Structures, magnetic properties, and XPS of one-dimensional cyanide-bridged CuII–NiII/PtII bimetallic assembly complexes

Synthesis, crystal structures, and spectroscopic and magnetic properties of new one-dimensional cyano-bridged bimetallic complexes, [CuII(N-Eten)2][MII(CN)4] (N-Eten = N-ethylethylenediamine; MII = NiII (1) and PtII (2)), have been reported. Both complexes consist of one-dimensional alternate chains of CuII and MII moieties. The Pt–C bond distances of 1.997(3) and 2.001(3) Å for 2 are considerably longer than the Ni–C bond lengths of 1.866(3) and 1.872(3) Å for 1. Because of pseudo Jahn–Teller distortion, the axial Cu–N bond distances of 2.554(2) and 2.550(3) Å for 1 and 2 are longer than those of equatorial ones of 2.008(2) and 2.056(2) Å for 1 and 2.010(2) and 2.054(2) Å for 2. In contrast to MII–C bond distances, the Cu–N ones of 1 are similar to those of 2 regardless of element-substitution. These complexes indicate weak antiferromagnetic interactions with Weiss constants = − 4.68 and −3.95 K for 1 and 2, respectively. The emission spectrum of 2 (λex = 360 nm) exhibits a broad band with peaks at 22 800 and 24 000 cm−1 at 298 K. The Cu 2p1/2 and 2p3/2 peaks of XPS spectra are compared systematically to various copper(II) complexes showing different bridging features or distorted coordination geometries as models for excited structures induced by external physical conditions. The spectroscopic properties are discussed from the viewpoint of magneto-optical properties.