Spectroscopy and femtosecond dynamics of excited-state proton transfer induced charge transfer reaction.
Fluorescence spectroscopy and femtosecond relaxation dynamics of 2-{[2-(2-hydroxyphenyl)benzo[d]oxazol-6-yl]methylene}malononitrile (diCN-HBO) and 2-{[2-(2-hydroxyphenyl)benzo[d]thiazol-6-yl]methylene}malononitrile (diCN-HBT) are studied to probe the excited-state proton transfer (ESPT) coupled charge transfer (ESCT) reaction. Unlike most of the ESPT/ESCT systems previously designed, in which ESCT takes place prior to ESPT, both diCN-HBO and diCN-HBT undergo ESPT, concomitantly accompanied with the charge transfer process, such that the ESPT reaction dynamics are directly coupled with solvent polarization effects. The long-range solvent polarization interactions result in a solvent-induced barrier that affects the overall proton transfer reaction rate. In cyclohexane, the rate constant of ESPT of diCN-HBO is measured to be 1.1 ps (9.1 x 10(11) s(-1)), which is apparently slower than that of 150 fs for the parent molecule 2-(2'-hydroxyphenyl)benzoxazole (HBO). Upon increasing solvent polarity to, for example, CH 3CN, the rate of ESPT is increased to 300 fs (3.3 x 10(12) s(-1)). The results are rationalized by the stabilization of proton transfer tautomer, which possesses a large degree of charge transfer character via an increase of the solvent polarity, such that the corresponding solvent-induced barrier is reduced. We thus demonstrate a prototypical system in which the photon-induced nuclear motion (proton transfer) is directly coupled with solvent polarization and the corresponding mechanism is reminiscent of that applied in an electron transfer process.
Hsieh
Cheng-Chih
CC
Department of Chemistry, National Taiwan University, Taipei, 106, Taiwan, Republic of China.
Cheng
Yi-Ming
YM
Hsu
Chia-Jung
CJ
Chen
Kew-Yu
KY
Chou
Pi-Tai
PT