Stereochemistry and chiroptical properties of bimetallic single helicates of hexapyrrole-α,ω-dicarbaldimines with high diastereoselectivity

Abstract

Bimetallic complexes of hexapyrrole-[Formula: see text],[Formula: see text]-dicarbaldimines consisting of a pair of four-coordinate metal sites adopt a helical closed [Formula: see text]-symmetric form or sigmoidal open forms depending on whether the 2,2[Formula: see text]-bipyrrole subunit at the center of the hexapyrrole chain takes cis- or trans-conformation. X-ray crystallography of a bisNi complex having N-[([Formula: see text]-1-cyclohexylethyl]carbaldimine units at both ends of the hexapyrrole chain revealed a non-symmetric heterohelical open form where the metal coordination sites of opposite helical sense sit on opposite sides of the central 2,2[Formula: see text]-bipyrrole subunit. BisPd complexes preferred a closed [Formula: see text] form and a steric bulk at the 3,3[Formula: see text]-position of the 2,2[Formula: see text]-bipyrrole subunit improved the helical sense bias. A bisPd complex with N-[([Formula: see text]-1-cyclohexylethyl]carbaldimine units adopts a helical closed [Formula: see text] form exclusively with full bias for a [Formula: see text]-helical sense. These bimetallic single stranded helicates were reversibly oxidized to [Formula: see text]-cation radicals at 0.1[Formula: see text]0.3 V vs. a ferrocene/ferrocenium couple and spectroelectrochemistry revealed remarkable absorption and CD spectral changes in the Vis-NIR region.