title: Multistep Electron Transfer Systems Containing [2.2]- or [3.3]Paracyclophane.
abstract: Paracyclophanes (PCPs), which exhibit interesting properties due to their transannular interactions, have been employed as a spacer in various electron transfer (ET) systems. In the present work, we investigated ET processes in dyads and triads containing [2.2]PCP or [3.3]PCP as donors to study their properties in multistep ET processes. The dyad molecules of PCP and 1,8-naphthalimide (NI) as a photosensitizing electron acceptor exhibited charge separation (CS) upon excitation of NI. In addition, triads of NI, PCP, and carbazole showed charge shift after an initial CS, thus confirming multistep ET. In this study, we demonstrated that use of [3.3]PCP in place of [2.2]PCP enhanced the initial CS rate. Lower oxidation potentials and a smaller reorganization energy for [3.3]PCP are shown to be key factors for this enhanced CS rate. Both of these properties are closely related to the strained structure of PCP; hence, the present results demonstrate the importance of strain in ET chemistry.
authors: The Institute of Scientific and Industrial Research (SANKEN), Osaka University , Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors: Mamoru
authors: M
authors: Fujitsuka
authors: Institute for Materials Chemistry and Engineering (IMCE), Kyushu University , Hakozaki 6-10-1, Fukuoka 812-8581, Japan.
authors: Takaaki
authors: T
authors: Miyazaki
authors: The Institute of Scientific and Industrial Research (SANKEN), Osaka University , Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors: Chao
authors: C
authors: Lu
authors: Institute for Materials Chemistry and Engineering (IMCE), Kyushu University , Hakozaki 6-10-1, Fukuoka 812-8581, Japan.
authors: Teruo
authors: T
authors: Shinmyozu
authors: The Institute of Scientific and Industrial Research (SANKEN), Osaka University , Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors: Tetsuro
authors: T
authors: Majima