Experimental and theoretical study of the exited state of aminostyryl terpyridine derivatives: hydrogen-bonding effects.

The synthesis, structure and photophysical behavior of the aminostyryl terpyridine derivatives, named 4'-(4-{2-[4-(N,N-dimethylaniline)]vinyl}phenyl)-2,2':6',2″-terpyridine (M(1)) and the related model compounds 4'-(4-{2-[4-(N,N-diphenylammino)phenyl]vinyl}phenyl)-2,2':6',2″-terpyridine (M(2)), respectively, are reported. Large solvatochromic shifts of the first excited-state fluorescence maximum suggest the intramolecular charge transfer characters for both compounds. In addition, with N,N-dimethyl substituents, its fluorescence is quenched a lot in protic solvents. This is consisted with the decay of its S(1) state, through nonradiative internal conversion, to the ground state, which is facilitated by the formation of the hydrogen bond between M(1) and alcohols. Whereas, the introduction of N,N-diphenyl substituents has been proved to be a hydrogen-bond-free case with the unchanged Φ(f). Furthermore, the formation of TICT state via diffusive twisting motion of the dimethyl/phenylamino group is the major relaxation process, which is proved by the ultrafast relaxation dynamics experiment and theoretically conformational optimization of the first excited-state of both the compounds.