期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 18, 期 44, 页码 14008-14016出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201202245
关键词
density functional calculations; electron transfer; fullerenes; porphyrinoids; semiempirical calculations
资金
- Universitat Bayern e.V.
- Graduate School of Molecular Science
- Italian PRIN
A frozen electron donor-acceptor array that bears porphyrin and fullerene units covalently linked through the ortho position of a phenyl ring and the nitrogen of a pyrrolidine ring, respectively, is reported. Electrochemical and photophysical features suggest that the chosen linkage supports both through-space and through-bond interactions. In particular, it has been found that the porphyrin singlet excited state decays within a few pico-seconds by means of a photoinduced electron transfer to give the rapid formation of a long-lived charge-separated state. Density functional theory (DFT) calculations show HOMO and LUMO to be localized on the electron-donating porphyrin and the electron-accepting fullerene moiety, respectively, at this level of theory. More specifically, semiempirical molecular orbital (MO) configuration interaction (CI) and unrestricted natural orbital (UNO)-CI methods shed light on the nature of the charge-transfer states and emphasize the importance of the close proximity of donor and acceptor for effective electron transfer.
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