Spectroscopic and photophysical properties of complexes of 4{prime}ferrocenyl2,2{prime}:6{prime},2{double_prime}terpyridine and related ligands
Abstract
4{prime}(Ferrocenyl)2,2{prime}:6{prime}2{double_prime}terpyridine (Fctpy) and 4{prime}(4pyridyl)2,2{prime}:6{prime},2{double_prime}terpyridine (pytpy) were prepared from the corresponding ferrocene and pyridinecarboxaldehyle and 2acetylpyridine 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}, excitedstate emission and lifetime measurements indicated an upperlimit emission quantum yield of 0.003 and an upperlimit emission lifetime of 0.025 {micro}s. The influence of the ferrocenyl site on excitedstate decay is discussed, and an excitedstate energy level diagram is proposed.
 Authors:
 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)
 Publication Date:
 Sponsoring Org.:
 USDOE, Washington, DC (United States)
 OSTI Identifier:
 354364
 Resource Type:
 Journal Article
 Resource Relation:
 Journal Name: Inorganic Chemistry; Journal Volume: 38; Journal Issue: 10; Other Information: PBD: 17 May 1999
 Country of Publication:
 United States
 Language:
 English
 Subject:
 36 MATERIALS SCIENCE; PYRIDINES; RUTHENIUM COMPLEXES; IRON COMPLEXES; ZINC COMPLEXES; REDOX POTENTIAL; ENERGYLEVEL TRANSITIONS; QUANTUM EFFICIENCY; LIFETIME
Citation Formats
Hutchinson, K., Morris, J.C., Nile, T.A., Walsh, J.L., Thompson, D.W., Petersen, J.D., and Schoonover, J.R. Spectroscopic and photophysical properties of complexes of 4{prime}ferrocenyl2,2{prime}:6{prime},2{double_prime}terpyridine and related ligands. United States: N. p., 1999.
Web. doi:10.1021/ic980798b.
Hutchinson, K., Morris, J.C., Nile, T.A., Walsh, J.L., Thompson, D.W., Petersen, J.D., & Schoonover, J.R. Spectroscopic and photophysical properties of complexes of 4{prime}ferrocenyl2,2{prime}:6{prime},2{double_prime}terpyridine and related ligands. United States. doi:10.1021/ic980798b.
Hutchinson, K., Morris, J.C., Nile, T.A., Walsh, J.L., Thompson, D.W., Petersen, J.D., and Schoonover, J.R. Mon .
"Spectroscopic and photophysical properties of complexes of 4{prime}ferrocenyl2,2{prime}:6{prime},2{double_prime}terpyridine and related ligands". United States.
doi:10.1021/ic980798b.
@article{osti_354364,
title = {Spectroscopic and photophysical properties of complexes of 4{prime}ferrocenyl2,2{prime}:6{prime},2{double_prime}terpyridine and related ligands},
author = {Hutchinson, K. and Morris, J.C. and Nile, T.A. and Walsh, J.L. and Thompson, D.W. and Petersen, J.D. and Schoonover, J.R.},
abstractNote = {4{prime}(Ferrocenyl)2,2{prime}:6{prime}2{double_prime}terpyridine (Fctpy) and 4{prime}(4pyridyl)2,2{prime}:6{prime},2{double_prime}terpyridine (pytpy) were prepared from the corresponding ferrocene and pyridinecarboxaldehyle and 2acetylpyridine 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}, excitedstate emission and lifetime measurements indicated an upperlimit emission quantum yield of 0.003 and an upperlimit emission lifetime of 0.025 {micro}s. The influence of the ferrocenyl site on excitedstate decay is discussed, and an excitedstate energy level diagram is proposed.},
doi = {10.1021/ic980798b},
journal = {Inorganic Chemistry},
number = 10,
volume = 38,
place = {United States},
year = {Mon May 17 00:00:00 EDT 1999},
month = {Mon May 17 00:00:00 EDT 1999}
}

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