Synthesis of directly fused porphyrin dimers through Fe(OTf)3-mediated oxidative coupling.

An efficient and general Fe(OTf)3-mediated oxidative coupling method was developed for the synthesis of doubly or triply linked porphyrin dimers. Besides the central metal and peripheral substituent, regioselectivity of the oxidative coupling was found to be closely relevant to the onset oxidation potential of the porphyrin substrate, and the reactant with higher E(onset(ox)) tends to generate meso-ß doubly fused porphyrin dimer.

Switchable regioselectivity in the PIFA-BF3·Et2O mediated oxidative coupling of meso-brominated Ni(II) porphyrin.

A simple and efficient method has been developed for the switchable synthesis of directly linked meso-brominated Ni(II) porphyrin dimers through PIFA-BF3·Et2O mediated oxidative coupling. The respective syntheses of meso-meso or meso-ß singly, doubly, and triply linked porphyrin dimers can be easily realized with the same reagent system.