title: Meta conjugation effect on the torsional motion of aminostilbenes in the photoinduced intramolecular charge-transfer state.
abstract: The photochemical behavior of a series of trans-3-(N-arylamino)stilbenes (m1, aryl = 4-substituted phenyl with a substituent of cyano (CN), hydrogen (H), methyl (Me), or methoxy (OM)) in both nonpolar and polar solvents is reported and compared to that of the corresponding para isomers (p1CN, p1H, p1Me, and p1OM). The distinct propensity of torsional motion toward a low-lying twisted intramolecular charge-transfer (TICT) state from the planar ICT (PICT) precursor between the meta and para isomers of 1CN and 1Me reveals the intriguing meta conjugation effect and the importance of the reaction kinetics. Whereas the poor charge-redistribution (delocalization) ability through the meta-phenylene bridge accounts for the unfavorable TICT-forming process for m1CN, it is such a property that slows down the decay processes of fluorescence and photoisomerization for m1Me, facilitating the competition of the single-bond torsional reaction. In contrast, the quinoidal character for p1Me in the PICT state kinetically favors both fluorescence and photoisomerization but disfavors the single-bond torsion. The resulting concept of thermodynamically allowed but kinetically inhibited TICT formation could also apply to understanding the other D-A systems, including trans-4-cyano-4'-(N,N-dimethylamino)stilbene (DCS) and 3-(N,N-dimethylamino)benzonitrile (3DMABN).
authors.affiliation: Department of Chemistry, National Taiwan University, Taipei, Taiwan 10617. jsyang@ntu.edu.tw
authors.forename: Jye-Shane
authors.initials: JS
authors.lastname: Yang
authors.forename: Kang-Ling
authors.initials: KL
authors.lastname: Liau
authors.forename: Chun-Yi
authors.initials: CY
authors.lastname: Li
authors.forename: Mon-Yao
authors.initials: MY
authors.lastname: Chen