Fukuzumi Shunichi, Yoshida Yutaka, Okamoto Ken, Imahori Hiroshi, Araki Yasuyuki, Ito Osamu
Department of Material and Life Science, Graduate School of Engineering, Osaka University, CREST, Japan Science and Technology Corporation (JST), 2-1, Yamada-oka, Suita, Osaka 565-0871, Japan.
J Am Chem Soc. 2002 Jun 19;124(24):6794-5. doi: 10.1021/ja0157604.
A newly designed ferrocene-quinone dyad with an amide space (Fc-Q) is employed to examine formation of the hydrogen bonding in the one-electron reduced form (Q*-) and the dynamics in the photoinduced electron-transfer reaction from the ferrocene to the quinone moiety. Photoexcitation of the Q moiety in Fc-Q in deaerated PhCN with 388 nm results in intramolecular electron transfer from Fc to the singlet excited state of Q to produce Fc+-Q*- without changing the conformation (<1 ps), followed by hydrogen bond formation with the amide proton of the spacer (tau = approximately 5 ps). The resulting radical ion pair decays via a back electron transfer to the ground state at a longer time scale with a rate constant of 2.6 x 108 s-1.
一种新设计的带有酰胺间隔基的二茂铁-醌二元体系（Fc-Q）被用于研究单电子还原形式（Q* -）中氢键的形成以及从二茂铁到醌部分的光诱导电子转移反应中的动力学。在脱气的苯腈中用388 nm光激发Fc-Q中的Q部分，导致分子内电子从Fc转移到Q的单重激发态，产生Fc + -Q* -，且构象不变（<1 ps），随后与间隔基的酰胺质子形成氢键（τ约为5 ps）。产生的自由基离子对在更长的时间尺度上通过反向电子转移衰减到基态，速率常数为2.6×108 s-1。
