Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2018 Redox and Coordination Chemistry DFrainfkfiee Dr. Wehniteces of the 4f and 5f Elements Follow this and additional works at the DigiNole: FSU's Digital Repository. For more information, please contact [email protected] FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES REDOX AND COORDINATION CHEMISTRY DIFFERENCES OF THE 4f AND 5f ELEMENTS By FRANKIE D. WHITE A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy 2018 Frankie D. White defended this dissertation on September 28, 2018. The members of the supervisory committee were: Thomas E. Albrecht-Schmitt Professor Directing Dissertation Samuel L. Tabor University Representative Kenneth G. Hanson Committee Member Yan-Yan Hu Committee Member The Graduate School has verified and approved the above-named committee members and certifies that the dissertation has been approved in accordance with university requirements. ii This work is dedicated to God, my parents, Frankie D. White Sr. and Pamella Potter White, my family, and supporting friends. I am extremely grateful for all the love and support you have given me and would not be here without you. iii ACKNOWLEDGMENTS First, I would like to thank God, who provided me with the abilities and gift to pursue my goals in life. Secondly, I would like to thank my parents. You two have provided me with everything that I ever needed. You continuously have placed me before yourselves in every aspect to make sure I was able to strive to be the best I could be. You constantly reminded me to keep my priorities in order. Thank you. To my sisters and brothers, Kia, Ty, Trey, and Calvin, thank you for all the love and support you have given me throughout all my academic years. I would also like to thank my friends Amanda, Elijah, and Jeff. You always supported my decisions to obtain a higher education. I tremendously thank my two academic mentors Dr. Richard Sykora and Dr. Thomas Albrecht-Schmitt. Dr. Sykora, I spent the first part half of my research years under you at the University of South Alabama. You were a large part of my decision to obtain a doctorate in chemistry and I am forever thankful for your presence in my life. Additionally, you introduced me to Tom, my current mentor who I also want to thank. Tom, you have had a substantial impact on my life and have always been supportive of me. You challenged me tremendously, but also had the same amount of faith in me. Thank you both. I would also like to thank all of the members of the Albrecht-Schmitt group that I had the pleasure of working. Samantha Cary, you got me started in the lab and had a major impact on my beginnings. I would also like to thank all of the following: Teresa Eaton, Shane Galley, Ali Arico, Kevin Seidler, Matt Marsh, Sasha Chemey, Wes Potter, David Dan, Alyssa Gaiser, Evan Warzecha, Ryan Greer, Joe Sperling, Carla McKinley Bonnie Klamm, David Meeker, Brian Long, Joanna Campbell, Vanessa Proust, Renaud Jeanine, Cory Windorff, and Ashini Jayasinghe. In addition to these research members, I would also like to thank the Alabugin group for constantly letting me borrow materials and the Hanson group for performing all my spectroscopic studies that I needed, especially Yan Zhou and Tristan Dilbeck. Lastly, I would like to thank Florida State University and my committee for extending my educational knowledge and for allowing me to be a graduate student and researcher in their facilities. I also would like to thank the Department of Energy Grant under the award number of DE-FG02-13ER16414 for providing the funding for my research. iv TABLE OF CONTENTS List of Tables ............................................................................................................................... viii List of Figures ..................................................................................................................................x Abstract ........................................................................................................................................ xiii 1. INTRODUCTION ......................................................................................................................1 1.1 History of f-elements............................................................................................................1 1.2 Problems in f-elements .........................................................................................................2 1.3 Chemistry of f-elements .......................................................................................................3 1.3.1 The Characteristics of 4f and 5f-elements .................................................................4 1.3.2 Trends in the f-elements ............................................................................................5 1.3.3 Dissertation Objectives .............................................................................................7 1.4 Figures..................................................................................................................................7 2. SYNTHESIS AND CHARACTERIZATION METHODS ......................................................10 2.1 Past and Current Methods for f-element Crystal Growth ..................................................10 2.2 Characterization Techniques ..............................................................................................10 2.2.1 Single Crystal X-ray Diffraction .............................................................................10 2.2.2 Spectroscopic Measurements ..................................................................................11 2.2.3 Computational Details .............................................................................................12 2.2.4 Electrochemical Studies ..........................................................................................12 2.2.5 Syntheses of Reactions ............................................................................................13 2.2.6 Recycling of 243Am and 249Cf .................................................................................13 2.3 Figures................................................................................................................................14 3. EXAMINATION OF STRUCTURE AND BONDING IN 10-COORDINATE EUROPIUM AND AMERICIUM TERPYRIDYL COMPLEXES ....................................................................15 3.1 Introduction ........................................................................................................................15 3.2 Results and Discussion ......................................................................................................17 3.2.1 Structural Characterization .......................................................................................17 3.2.2 Ionic Radii Calculations ............................................................................................19 3.2.3 Spectroscopic Measurements ....................................................................................20 3.2.4 Computational Analysis ............................................................................................21 3.3 Conclusion .........................................................................................................................21 3.4 Methods and Characterizations ..........................................................................................22 3.4.1 Syntheses .................................................................................................................22 3.4.2 Single Crystal X-ray Diffraction .............................................................................23 3.4.3 Computational Details .............................................................................................23 3.5 Figures................................................................................................................................24 v 4. STRUCTURAL, PHOTOPHYSICAL, AND ELECTROCHEMICAL INVESTIGATIONS OF F-ELEMENTS IN NON-AQUEOUS CONDITIONS ............................................................26 4.1 Introduction ........................................................................................................................26 4.2 Results and Discussion ......................................................................................................27 4.2.1 Structural Characterization .......................................................................................27 4.2.2 Spectroscopic Studies ...............................................................................................28 4.2.3 Electrochemical Studies ............................................................................................29 4.3 Conclusion .........................................................................................................................30 4.4 Methods and Characterization ...........................................................................................31 4.4.1 Syntheses...................................................................................................................31 4.4.2 Single Crystal Crystallography .................................................................................32 4.4.3 Spectroscopic Studies ...............................................................................................32