Synthesis, crystal structure and magnetic properties of mer-tricyanidoiron(III) precursor-based 1D heterobimetallic complexes

Abstract

Three new cyanide-bridged heterometallic complexes {{[Cu(S,S-Chxn)2][Fe(bbp)(CN)3]}2·2 H2O} n (1), {{[Cu(R,R-Chxn)2][Fe(bbp)(CN)3]}2·2 H2O} n (2) and {{[Cu(Cycam)][Fe(bbp)(CN)3]}·CH3OH·2 H2O} n (3) (bbp = bis(2-benzimidazolyl)pyridine dianion, Chxn = 1,2-diaminocyclo hexane, cyclam = 1,4,8,11-tetraazacyclodecane) have been assembled from the rarely used mer-tricyanidoiron(III) building block [PPh4]2[Fe(bbp)(CN)3] and three copper(II) compounds. The complexes have been characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. For the chiral enantiomers 1 and 2, the circular dichroism (CD) spectrum was also investigated. X-ray structural analyses revealed that the structures of the cyanide-bridged Fe-Cu complexes 1 and 2 are characterized by two crystallographically independent but structurally very similar homochiral neutral chains, each consisting of the repeating units {[Cu(S,S-Chxn)2][Fe(bbp)(CN)3]} (1) or {[Cu(R,R-Chxn)2][Fe(bbp)(CN)3]} (2). The crystal structure of 3 likewise is build up of chains consisting of {[Cu(Cyclam)][Fe(bbp)(CN)3]} building blocks. The temperature-dependent magnetic susceptibility and field dependent magnetization of the complexes showed antiferromagnetic interactions in complex 1 between the Fe(III) and Cu(II) ions, while complex 3 is ferromagnetic, indicating that the magnetic coupling through cyanide linkage is very sensitive to the structure parameters around the paramagnetic metal ions. These results have been further confirmed by fitting of the experimental data using a uniform chain model, leading to the coupling constants J = −6.35 cm−1, g = 2.08, R = 4.42 × 10−4 and J = 1.24 cm−1, g = 2.09, R = ∑(χ obsd T − χ cald T)2/∑(χ obsd T)2 = 4.67 × 10−4 for complexes 1 and 3, respectively.