Synthesis and electron donating property of novel porphyrazines containing tetrathiacrown ether-linked tetrathiafulvalene moieties

Novel magnesium and metal-free porphyrazines (4 and 5) containing four peripheral tetrathiacrown ether-linked tetrathiafulvalene moieties have been synthesized and characterized. Their solution electrochemical data showed two reductive and three oxidative processes within a −1500 mV to +1500 mV potential window. UV/Vis spectroscopy and electron paramagnetic resonance (EPR) measurements reveal the formation of a charge-transfer complex between porphyrazine 4 with F4TCNQ. The single-crystal structure of the TTF-dicyanocrown ether 3 is presented.