies Date: 11/28/17 To the late R. A. Dandl ACKNOWLEDGMENTS I would like to thank my parents, Cathy and Gary Burriss, not only for their continued support throughout the PhD process, but also for raising me to be the person I am today. I would not be where I am today without their support, discipline, and understanding. They have always been there to lend a listening ear and suggestions, which I relied on several times throughout this process. I would like to also thank my brother, Nathan Burriss, for being a positive role model. His drive in his academic journey has pushed me to continue with mine. Words cannot express my deepest gratitude to my advisor, Dr. David Atwood, for giving me this opportunity. He has been supportive and offered constructive criticism throughout the PhD process. I appreciate the amount of independence he allowed me to have in his lab and giving me the opportunity to take on projects that I found interesting, which I feel led to some great discoveries. While he did allow me to have a lot of independence, he always kept me on track and was available to address any concerns I had. Every time I thought something had reached a dead end, he was there to suggest an alternate route or different way to approach the problem. I would like to thank my committee members, Dr. Beth Guiton and Dr. Robert Lodder, for offering their guidance, suggestions, and corrections during my committee meetings. I would like to give special thanks to Dr. John Selegue for agreeing to join my committee to fill a vacancy created during the final leg of my PhD. I would like to thank Dr. Qiou Wei for serving as my outside examiner during my PhD defense. Some key findings in my research would not have been possible without the assistance of John Layton and Dr. Sean Parkin. I would like to thank John Layton for all his help with everything NMR related, but his help with 77Se NMR provided data that allowed me to complete a publication. I cannot thank Dr. Sean Parkin enough for lending his expertise in X-ray crystallography. Even though 95% of the crystals I brought him were sodium chloride or another unwanted product, he continued to solve crystal structures for me, which eventually led to a structure that was pivotal to my research. Last but not least, I would like to extend my thanks to my extended family, lab mates, and friends. You all know who you are. This would not have been possible without all of your support. iii TABLE OF CONTENTS ACKNOWLEDGMENTS ......................................................................................................... iii LIST OF TABLES .................................................................................................................... vi LIST OF SCHEMES ............................................................................................................... vii LIST OF FIGURES ................................................................................................................ viii LIST OF ABBREVIATIONS AND SYMBOLS .............................................................................. x Chapter 1 Introduction ....................................................................................................... 1 1.1. Introduction .......................................................................................................................... 1 1.2. Cadmium ............................................................................................................................... 1 1.3. Selenium ............................................................................................................................... 7 1.4. Quantum Dots ..................................................................................................................... 14 1.5. Overview of Research Conducted ....................................................................................... 19 Chapter 2 Interaction of Selenium with Synthetic Dithiol ................................................ 23 2.1. Introduction ........................................................................................................................ 23 2.2. Experimental ....................................................................................................................... 28 2.3. Results and Discussion .......................................................................................................