Photoinduced Electron Transfer in Covalently Linked Ruthenium Tris(bipyridyl)-Viologen Molecules: Observation of Back Electron Transfer in the Marcus Inverted Region

Edward H. Yonemoto, Richard L. Riley, Yeong Il Kim, Stephen J. Atherton, Russell H. Schmehl, Thomas E. Mallouk

Research output: Contribution to journalArticle

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Abstract

The rates of photoinduced electron transfer (ET) in a series of donor-acceptor molecules (4,4′-R 2 -2,2′-bipyridine) 2 Ru(1-(4-CH 3 -2,2′,-bipyridine-4′,-yl-(CH 2 ) n )-4,4′-bipyridinediium-1′-R′) 4+ (R = H, CH 3 ; R′ = CH 3 , CH 2 CN; = 1, 2) were studied by picosecond flash photolysis/transient absorbance techniques. The rate of intramolecular forward ET (MLCT quenching) in acetonitrile varied with -ΔG° according to classical Marcus theory for n = 2, but not for n = 1. The back ET reactions for both n = 1 and n = 2 showed an inverted rate behavior described quantitatively by semiclassical Marcus theory. For the n = 2 compounds, the value of |V(r)| 2 (V(r) ≡ electron-exchange matrix element) was approximately 1 order of magnitude higher for the forward than for the back ET reactions. This difference was rationalized in terms of a larger distance over which the back reaction (viologen-to-metal) occurs relative to the forward reaction (bipyridine-to-viologen). Cage-escape efficiencies for a series of Ru(bpy) 3 2+ electron donors and viologen acceptors did not show any apparent relationship to driving force for the back ET reaction. In this case, geometric factors are more important than energetic factors in controlling the rates of back reaction and cage escape.

Original languageEnglish (US)
Pages (from-to)8081-8087
Number of pages7
JournalJournal of the American Chemical Society
Volume114
Issue number21
DOIs
StatePublished - Oct 1 1992

Fingerprint

Viologens
2,2'-Dipyridyl
Ruthenium
Observation
Electrons
Molecules
Escape Reaction
Photolysis
Acetonitrile
Quenching
Metals

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Yonemoto, Edward H. ; Riley, Richard L. ; Kim, Yeong Il ; Atherton, Stephen J. ; Schmehl, Russell H. ; Mallouk, Thomas E. / Photoinduced Electron Transfer in Covalently Linked Ruthenium Tris(bipyridyl)-Viologen Molecules : Observation of Back Electron Transfer in the Marcus Inverted Region. In: Journal of the American Chemical Society. 1992 ; Vol. 114, No. 21. pp. 8081-8087.
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abstract = "The rates of photoinduced electron transfer (ET) in a series of donor-acceptor molecules (4,4′-R 2 -2,2′-bipyridine) 2 Ru(1-(4-CH 3 -2,2′,-bipyridine-4′,-yl-(CH 2 ) n )-4,4′-bipyridinediium-1′-R′) 4+ (R = H, CH 3 ; R′ = CH 3 , CH 2 CN; = 1, 2) were studied by picosecond flash photolysis/transient absorbance techniques. The rate of intramolecular forward ET (MLCT quenching) in acetonitrile varied with -ΔG° according to classical Marcus theory for n = 2, but not for n = 1. The back ET reactions for both n = 1 and n = 2 showed an inverted rate behavior described quantitatively by semiclassical Marcus theory. For the n = 2 compounds, the value of |V(r)| 2 (V(r) ≡ electron-exchange matrix element) was approximately 1 order of magnitude higher for the forward than for the back ET reactions. This difference was rationalized in terms of a larger distance over which the back reaction (viologen-to-metal) occurs relative to the forward reaction (bipyridine-to-viologen). Cage-escape efficiencies for a series of Ru(bpy) 3 2+ electron donors and viologen acceptors did not show any apparent relationship to driving force for the back ET reaction. In this case, geometric factors are more important than energetic factors in controlling the rates of back reaction and cage escape.",
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Photoinduced Electron Transfer in Covalently Linked Ruthenium Tris(bipyridyl)-Viologen Molecules : Observation of Back Electron Transfer in the Marcus Inverted Region. / Yonemoto, Edward H.; Riley, Richard L.; Kim, Yeong Il; Atherton, Stephen J.; Schmehl, Russell H.; Mallouk, Thomas E.

In: Journal of the American Chemical Society, Vol. 114, No. 21, 01.10.1992, p. 8081-8087.

Research output: Contribution to journalArticle

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T1 - Photoinduced Electron Transfer in Covalently Linked Ruthenium Tris(bipyridyl)-Viologen Molecules

T2 - Observation of Back Electron Transfer in the Marcus Inverted Region

AU - Yonemoto, Edward H.

AU - Riley, Richard L.

AU - Kim, Yeong Il

AU - Atherton, Stephen J.

AU - Schmehl, Russell H.

AU - Mallouk, Thomas E.

PY - 1992/10/1

Y1 - 1992/10/1

N2 - The rates of photoinduced electron transfer (ET) in a series of donor-acceptor molecules (4,4′-R 2 -2,2′-bipyridine) 2 Ru(1-(4-CH 3 -2,2′,-bipyridine-4′,-yl-(CH 2 ) n )-4,4′-bipyridinediium-1′-R′) 4+ (R = H, CH 3 ; R′ = CH 3 , CH 2 CN; = 1, 2) were studied by picosecond flash photolysis/transient absorbance techniques. The rate of intramolecular forward ET (MLCT quenching) in acetonitrile varied with -ΔG° according to classical Marcus theory for n = 2, but not for n = 1. The back ET reactions for both n = 1 and n = 2 showed an inverted rate behavior described quantitatively by semiclassical Marcus theory. For the n = 2 compounds, the value of |V(r)| 2 (V(r) ≡ electron-exchange matrix element) was approximately 1 order of magnitude higher for the forward than for the back ET reactions. This difference was rationalized in terms of a larger distance over which the back reaction (viologen-to-metal) occurs relative to the forward reaction (bipyridine-to-viologen). Cage-escape efficiencies for a series of Ru(bpy) 3 2+ electron donors and viologen acceptors did not show any apparent relationship to driving force for the back ET reaction. In this case, geometric factors are more important than energetic factors in controlling the rates of back reaction and cage escape.

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