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Volumn 11, Issue 8, 2010, Pages 1685-1692

Exciplex formation and excited state deactivation of difluoroborondipyrromethene (Bodipy) dyads

Author keywords

Bodipy; Charge recombination; Electron transfer; Exciplex; Fluorescence probes

Indexed keywords

FLUORESCENCE; FREE RADICAL REACTIONS; GROUND STATE; ORGANIC SOLVENTS; QUINONE;

EID: 77953209842     PISSN: 14394235     EISSN: 14397641     Source Type: Journal    
DOI: 10.1002/cphc.201000127     Document Type: Article
Times cited : (22)

References (92)
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    • -1 and generally there is a good agreement with kRAD calculated by the Stricker Berg equation. The non-radiative rate constant is more dependent on the structure.
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    • Although samples were purified by tlc immediately prior to the spectroscopic measurements, tiny traces of the hydroquinone form can be left behind in the sample. The lifetimes of the directly linked meso and side-substituted hydroquinone dyads are long enough to show up as the tail in the up-conversion lifetime measurements. The small amounts of impurity turned out to be less of a problem for the femtosecond transient absorption experiments, and there was no obvious degradation of the quinone to the hydroquione during collection times.
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    • A sample of BD-MPQ in N2-purged toluene when excited at 355 nm with a 4 nsns laser pulse produced a transient profile that was consistent with the triplet-triplet absorption spectrum for a Bodipy-based molecule.
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    • The term exciplex originating from excited state complex applies equally well to intermolecular and intramolecular species. Distinction between exciplex and excited charge transfer state is less clear-cut. Exciplex-like emission has been observed for what appear rigid systems see J. W. Verhoeven, T. Scherer, R. J. Willemse, Pure Appl. Chem. 1993, 65, 1717-1722.
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    • A. C. Benniston, A. Harriman, S. L. Howell, P. Li, D. P. Lydon, J. Org. Chem. 2007, 72, 888-897. The structure of the exciplex in the phenylene spacer cases is likely to be controlled by the degree of electronic coupling between the Bodipy and quinone group, and bending in the molecule as the phenylene and quinone come into partial conjugation.
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    • This situation where tCS is independent on solvation dynamics falls within the regime of the Sumi-Marcus model for which vibrational dynamics control the electron transfer process. In truth, such behavior is not unusual and has been reported previously by Barbara et al. for a series of closely-spaced donor-acceptor molecules in aprotic solvents see, G. C. Walker, E. kesson, A. E. Johnson, N. E. Levinger, P. F. Barbara, J. Phys. Chem. 1992, 96, 3728-3736.
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    • It is also feasible that electron transfer takes place from the S2 state during the known fast internal conversion S2-S1 process (see ref. 23). This type of upper excited state quenching has been seen previously in porphyrin-based systems, see: a) H. Chosrowjan, S. Tanagichi, T. Okada, S. Takagi, T. Arai, K. Tokumaru, Chem. Phys. Lett. 1995, 242, 644-649.
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    • That photoinduced electron transfer rate constants approach nuclear vibrational frequencies has also been seen previously in porphyrin-qui-none dyads, see: A. N. Macpherson, P. A. Liddell, S. Lin, L. Noss, G. R. Seely, J. M. DeGrazioano, A. L. Moore, T. A. Moore, D. Gust, J. Am. Chem. Soc. 1995, 117, 7202-7112. It may be that the structural motif that controls excited-state electron transfer is the dipyrromethene group since this represents the direct structural link between porphyrins and Bodipy compounds.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.