Conformational Changes and Redox Properties of Bimetallic Single Helicates of Hexapyrrole-α,ω-dicarbaldehydes

Abstract

The hexapyrrole-α,ω-dicarbaldehydes 1 a and 1 b were metallated with Cu^II , Ni^II , and Pd^II to give bimetallic complexes where a pair of 3 N+O four-coordinate metal planes are helically distorted and the central 2,2'-bipyrrole subunit adopts a cis or trans conformation. X-ray crystallographic analysis of the bisCu complex revealed a closed form with a cis-2,2'-bipyrrole subunit and an open form with a trans-2,2'-bipyrrole subunit. The bisPd complexes took a closed form both in the solid state and in solution. They are regarded as single helicates of two turns and the energy barrier for the interchange between an M helix and a P helix was remarkably influenced by the bulky 3,3'-substituent of the central 2,2'-bipyrrole subunit. Although the bisNi complexes adopt a closed form in the solid state, they exist as a homohelical open C₂ -symmetric form or a heterohelical open C_i -symmetric form in solution. A theoretical study suggested that the closed form of 1 aPd was stabilized by the Pd-Pd interaction. Compound 1 aPd was reversibly oxidized by one electron at 0.14 V versus ferrocene/ferrocenium (Fc/Fc⁺ ) and this oxidized species showed Vis/NIR absorption bands at λ=767 and 1408 nm.

Keywords: NIR absorption; foldamers; helical structures; metal-metal interactions; oligopyrroles; redox chemistry.