Synthesis, structures, and photoinduced electron transfer reaction in the 9,9'-spirobifluorene-bridged bipolar systems.
[reaction: see text] A series of 9,9'-spirobifluorene-bridged bipolar compounds DnAm bearing various n:m ratios for triarylamine (D) versus 1,3,4-oxadiazole-conjugated oligoaryl moiety (A) have been synthesized to investigate the corresponding photoinduced electron transfer (PET) property. The excitation behaviors were probed by steady-state absorption, emission, fluorescence solvatochromism, and femtosecond fluorescence up-conversion spectroscopy. The overall reaction dynamics can be rationalized by the rate of PET, in combination with solvent relaxation dynamics. It was found that the rate of PET is dependent on the anchored D/A ratio. The rate of D1A1 and D2A1 was resolved to be approximately 2.44 x 10(12) and 2.32 x 10(12) s(-)(1), respectively, while it is irresolvable in D1A2 and D2A2 (>6.6 x 10(12) s(-)(1)). In another approach, based on the comprehensive X-ray data, cyclic voltammetry, and absorption/emission spectra, the rate of photoinduced electron transfer was also qualitatively estimated. Fair comparisons were made between experimental and theoretical approaches to gain detailed insight into the PET for the titled systems.
Wong
Ken-Tsung
KT
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan. kenwong@ntu.edu.tw
Ku
Sung-Yu
SY
Cheng
Yi-Ming
YM
Lin
Xiauo-Yun
XY
Hung
Ying-Yueh
YY
Pu
Shih-Chieh
SC
Chou
Pi-Tai
PT
Lee
Gene-Hsiang
GH
Peng
Shie-Ming
SM