Metal effects on electronic structures of directly linked tribenzotetraazachlorin-fullerene conjugates

摘要

Mixed condensation of 1,2-dicyanofullerene (1) and 4,5-dibutyloxyphthalonitrile (2a) in the presence of vanadium(Ill) chloride (VCl3) in quinoline forms the hexabutyloxy-substituted tribenzotetraazachlorin (TBTAC) - fullerene (C-60) vanadyl complex (3). UV-vis absorption and magnetic circular dichroism (MCD) spectroscopy demonstrated that 3 shows two intense Q-band components, whereas the previously reported nickel complex possessing the identical peripheral substituents (4) shows one intense and two medium-intense bands in the 600-800 nm region, indicating that the electronic mixing states of 3 are different from those of the nickel complex (4). The metal effects on electronic structures of the conjugates were interpreted using density functional theory (DFT) calculations.