The development and investigation of bimetallic systems that undergo proton-coupled intramolecular electron-transfer are reported. Initial studies involved the synthesis of a new family of synthetically versatile ruthenium complexes containing various $\beta$-diketonates (R$\sb2$mal) and 2,6-bis(N-pyrazolyl)pyridine and its methyl substituted derivatives (Me$\sb{\rm n}$bpp). These coordinatively saturated complexes are stable in water and exhibit low redox potentials which can be fine-tuned over a broad potential range. These complexes were used to prepare bimetallic systems in order to study optical electron transfer as a function of ligand substituent effects. In subsequent studies these (Me$\sb{\rm n}$bpp)(R$\sb2$mal)Ru- metal centers were linked to ruthenium centers containing a ligand with an ionizable proton. The general formula of these bimetallic complexes is (((Et$\sb2$N)$\sb2$bpy)$\sb2$Ru(pyz-LH)Ru(Me$\sb{\rm n}$bpp)(R$\sb2$mal)) $\sp{3+}$, where (Et$\sb2$N)$\sb2$bpy is 4,4$\sp\prime$-bis($N,N \sp\prime$-diethylamino)-2,2$\sp\prime$-pyridine and pyz-LH is 3-methyl-5-pyrazyl-pyrazole or 2-pyrazylbenzimidazole. These bimetallic complexes were specifically designed to investigate the relationships between the electrochemically measured proton-coupled electron-transfer process and the spectroscopically measured intervalence (IT) band in the mixed-valence complex. The reversible pH-dependent behavior of the IT-bands gives direct evidence of reversible pH-induced electron transfer between the metal centers. / Source: Dissertation Abstracts International, Volume: 54-12, Section: B, page: 6199. / Major Professor: Kenneth A. Goldsby. / Thesis (Ph.D.)--The Florida State University, 1993.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_77080 |
| Contributors | Slattery, Spencer James., Florida State University |
| Source Sets | Florida State University |
| Language | English |
| Detected Language | English |
| Type | Text |
| Format | 245 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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