Hydrothermal Syntheses, Crystal Structures, and Properties of Two-Dimensional Homo- and Heterometallic Cyanide-Bridged Complexes: [Cu2(CN)2 (bpym)] and [Fe(bipy)2(CN)4Cu2] (bpym = 2,2-Bipyrimidine, bipy = 2,2-Bipyridine)

The hydrothermal reaction of K3[Fe(CN)6], CuCl2, and 2,2ʹ-bipyridine (bipy) resulted in the formation of a 2D cyanide-bridged heterobimetallic Fe(II)-Cu (I) complex, [Fe(bipy)2(CN)4Cu2], 1. Working in the same conditions, but using 2,2ʹ-bipyrimidine (bpym) instead of bipy and methanol as solvent, we obtained the homometallic Cu(I) complex [Cu2(CN)2(bpym)]2, 2. The structure of 1 consists of cyanide-bridged Fe(II)-Cu(I) layers, constructed from alternately fused 6 (Fe2Cu4) and 10 (Fe2Cu8) metal-membered centrosymmetric rings, in which copper(I) and iron(II) ions exhibit distorted trigonal planar and octahedral cooordination environments, respectively. The formation of 1 can be explained by assuming that, under high pressure and temperature, iron(III) and copper(II) ions are reduced with the simultaneous and/or subsequent substitution of four cyanide ligands by two bipy molecules in the ferricyanide anions. It is interesting to note that 1 is the first cyanide-bridged heterobimetallic complex prepared by solvothermal methods. The structure of 2 consists of neutral 2D honeycomb layers constructed from fused Cu6(CN)4(bpym)2 rings, in which copper(I) atoms exhibit distorted tetrahedral geometry. The isolation of 1 and 2, by using K3[Fe(CN)6] as starting material, demonstrates that hydrothermal chemistry can be used not only to prepare homometallic materials but also to prepare cyanide-bridged bimetallic materials. The temperature dependence of (chi)MT and Mossbauer measurements for 1 reveal the existence of a high spin (left right arrow) low spin equilibrium involving the Fe(II) ions.