title: Properties of triplet-excited [N]cycloparaphenylenes (N = 8-12): excitation energies lower than those of linear oligomers and polymers.
abstract: 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 Tn-T1 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.
authors.affiliation: The Institute of Scientific and Industrial Research (SANKEN), Osaka University , Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Mamoru
authors.initials: M
authors.lastname: Fujitsuka
authors.forename: Chao
authors.initials: C
authors.lastname: Lu
authors.forename: Takahiro
authors.initials: T
authors.lastname: Iwamoto
authors.forename: Eiichi
authors.initials: E
authors.lastname: Kayahara
authors.forename: Shigeru
authors.initials: S
authors.lastname: Yamago
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Majima