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Volumn 111, Issue 24, 2007, Pages 6655-6666

Reversible interchange of charge-transfer versus electron-transfer states in organic electron transfer via cross-exchanges between diamagnetic (donor/acceptor) dyaos

Author keywords

[No Author keywords available]

Indexed keywords

DIAMAGNETIC MATERIALS; INTERCHANGES; OPTICAL TRANSITIONS; REDOX REACTIONS;

EID: 34547305429     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp068994o     Document Type: Article
Times cited : (37)

References (99)
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    • The electron-donor/acceptor dyads enclosed in brackets, [D,A], are hereinafter referred to interchangeably as either charge-transfer complexes or charge-transfer states.
    • The electron-donor/acceptor dyads enclosed in brackets, [D,A], are hereinafter referred to interchangeably as either charge-transfer complexes or charge-transfer states.
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    • The ion-radical product derived by an adiabatic electron-transfer process is designated hereinafter as {D+.A, which can consist of either the contact ion pair (CIP) or the separated ion pair SIP, 29 as we recently elaborated
    • -.} which can consist of either the contact ion pair (CIP) or the separated ion pair (SIP), 29 as we recently elaborated:
  • 24
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    • Although spectral (UV-vis) studies alone are unlikely to elucidate such a CIP/SIP distinction, we hope that the solvent dependence in the combined electronic/EPR spectroscopic study will shed light on this problem
    • Although spectral (UV-vis) studies alone are unlikely to elucidate such a CIP/SIP distinction, we hope that the solvent dependence in the combined electronic/EPR spectroscopic study will shed light on this problem.
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    • -.}
    • -.}
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    • 22c donors were prepared via literature procedures.
    • 22c donors were prepared via literature procedures.
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    • The structural changes accompanying the one-electron oxidation and leading to the planarization of the cation radical can be qualitatively described as shown in Scheme 1
    • The structural changes accompanying the one-electron oxidation and leading to the planarization of the cation radical can be qualitatively described as shown in Scheme 1.
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    • +..
    • +..
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    • Compare with Figure 9
    • Compare with Figure 9.
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    • -.
    • -.
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    • -. ion pair consisted of only a single broadened line owing to the rapid interionic spin-exchange and self-exchange processes.
    • -. ion pair consisted of only a single broadened line owing to the rapid interionic spin-exchange and self-exchange processes.
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    • Note that, in Figure 5, the null point at 625 nm is, strictly speaking, not a true isosbestic point but arises as a result of the weak absorptions of all components (donor/acceptor dyad, charge-transfer complex, and ionradical pair) at this wavelength.
    • Note that, in Figure 5, the null point at 625 nm is, strictly speaking, not a true isosbestic point but arises as a result of the weak absorptions of all components (donor/acceptor dyad, charge-transfer complex, and ionradical pair) at this wavelength.
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    • Mixed at -95 °C to obviate any further chemical processes (vide infra).
    • Mixed at -95 °C to obviate any further chemical processes (vide infra).
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    • Notation: 1, benzene; 2, toluene; 3, cumene; 4, ethylbenzene; 5, o-xylene; 6, mesitylene; 7, p-xylene; 8, durene; 9, naphthalene; 10, hexamethylbenzene; 11, hexaethylbenzene; 12, biphenylene; 13, 2,5dimethyl-p-dimethoxybenzene; 14, pyrene; 15, octamethylbiphenylene; 16, pentamethylbenzene; 17, fluorene; 18, perylene. Data are from ref 16.
    • Notation: 1, benzene; 2, toluene; 3, cumene; 4, ethylbenzene; 5, o-xylene; 6, mesitylene; 7, p-xylene; 8, durene; 9, naphthalene; 10, hexamethylbenzene; 11, hexaethylbenzene; 12, biphenylene; 13, 2,5dimethyl-p-dimethoxybenzene; 14, pyrene; 15, octamethylbiphenylene; 16, pentamethylbenzene; 17, fluorene; 18, perylene. Data are from ref 16.
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    • 2 = 1.
    • 2 = 1.
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    • Although this expression was derived originally for weakly interacting mixed-valence complexes, Creutz, Newton, and Sutin showed40 its applicability (within the intermolecular two-state model) to strongly interacting systems, such as that considered in the current work
    • 40 its applicability (within the intermolecular two-state model) to strongly interacting systems, such as that considered in the current work.
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    • π) of the redox centers, which imply that the correct coupling element may be up to 50% higher than that calculated from the crystallographic data.
    • π) of the redox centers, which imply that the correct coupling element may be up to 50% higher than that calculated from the crystallographic data.
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    • For the formation of diamagnetic ion-radical dimers, see Supporting Information Figure S8 which points to the existence of freely diffusing paramagnetic precursors.
    • (a) For the formation of diamagnetic ion-radical dimers, see Supporting Information Figure S8 which points to the existence of freely diffusing paramagnetic precursors.
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    • For charge-transfer complexes of the same acceptor with various donors in the strongly endergonic electron-transfer region, the variation of the CT transition is essentially linearly related to the change of redox potentials owing to the similarity of the coupling element and reorganization energies for related donor/acceptor pairs
    • For charge-transfer complexes of the same acceptor with various donors in the strongly endergonic electron-transfer region, the variation of the CT transition is essentially linearly related to the change of redox potentials owing to the similarity of the coupling element and reorganization energies for related donor/acceptor pairs.
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    • A similar potential-energy surface was described in the chargetransfer vs electron-transfer interchanges between arene donors and the diamagnetic nitrosonium and other acceptors.23b,34,53
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    • Such a measurable contraction of the interplanar separation is taken to represent the inner-sphere character of the intermolecular interaction as spectrally revealed by the charge-transfer transition.13
    • 13
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    • Stated alternatively, is the two-state Mulliken-Hush methodology applicable (in varying degrees) to the generalized kinetic description in eq 7 to cover all donor/acceptor systems, irrespective of the driving force?
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.