Combinatorial experimental and DFT theoretical investigation over the formation mechanism of a binuclear phthalocyanine dimer

Herein, a density functional calculation method was used to explore the formation mechanism of a metal-free, homobinuclear phthalocyanine dimer. The result not only well rationalizes the Pc dimer formation starting from 1,2-diamino-9,10,16,17,23,24-hexa-(2,6-dimethylphenoxy)-tribenzotetrazaporphyrin (1-OR) through an intricate pathway but, more importantly, also predicts the formation of ammonia during the reaction process; this results in the successful experimental detection of NH4+ in the acidic reaction system. Further experimental efforts have facilitated the isolation of one of the theoretically revealed reaction intermediates di-[2-amino-7,8,14,15,21,22-hexa-(2,6-dimethylphenoxy)-tribenzotetrazaporphyrinato]-amine (9-OR); this indicates the significance of combining experimental with DFT calculation method towards clarifying the reaction mechanisms.