Synthetic, Physical, and Photolytic Properties of Linear, Branched, and Cyclic Oligogermanes
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SYNTHETIC, PHYSICAL, AND PHOTOLYTIC PROPERTIES OF LINEAR, BRANCHED, AND CYCLIC OLIGOGERMANES By SANGEETHA P. KOMANDURI Bachelor of Science in Specialized Chemistry University of Illinois at Urbana-Champaign Urbana-Champaign, Illinois 2013 Submitted to the Faculty of the Graduate College of the Oklahoma State University in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY July, 2018 SYNTHETIC, PHYSICAL, AND PHOTOLYTIC PROPERTIES OF LINEAR AND CYCLIC OLIGOGERMANES Dissertation Approved: Dr. Charles S. Weinert Dissertation Adviser Dr. Allen W. Apblett Dr. Richard A. Bunce Dr. Toby L. Nelson Dr. John N. Veenstra ii ACKNOWLEDGEMENTS This work is dedicated to the many people who have supported and helped me during my time as a graduate student. First and foremost, I’d like to thank my committee members Dr. Bunce, Dr. Apblett, Dr. Nelson, and Dr. Veenstra for their assistance and the knowledge they have imparted onto me over the years. In addition to their help in the classroom, their advice has been vital. Of course the biggest influence on my time here has been my research advisor Dr. Weinert. He has provided me with the mentorship and practical knowledge which I have used daily in and outside of the lab. None of this work could have been completed without his valuable guidance and consistent help, all which has molded me into an independent researcher. Within the laboratory and the chemistry department at OSU, my colleges, friends, and staff members have given me great support during the technical aspects of my research. My lab mates Alex Shumaker, Miguel Leal, and Ardalan Hayatifar are the research family who encouraged, taught, and gave me the structural criticism to push me further and improve my skills. Along with my fellow colleges I’d also like to thank former students Kimberly Roewe, Aaron Schrick, Evangeline Renuko, Wes Honeycutt, Eric Butson, Claire Spice, Chen, and Heather Storm who have aided me both mentally and technically throughout this process. In addition to my lab mates in the states, I would also like to give my appreciation to our collaborators in Graz, Austria. My gratitude to Melanie Wolf, Beate Steller, Micheal Traxler, Astrid Falk, Ana Torvisco, Elli Schwarz, Judith Biedermann, and others at Graz Technical University who gave advice, company, and stimulating conversations on a regular basis. I’m also very grateful to Dr. Frank Uhlig for providing me the unique opportunity to study and work in his laboratories. Finally, I’d like to give thanks to my parents and family who have been by my side and assisted me to achieve more. Their constant reinforcement during the challenges has given me the motivation to pursue my PhD and has bolstered my drive. I’d like to partially dedicate this work to my late father, who has always instilled the value of hard work in any task I undertake. My mother, on the other hand, has been my rock all throughout my studies. Her continued love and support have been immeasurable, and without either of them I would not be where I am today. I am sincerely thankful for my family, both academic and personal, who have helped me along this journey to accomplish my goals now and in the future. iii Acknowledgements reflect the views of the author and are not endorsed by committee members or Oklahoma State University. Name: SANGEETHA P. KOMANDURI Date of Degree: JULY, 2018 Title of Study: SYNTHETIC, PHYSICAL, AND PHOTOLYTIC PROPERTIES OF LINEAR, BRANCHED, AND CYCLIC OLIGOGERMANES Major Field: CHEMISTRY Abstract: The following dissertation focuses on the synthesis and characterization of unique linear, branched, cyclic germanium compounds to further the knowledge and scope of organometallic chemistry of the element. In chapter II a 2-germanium atom end capping reagent was used for synthesis of longer linear oligomer using monohydride Ph 3GeGePh 2H. This species was observed to be thermally unstable upon heating the material to 200 °C. Thermal decomposition products were identified as Ph 3GeH and assumed germylene (Ph 2Ge:), which subsequently polymerized. Reactions were monitored by NMR ( 1H and 13 C) spectroscopy and characterized using X-ray crystallography. A series of linear oligomers R 3Ge(GePh 2)nGeR 3 (n = 0 or 1), were synthesized and subsequently photolyzed. The photodecomposition pathways of these compounds were analyzed after exposure to UV-C light (280-100 nm) in the presence of acetic acid, acting as a germylene trapping agent. Resulting photoproducts showed germylene (Ph 2Ge:) extrusion and germyl radical formation (R 3Ge ･) to yield R 2Ge(H)OAc and R3GeOAc, R 3GeH and R 3GeGeR 3 respectively. Photoproducts were identified by 1H NMR, electron impact gas-chromatography (EI-GC/MS), and high resolution accurate