Spectroscopic and photophysical properties of complexes of 4{prime}-ferrocenyl-2,2{prime}:6{prime},2{double_prime}-terpyridine and related ligands
- Univ. of North Carolina, Greensboro, NC (United States). Dept. of Chemistry
- Wayne state Univ., Detroit, MI (United States). Dept. of Chemistry
- Los Alamos National Labs., Los Alamos, NM (United States)
4{prime}-(Ferrocenyl)-2,2{prime}:6{prime}2{double_prime}-terpyridine (Fctpy) and 4{prime}-(4-pyridyl)-2,2{prime}:6{prime},2{double_prime}-terpyridine (pytpy) were prepared from the corresponding ferrocene- and pyridinecarboxaldehyle and 2-acetylpyridine using the Krohnke synthetic methodology. Metal complexes, [M(Fctpy){sub 2}](PF{sub 6}){sub 2} (M = Ru, Fe, Zn), [Ru(tpy)(Fctpy)](PF{sub 6}){sub 2} (tpy = 2,2{prime}:6{prime},6{double_prime}-terpyridine), and [Ru(pytpy){sub 2}](PF{sub 6}){sub 2} were prepared and characterized. Cyclic voltammetric analysis indicated Ru(III/II) and ferrocenium/ferrocene redox couples near expected potentials (Ru{sup III/II} {approximately}1.3 V and ferrocenium/ferrocene {approximately}0.6 V vs Ag/AgCl). In addition to dominant {pi}{sub tpy} {r_arrow} {pi}{sub tpy}{sup *} UV absorptions near 240 and 280 nm and d{sub {pi}}{sup Ru} {r_arrow} {pi}{sub tpy}{sup *} MLCT absorptions around 480 nm, the complexes [Ru(Fctpy){sub 2}](PF{sub 6}){sub 2} and [Ru(tpy)(Fctpy)](PF{sub 6}){sub 2} exhibit an unusual absorption band around 530 nm. Resonance Raman measurements indicate that this band is due to a {sup 1}[(d({pi}){sub Fc}){sup 6}] {r_arrow} {sup 1}[(d({pi}){sub Fc}){sup 5}({pi}{sup *}{sub tpy}{sup Ru}){sup 1}] transition. For [Ru(Fctpy){sub 2}](PF{sub 6}){sub 2} and [Ru(tpy)(Fctpy)](PF{sub 6}){sub 2}, excited-state emission and lifetime measurements indicated an upper-limit emission quantum yield of 0.003 and an upper-limit emission lifetime of 0.025 {micro}s. The influence of the ferrocenyl site on excited-state decay is discussed, and an excited-state energy level diagram is proposed.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- OSTI ID:
- 354364
- Journal Information:
- Inorganic Chemistry, Vol. 38, Issue 10; Other Information: PBD: 17 May 1999
- Country of Publication:
- United States
- Language:
- English
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