Structure and magnetism of [M3](6/7+) metal chain complexes from density functional theory: analysis for copper and predictions for silver.

摘要: The ground-state electronic structure of the trinuclear complex Cu3(dpa)4Cl2 (1), where dpa is anion di(2-pyridyl)amine, has been investigated within framework density functional theory (DFT) and compared with that obtained for other known M3(dpa)4Cl2 complexes (M = Cr, Co, Ni) still hypothetical Ag3(dpa)4Cl2 compound. Both coinage metal compounds display three singly occupied x2−y2-like (δ) orbitals oriented toward nitrogen environment each atom, generating antibonding M−(N4) interactions. All orbital combinations are doubly occupied, resulting in no delocalized metal−metal bonding. This at variance symmetric first transition series, which all some bonding through backbone, formal bond multiplicity decreasing order Cr > Co Ni. An antiferromagnetic coupling develops between MOs via a superexchange mechanism involving bridging ligand...