期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 15, 期 44, 页码 12005-12017出版社
WILEY-BLACKWELL
DOI: 10.1002/chem.200901671
关键词
absorption; charge transfer; donor-acceptor systems; photophysics; porphyrinoids
资金
- Ministry of Education, Science and Technology of Korea [2008-8-1955]
- AFSOR/AOARD [FA4869-08-1-4097]
- BK21 fellowships
- MEXT [19205006, 20108001]
- JSPS
Donor-acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso-phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge-transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent-polarity-dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry-broken, and relaxed excited states, whereas the non-solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso-(4-aminophenyl) rotation at low temperature prevents the intramolecular charge-transfer (ICT)-forming process. The two-photon absorption (TPA) cross-section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross-section value of approximately 3200 GM (1 GM = 10(-50) cm(4)s photon(-1)) with donor-acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found between the electron-donating/-withdrawing abilities of the peripheral groups and the TPA cross-section values, that is, p-aminophenyl > m-aminophenyl > nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross-section value by a factor of approximately 2 and 4, respectively, for p-amino- and m-nitrophenyl-substituted subporphyrins. On the other hand, the stabilization of the symmetry-broken, dipolar ICT state gives rise to a negligible impact on the TPA processes.
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