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Published on: August 2, 2019
Switchable π-electronic network of bis(α-oligothienyl)-substituted hexaphyrins between helical versus rectangular
Juwon Oh1, Hirotaka Mori2, Young Mo Sung1
1Spectroscopy Laboratory for Functional π-Electronic Systems , Department of Chemistry , Yonsei University , 50 Yonsei-ro , Seoul 120-749 , Korea .
Abstract:
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(1.1.1.1.1.1). 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.
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