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Volumn 130, Issue 14, 2008, Pages 4708-4724

Distinguishing between Dexter and rapid sequential electron transfer in covalently linked donor-acceptor assemblies

Author keywords

[No Author keywords available]

Indexed keywords

MATHEMATICAL MODELS; METAL COMPLEXES; PHENOLS; QUENCHING; SPECTROSCOPIC ANALYSIS; SYNTHESIS (CHEMICAL);

EID: 41849114594     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja077096i     Document Type: Article
Times cited : (39)

References (126)
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    • For information on issues pertaining to solar energy conversion see: "Basic Research Needs for Solar Energy Utilization", Office of Basic Energy Science, U.S. Department of Energy, Washington, D.C., 2005 (available on the U.S. Department of Energy website).
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    • B. Further details concerning the magnetic properies of these compounds will be published elsewhere.
    • B. Further details concerning the magnetic properies of these compounds will be published elsewhere.
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    • 6) (1) indicates that such effects are minor in the present case.
    • 6) (1) indicates that such effects are minor in the present case.
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    • 2 analogs. Unfortunately, we were unable to obtain reasonable quality electrochemical data on these compounds. The underlying reason for this is unclear.
    • 2 analogs. Unfortunately, we were unable to obtain reasonable quality electrochemical data on these compounds. The underlying reason for this is unclear.
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    • The energy of an MLCT excited state can be approximated as the difference between the oxidation potential of the metal and the reduction potential of the ligand. For a given metal complex, then, the lowest energy MLCT state will be associated with the most easily reduced ligand
    • The energy of an MLCT excited state can be approximated as the difference between the oxidation potential of the metal and the reduction potential of the ligand. For a given metal complex, then, the lowest energy MLCT state will be associated with the most easily reduced ligand.
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    • An extremely weak signal was detected in both the steady-state and the time-resolved emission measurements on complex 3. A careful analysis of these data (Figure S4, which included a comparison with analogous data acquired for [Ru((CH3)2-bpy)2(mcbEt, PF 6)2, indicated that this residual emission most likely arises from a trace amount of free [Ru((CH3)2-bpy) 2-mcb, present in solutions of complex 3. The amount of dissociated RuII species is well below 1% and therefore does not contribute to data from time-resolved absorption experiments
    • II species is well below 1% and therefore does not contribute to data from time-resolved absorption experiments.
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    • 3MLCT state of complex 3 was taken from the spectral fitting analysis of the room-temperature spectrum of complex 5.
    • 3MLCT state of complex 3 was taken from the spectral fitting analysis of the room-temperature spectrum of complex 5.
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    • In the limit of weak coupling among the bipyridyl ligands, the charge-transfer band of metal polypyridyl complexes can be considered as a superposition of transitions associated with each ligand. Reductive quenching of the 3MLCT excited state will therefore result in recovery of roughly 2/3 of the original oscillator strength of the ground-state absorption
    • 3MLCT excited state will therefore result in recovery of roughly 2/3 of the original oscillator strength of the ground-state absorption.
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    • 1MLCT excitation occurs on a subpicosecond time scale. See: Damrauer, N. H.; Cerullo, G.; Yeh, A.; Boussie, T. R.; Shank, C. V.; McCusker, J. K. Science 1997, 275, 54-57.
    • 1MLCT excitation occurs on a subpicosecond time scale. See: Damrauer, N. H.; Cerullo, G.; Yeh, A.; Boussie, T. R.; Shank, C. V.; McCusker, J. K. Science 1997, 275, 54-57.
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    • (6) are the observed rate constants for complexes 4 and 6, respectively.
    • (6) are the observed rate constants for complexes 4 and 6, respectively.
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    • Although photosubstitution chemistry is often associated with thermally accessible ligand-field excited states in charge-transfer complexes, its absence does not necessarily discount the existence of such states. See: Thompson, D. W, Wishart, J. F, Brunschwig, B. S, Sutin, N. J. Phys. Chem. A 2001, 105, 8117-8122
    • Although photosubstitution chemistry is often associated with thermally accessible ligand-field excited states in charge-transfer complexes, its absence does not necessarily discount the existence of such states. See: Thompson, D. W.; Wishart, J. F.; Brunschwig, B. S.; Sutin, N. J. Phys. Chem. A 2001, 105, 8117-8122.
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    • obs.
    • obs.
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    • The lack of emission in the low-temperature glass is strongly suggestive of an energy-transfer mechanism but is not necessarily definitive. For a more detailed discussion of the issues surrounding electron transfer in rigid media, see: Chen, P. Y, Meyer, T. J. Chem. Rev. 1998, 98, 1439-1477
    • The lack of emission in the low-temperature glass is strongly suggestive of an energy-transfer mechanism but is not necessarily definitive. For a more detailed discussion of the issues surrounding electron transfer in rigid media, see: Chen, P. Y.; Meyer, T. J. Chem. Rev. 1998, 98, 1439-1477.
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    • It should be noted that, due to the fact that Hab is proportional to the fourth root power of both λ and temperature (eq 5, the magnitude of the coupling constant is relatively insensitive to either of these variables and is instead dominated by the value of k0 as well the barrier reflected in exponential term in eq 2. With regard to the latter, the high density of acceptor states present in the MnII 2 core due to spin exchange between these ions makes coupling to state(s) that allow for a barrierless reaction pathway a reasonable assumption
    • 2 core due to spin exchange between these ions makes coupling to state(s) that allow for a barrierless reaction pathway a reasonable assumption.
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    • The shift in E00 with decreasing temperature is related to the entropy change in the solvent according to ∂E/∂T ≈ ΔSlib, where ΔSlib arises mainly from librational motion of the solvent due to excited-state decay (ref 32, For complex 5, a plot of E00 versus temperature yielded a linear correlation (R2, 0.986) with a slope ΔSlib ≈ 2 eu, a value that is roughly a factor of 2-3 smaller than what has been seen for isolated MLCT chromophores (e.g, the ReI and OsII complexes discussed in ref 32) but larger than what is seen for complex 6 (ΔSlib ≈ 0, These results are consistent with the notion that solvent interaction with the 3MLCT state in complex 5 is more substantial (thus leading to a larger value of λo) than in complex 6
    • o) than in complex 6.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.