Synthesis, Crystal Structures and Magnetic Properties of a Linear Trinuclear Cu(II) Complex [Cu₃(ClCH₂COO)₆(bpy)₂] and a Dinuclear Complex [Cu₂(bpy)₂(μ‐OH)(μ‐OH₂) (μ‐ClCH₂COO)](ClO₄)₂

Abstract

Two new triply bridged Cu(II) compounds [Cu3(bpy)2(μ‐ClCH2COO)6] (1) and [Cu2(bpy)2(μ‐OH)(μ‐OH2)(μ‐ClCH2COO)](ClO4)2 (2) (where, bpy=2,2’‐bipyridine) have been synthesized and their magnetic properties have been measured and correlated with structure. Compound 1 is a novel centrosymmetric tricopper compound with only carboxylate bridges. The terminal Cu2+ ions have [5 + 1] coordination while the central ion has [4 + 2] coordination. The three centres are antiferromagnetically coupled, the exchange parameters for the neighbouring and distant pairs of Cu(II) atoms being 2 J=–28.6 cm–1 and 2 J'=–1.0 cm–1, respectively. In compound 2 three types bridging modes are observed, viz., hydroxo, aquo and carboxylato. The two Cu(II) centers are ferromagnetically coupled (2 J=73.8 cm–1) as previously observed for several di‐copper complexes with the same bridges. DFT calculations are in reasonable agreement with the magnetic exchange parameters for both dinuclear and trinuclear compounds.