期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 118, 期 25, 页码 4527-4532出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp504689q
关键词
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资金
- Ministry of Education, Culture, Sports, Science, and Technology (MEXT) of the Japanese Government [25220806, 25288035]
- Grants-in-Aid for Scientific Research [25288035, 26410043] Funding Source: KAKEN
Cycloparaphenylenes (CPPs), a class of hoop-shaped conjugated macrocycles, have attracted the attention of researchers in various fields because of their interesting properties. Although their properties in the singlet-excited state have been reported, there is no systematic information on the triplet-excited state. In the present study, the properties of triplet-excited [n]CPP (n = 8-12, where n denotes the number of phenyl rings) were comprehensively investigated. The phosphorescence peak shifted to the shorter-wavelength side with increasing ring size of the CPPs, indicating smaller triplet energy for smaller CPPs. It was found that the triplet energy of a smaller CPP is even smaller than those of poly(p-phenylene)s, indicating that small hoop-shaped conjugated macrocycles are effective in realizing low-band gap materials. By applying laser flash photolysis, the T-n-T-1 absorption spectra of CPPs were obtained, from which the size-dependence of energy levels of higher triplet states were also determined. Generation of singlet oxygen by the energy transfer from a triplet-excited CPP was confirmed. The generation yield became smaller with increasing size of the CPP in accordance with the triplet yield. From these observations, the size-dependence of the deactivation pathways is explained.
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