Conformational control of [26]hexaphyrins(1.1.1.1.1.1) by moso-thienyl substituents

Abstract

Conformational preference and chemical stability of meso-aryl-substituted [26]hexaphyrins(1.1.1.1.1.1) ([26]ArH) depend upon meso-aryl substituents. Although only a planar and rectangular conformation (type-II conformation) has been identified for [26]ArH so far, we have demonstrated here that a different conformation with all the pyrroles pointing inward (type-I conformation) is preferred for [26]ArH (7 and 11-I) bearing small 2-thienyl or 3-thineyl substituents at 15- and 30-positions. Both type-I and type-II [26]ArH exhibit diatropic ring currents, reflecting aromatic character. Type-I [26]ArH, such as 7 and 11-I, have been shown to serve as an effective ligand for PdII ions to provide bis-PdII complexes 12 and 13 with N3C 1 coordination through facile C-H bond activation. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.