Spectroscopic and Photophysical Properties of Complexes of 4'-Ferrocenyl-2,2':6',2' '-terpyridine and Related Ligands
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- 作者：Kimberly Hutchison ; James C. Morris ; Terence A. Nile ; Jerry L. Walsh ; David W. Thompson ; John D. Petersen ; and Jon R. Schoonover
- 刊名：Inorganic Chemistry
- 出版年：1999
- 出版时间：May 17, 1999
- 年：1999
- 卷：38
- 期：10
- 页码：2516 - 2523
- 全文大小：110K
- 年卷期：v.38,no.10(May 17, 1999)
- ISSN：1520-510X
文摘
4'-(Ferrocenyl)-2,2':6',2' '-terpyridine (Fctpy) and 4'-(4-pyridyl)-2,2':6',2' '-terpyridine (pytpy) were prepared fromthe corresponding ferrocene- and pyridinecarboxaldehyle and 2-acetylpyridine using the Krohnke syntheticmethodology. Metal complexes, [M(Fctpy)2](PF6)2 (M = Ru, Fe, Zn), [Ru(tpy)(Fctpy)](PF6)2 (tpy = 2,2':6',6' '-terpyridine), and [Ru(pytpy)2](PF6)2 were prepared and characterized. Cyclic voltammetric analysis indicated RuIII/IIand ferrocenium/ferrocene redox couples near expected potentials (RuIII/II ~1.3 V and ferrocenium/ferrocene ~0.6V vs Ag/AgCl). In addition to dominant 
tpy 
tpy* UV absorptions near 240 and 280 nm and dRu tpy*MLCT absorptions around 480 nm, the complexes [Ru(Fctpy)2](PF6)2 and [Ru(tpy)(Fctpy)](PF6)2 exhibit an unusualabsorption band around 530 nm. Resonance Raman measurements indicate that this band is due to a 1[(d()Fc)6] 1[(d()Fc)5(*tpyRu)1] transition. For [Ru(Fctpy)2](PF6)2 and [Ru(tpy)(Fctpy)](PF6)2, excited-state emission andlifetime measurements indicated an upper-limit emission quantum yield of 0.003 and an upper-limit emissionlifetime of 0.025 
s. The influence of the ferrocenyl site on excited-state decay is discussed, and an excited-stateenergy level diagram is proposed.
tpy tpy* UV absorptions near 240 and 280 nm and dRu tpy*MLCT absorptions around 480 nm, the complexes [Ru(Fctpy)2](PF6)2 and [Ru(tpy)(Fctpy)](PF6)2 exhibit an unusualabsorption band around 530 nm. Resonance Raman measurements indicate that this band is due to a 1[(d()Fc)6] 1[(d()Fc)5(*tpyRu)1] transition. For [Ru(Fctpy)2](PF6)2 and [Ru(tpy)(Fctpy)](PF6)2, excited-state emission andlifetime measurements indicated an upper-limit emission quantum yield of 0.003 and an upper-limit emissionlifetime of 0.025 s. The influence of the ferrocenyl site on excited-state decay is discussed, and an excited-stateenergy level diagram is proposed.