mass-mass spectrometry (HRAM-MS). t Three branched oligogermanes (Me 3Ge) 3GePh, (Me 2Bu Ge) 3GePh, (Me 2PhGe) 3GePh, n and (Bu 3 Ge) 3GePh were synthesized and characterized. All species were prepared and characterized by NMR ( 1H, 13 C, and 73 Ge) and HRAM-MS. The varying substituent composition on the peripheral R 3Ge- groups provided insight on the electronic properties studied by cyclic/differential pulse voltammetry (CV and DPV) and UV-visible spectroscopy. i i Chapter V describes the synthesis of a series Pr 3Ge(GePh 2)nGePr 3 (n = 0-3) linear oligomers. Compounds were characterized using NMR (1H and 13 C), UV-vis, and CV/DPV. A bathochromic shift was seen via Ge – Ge chain elongation, and species became easier to oxidize. Crystals of the pentagermane showed dichroism and luminescence, the smallest discrete oligomer to exhibit polymeric like properties. The final chapter focuses on the synthesis of perarylated cyclotetra- (Ar 2Ge) 4 and cyclopentagermanes (Ar 2Ge) 5 (Ar = 2,5-xylyl), using Ar 2GeCl 2 as the precursor. These species were selected to increase solubility in ring opening reactions with an alkali metal. Crystals were only obtained in experimental conditions for (Ar 2Ge) 4. However, the expected product turned out to be a germyl-substituted cyclogermane ClGeAr 2(Ge 4Ar 7), the first compound of its class to be synthesized. iv TABLE OF CONTENTS Chapter Page I. INTRODUCTION .................................................................................................................... 1 II. SYNTHESIS AND THERMAL DECOMPOSITION OF Ph 3GeGePh 2H .............................. 9 2.1 Introduction ............................................................................................................... 9 2.2 Results and Discussion ............................................................................................ 13 2.3 Conclusion ............................................................................................................... 15 2.4 Experimental ........................................................................................................... 16 III. PHOTODECOMPOSITION PATHWAY OF LINEAR OLIGOGERMANES n n n Bu 3GeGePh 2GeBu 3 AND Bu 3GeGePh 3: PHOTOPRODUCT IDENTIFICATION BY SPECTROSCOPIC AND SPECTROMETRIC METHODS .............................................. 19 3.1 Introduction ............................................................................................................. 19 3.2 Results and Discussion ............................................................................................ 23 3.3 Conclusion ............................................................................................................... 42 3.4 Experimental ........................................................................................................... 43 IV. SYNTHESIS AND INVESTIGATION OF THE PHYSICAL PROPERTY AND STRUCTURE RELATIONSHIP OF BRANCHED OLIGOGERMANES (Me 3Ge) 3GePh, t (Me 2Bu Ge) 3GePh, AND (Me 2PhGe) 3GePh ........................................................................ 49 4.1 Introduction ............................................................................................................. 49 4.2 Results & Discussion .............................................................................................. 50 4.3 Conclusion ............................................................................................................... 60 4.4 Experimental ........................................................................................................... 60 V. SYNTHESIS OF A SERIES OF TRIISOPROPYL TERMINATED OLIGOGERMANES i i Pr 3Ge(GePh2)nGePr 3 (n = 0-3) HIGHLIGHTING A LUMINESCENT AND DICHROIC PENTAGERMANE .............................................................................................................. 63 5.1 Introduction ............................................................................................................. 63 5.2 Results and Discussion ............................................................................................ 64 i i 5.3 Physical Properties of Pr 3Ge(GePh 2)3GePr 3 .......................................................... 72 i i 5.4 Luminescent and Dichroic Behavior of Pr 3Ge(GePh 2)3GePr 3 ............................... 77 v Chapter Page 5.5 Conclusion ............................................................................................................... 80 5.6 Experimental ........................................................................................................... 81 VI. ATTEMPTED PREPARTION OF CYCLIC PERARYLATED OLIGOGERMANES (GeAr 2)4 AND (GeAr 2)5 VIA COUPLING REACTION WITH Ar 2GeCl 2 AND ALKALI METAL ..............................................................................................................................