Probing the intrachain and interchain effects on the fluorescence behavior of pentiptycene-derived oligo(p-phenyleneethynylene)s.
The synthesis, crystal structure, and fluorescence behavior of acetylene-bridged pentiptycene dimer (2), trimer (3), and tetramer (4) are reported. For comparison, a phenylene-pentiptycene-phenylene three-ring system (5) is also investigated. As a result of the unique intrachain pentiptycene-pentiptycene interactions in 3 and 4, their twisted conformers are populated in polar solvents and at low temperatures, and the phenomenon of nonequilibration of excited rotational conformers is observed. Twisting of the pi-conjugated backbones leads to blue-shifted absorption and fluorescence spectra and increased fluorescence quantum yields and lifetimes. The fluorescence spectra of 2-4 undergo small red shifts but large intensity variations in the 0-1 vs 0-0 bands on going from solutions to thin solid films, which can be accounted for by the reabsorption effect. However, the reduction in fluorescence quantum yields for 2-4 in films vs solutions is mainly attributed to efficient interchain exciton migration to nonfluorescent energy traps. In contrast, the behavior of nonequilibration of excited rotamers is not observed for 5 in solutions. Compound 5 forms J-type aggregates through terminal phenylene pi-stackings in the solid state, resulting in a new absorption band at 377 nm and large red shifts of the structured fluorescence spectra.
Yang
Jye-Shane
JS
Department of Chemistry, National Taiwan University, Taipei, Taiwan 10617. jsyang@ntu.edu.tw
Yan
Jyu-Lun
JL
Hwang
Chung-Yu
CY
Chiou
Shih-Yi
SY
Liau
Kang-Ling
KL
Gavin Tsai
Hui-Hsu
HH
Lee
Gene-Hsiang
GH
Peng
Shie-Ming
SM