Two-electron Quenching of Dinuclear Ruthenium (II) Polypyridyl Complexes

Content Provider	Semantic Scholar
Author	Zhang, Yinling
Copyright Year	2016
Abstract	A bridging ligand 5,5’-Bi1,10-phenanthroline, diphen, was prepared using dichlorobis(triphenylphosphine)Ni(II), Ni(PPh3)2Cl2 as catalyst with a yield of 40%. Yellow cubic crystals were able to obtain from the good purity product for single crystal analysis. The torsion angle between the planes of the subunit phenanthrolines is about 66 degrees. A dinuclear ruthenium (II) polypyridyl complex, (phen)2Ru(diphen)Ru(phen)2 , was synthesized by using polymeric ruthenium carbonyl compound as the entry point, diphen as the bridging ligand and 1,10-phenanthroline, phen, as the terminal legand. Brown needlelike crystals were precipitated from acetonitrile that were not suitable for single crystal diffraction. The photochemistry of the dimer was investigated in regards to the oxidation and reduction of the ruthenium centers through a series of quenching reactions excited by visible light. The analogous monomeric complexes Ru(bpy)3 2+ and Ru(phen)3 2+ were used as comparisions. In the photoinduced oxidation with peroxydisulfate, S2O8 , the dimer showed a higher Stern-Volmer quenching constant kq than Ru(phen)3 . The dimer showed faster laser flash photolysis transients than Ru(bpy)3 . In the photoinduced reduction with ascorbate, no significant difference between the dimer and Ru(phen)3 . ACKNOWLEDGEMENTS I’d like to thank my research advisor Dr. Bill Durham for all his guidance and help he has given me during my time at University of Arkansas. I have been fortunate to have him as my savior, not only academically as well as physically and emotionally, who always was encouraging me, never putting me down. I sincerely thank him for his wisdom and supporting which helped me to finish this dissertation. I would also like to thank the Chemistry department in general for providing a great learning environment. Thanks also to Dr. Jingyi Chen and Dr. Stefan Kilyanek for their willingness to serve on my graduate committee. Thanks to Dr. Nan Zheng for use of his lab. I would also want to thank Dr. Latisha Puckett who is the past member of the Durham’s research group for her help. I am grateful to my friends and colleagues for their encouragement and moral support which made my stay and studies in Fayetteville more unforgettable. Most of all, I would like to thank my lovely parents for all the understanding, patience, love, and support that they has given me during my studies. TABLE OF CONTENTS CHAPTER
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Alternate Webpage(s)	https://scholarworks.uark.edu/cgi/viewcontent.cgi?article=3214&context=etd
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article