From Chromium–Chromium Quintuple Bonds to Molecular Squares and Porous Coordination Polymers

Abstract

Reaction of the quintuply bonded chromium(I) dimer [ApCrCrAp] (Ap = sterically demanding 2-aminopyridinate) with pyrazine yields a chromium(II) complex with a η(4):η(4) face-on coordinated pyrazine dianion. Reaction with 4,4'-bipyridine, on the other hand, completely cleaves the metal-metal bond, leading to a chromium(II)-based molecular square. XRD and magnetic measurements show ligand radical anions and a ferrimagnetic alignment of alternating metal and ligand magnetic moments. Controlled polymerization of the molecular square with pyrazine yields a porous coordination polymer featuring both reduced and nonreduced linkers.