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Design And Synthesis Of A High Potential Ruthenium (II) Tetraazatetrapyridopentaphene Complex Capable Of Two-electron Reduction

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Design And Synthesis Of A High Potential Ruthenium (II) Tetraazatetrapyridopentaphene Complex Capable Of Two-electron Reduction

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dc.contributor.author Diaz, Nancy Ruth G. en_US
dc.date.accessioned 2010-03-03T23:30:24Z
dc.date.available 2010-03-03T23:30:24Z
dc.date.issued 2010-03-03T23:30:24Z
dc.date.submitted January 2009 en_US
dc.identifier.other DISS-10392 en_US
dc.identifier.uri http://hdl.handle.net/10106/1991
dc.description.abstract We report the synthesis of a complex, [(phen)₂Ru(tatpph)Ru(phen)₂]⁴⁺ (Ph⁴⁺), which like its predecessor compound, [(phen)₂Ru(tatppc)Ru(phen)₂]⁴⁺ (Pc ⁴⁺), can undergo two sequential 1-electron photoreductions in MeCN in the presence of a sacrificial reductant. The initial complex, Ph ⁴⁺, can be completely regenerated from the singly and doubly reduced forms by exposure to air, although the rate of regeneration for the second photoreduction is much slower than the first. Electrochemical studies have shown that this complex is not only capable of storing multiple reducing equivalents but these equivalents have stored potentials that are significantly higher than the complex Pc ⁴⁺ and are sufficient to reduce H⁺ to H₂. The first and second reduction potentials for Ph⁴⁺ were determined to be at -0.53 and -0.96 V respectively, while the corresponding reduction potentials for Pc ⁴⁺ were found to be at -0.02 and -0.51 V, all reported vs. NHE. These results correlate very well with the MO calculations which predicted a Ph ⁴⁺ LUMO that is 0.56 eV higher in energy than the Pc ⁴⁺ LUMO. The internal coordination site, born out of the bridging ligand's bent structure, is also accessible to further structural modifications that may lead to improve photocatalytic properties for the complex. en_US
dc.description.sponsorship MacDonnell, Frederick en_US
dc.language.iso EN en_US
dc.publisher Chemistry & Biochemistry en_US
dc.title Design And Synthesis Of A High Potential Ruthenium (II) Tetraazatetrapyridopentaphene Complex Capable Of Two-electron Reduction en_US
dc.type M.S. en_US
dc.contributor.committeeChair MacDonnell, Frederick en_US
dc.degree.department Chemistry & Biochemistry en_US
dc.degree.discipline Chemistry & Biochemistry en_US
dc.degree.grantor University of Texas at Arlington en_US
dc.degree.level masters en_US
dc.degree.name M.S. en_US
dc.identifier.externalLink https://www.uta.edu/ra/real/editprofile.php?onlyview=1&pid=105
dc.identifier.externalLinkDescription Link to Research Profiles

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