Probing the rotational dynamics of meso-(2-substituted)aryl substituents in A2B-type subporphyrins.

Abstract

A2 B-type B-methoxy subporphyrins 3 a-g and B-phenyl subporphyrins 7 a-c,e,g bearing meso-(2-substituted)aryl substituents are synthesized, and their rotational dynamics are examined through variable-temperature (VT) (1) H NMR spectroscopy. In these subporphyrins, the rotation of meso-aryl substituents is hindered by a rationally installed 2-substituent. The rotational barriers determined are considerably smaller than those reported previously for porphyrins. Comparison of the rotation activation parameters reveals a variable contribution of ΔH(≠) and ΔS(≠) in ΔG(≠). 2-Methyl and 2-ethyl groups of the meso-aryl substituents in subporphyrins 3 e, 3 f, and 7 e induce larger rotational barriers than 2-alkoxyl substituents. The rotational barriers of 3 g and 7 g are reduced by the presence of the 4-dibenzylamino group owing to its ability to stabilize the coplanar rotation transition state electronically. The smaller rotational barriers found for B-phenyl subporphyrins than for B-methoxy subporphyrins indicate a negligible contribution of SN 1-type heterolysis in the rotation of meso-aryl substituents.