||Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular circuit
Oh, Juwon ,
Mori, Hirotaka ,
Sung, Young Mo ,
Kim, Woojae ,
Osuka, AtsuhiroKim, Dongho
2245 , 2016-03 , Royal Society of Chemistry
The switching phenomena of conformation with π-electronic network through deprotonation-protonation processes were investigated by employing a series of 5, 20-bis(α-oligothienyl) substituted hexaphyrins(22.214.171.124.1.1). They showed significant changes in the absorption and emission spectra with deprotonation, and returned to the initial state with protonation. Through NMR measurements and single crystal X-ray diffraction analysis, we found that the 5, 20-bis(α-oligothienyl) substituted hexaphyrins, which possess acyclic, helical electronic networks involving oligothienyl chains in dumbbell conformations (type-I) in a neutral form, underwent effective deprotonation upon treatment with tetrabutylammonium fluoride (TBAF) to generate the corresponding dianions, which display cyclic electronic networks with enhanced aromaticity in rectangular conformations (type-II). Our quantum calculation results provide an unambiguous description for the switchable conformation and π-conjugation, which revealed that a deprotonation-induced enhanced aromatic conjugation pathway is involved in the switchable π-electronic network.