Photoinduced charge separation involving an unusual double electron transfer mechanism in a donor-bridge-acceptor molecule

被引:65
作者
Miller, SE [1 ]
Lukas, AS [1 ]
Marsh, E [1 ]
Bushard, P [1 ]
Wasielewski, MR [1 ]
机构
[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
关键词
D O I
10.1021/ja001298w
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A series of rodlike donor-bridge-acceptor D-B-A) molecules was synthesized to study the role of bridge energy levels on electron transfer (ET) rates. In these compounds, a 4-aminonaphthalene- 1,8-imide (ANI) electron donor is linked to a 1,8:4,5-naphthalenediimide acceptor (NI) via the 1,4 positions on a phenyl bridge. The phenyl bridge is substituted at the 2 and 5 positions with methyl or methoxy groups to yield ANI-diMe-NI and ANI-diMeO-NI. These molecules differ only in the energy levels of the bridge molecular orbitals. Other parameters affecting ET rates such as donor-acceptor distance, orientation, and driving force are constant between the two systems. The rate constants for charge separation (CS) and charge recombination (CR) within ANI-diMeO-NI in toluene are 32 and 1400 times larger, respectively, than the corresponding rate constants for ANI-diMe-NI. Solvents of higher polarity diminish these differences in rate constants, making them comparable to those observed for ANI-diMe-NI. The relative energies of the ion pair states suggest that it is possible for the reaction (1)*D-B-A --> D-B+-A(-) to occur via a double electron-transfer process that is somewhat analogous to Dexter energy transfer. The lowest excited singlet state of the donor, (1)*ANI, possesses about 70% charge-transfer character, so that significant positive charge is localized on its amine nitrogen, whereas significant negative charge is localized on its naphthalene-1,8-imide ring. Electron transfer from the naphthalene-1,8 imide ring of (1)*ANI to NI is concomitant with electron transfer from the p-dimethoxybenzene bridge to the electron-deficient amine nitrogen atom in (1)*ANI. A series of reference molecules in which the p-dimethoxybenzene bridge moiety is attached only to ANI or NI alone is used to establish the structural and electronic requirements for this unusual charge separation mechanism.
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页码:7802 / 7810
页数:9
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