Synthesis and Structural Characterization of meso ‐Thienyl Core‐Modified Porphyrins

A series of meso ‐thienyl‐substituted porphyrins with different porphyrin cores such as N 3 S, N 2 S 2 and N 3 O were synthesized and characterized. The thienyl groups at the meso ‐carbon atoms change the electronic properties of the porphyrin ring. The X‐ray structure solved for the N 2 S 2 porphyrin with four meso ‐thienyl groups showed supramolecular assembly formation in the solid state due to C−H ··· N hydrogen bonding between the CH group of the meso ‐thienyl group of one porphyrin ring with the pyrrole N atom of another porphyrin ring. The X‐ray analysis of the N 3 S porphyrin with two meso ‐thienyl groups and two meso ‐aryl groups did not show any supramolecular assembly formation in the solid state. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)