Abstract
This work discusses a new heterobimetallic nickel(II)–copper(II) complex of the formula [Ni(tpa)Cu(opba)]2·6H2O (1) {H4opba = N,N′‐1,2‐phenylenebis(oxamic acid) and tpa = tris(2‐pyridylmethyl)amine}. The molecular structure of 1 consists of neutral tetranuclear species with a 4R rack‐type architecture featuring two NiIICuII dinuclear units connected through two out‐of‐plane oxo(carboxylate‐oxamate) atoms from the opba ligands. The crystal packing of 1 exhibits a supramolecular 1D arrangement of tetranuclear entities connected by hydrogen bonds and π–π stacking interactions. The dc magnetic properties of 1 were interpreted according to its dimer‐of‐dimer structure; the spin Hamiltonian being defined as {H = –J[SNi1·SCu1 + SNi1ⁱ·SCu1ⁱ – jeff(SCu1·SCu1ⁱ)]}. The analysis of the magnetic data shows the occurrence of a strong intradimer antiferromagnetic coupling between the NiII and CuII ions [J = –115.2(4) cm–1] and a weak interdimer antiferromagnetic coupling between the CuII ions [jeff = –1.12(7) cm–1]. DFT‐type calculations were performed to visualize the exchange pathway through the oxamate bridge and substantiate the value of J.
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