Unraveling the formation mechanism of subphthalocyanine. Density functional theory studies
Abstract A systematic investigation over the formation mechanism of the subphthalocyanine, SubPc(Cl), with phthalonitrile as the initial reagent mediated by boron trichloride in the solvent of p -xylene has been carried out on the basis of density functional theory, revealing truly a long reaction pathway containing twenty-three elementary reactions. The calculation results well reproduce and rationalize the experimental findings including the selection of high boiling point reaction media of p -xylene, employment of excessive amount of BCl 3 reagent, and liberation of Cl 2 during the reaction process. In particular, the crucial catalytic nature of BCl 3 has been clearly disclosed: in addition to activating the cyano groups, boron trichloride also works as chloride-transfer shuttle to prompt the reactions occurring and proceeding. The present result will put forwards the exploration over the formation mechanisms of phthalocyanines and porphyrins. Highlights The results rationalize the optimized molar ratio between the two reagents. The rate determine steps of SubPcs synthesis are clarified through calculation. The catalysis role of BCl 3 in Cl-transfer shuttle manner is revealed. Graphical abstract Through several key steps including activation, oligomerization, dechlorination, cyclization, and ring closure, the subphthalocyanine (SubPc) macrocycle is finally generated from phthalonitrile along with the liberation of Cl 2 . Boron trichloride has been revealed to play a crucial role in the whole reaction route, not only as reagent and template but also as catalyst. [DISPLAY OMISSION]
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