Magnetostructural characterization of copper(II) hydroxide dimers and coordination polymers coordinated to apical isothiocyanate and cyanide-based counteranions

Abstract

Five Cu(II) hydroxo-bridged complexes of the type [Cu2(μ-OH)2(L)2][A]x·yH2O (where L = 1,10-phenanthroline, A = NCS–, x = 2, y = 2 (1); L = 2,2′-bipyridine, A = NCS–, x = 2, y = 1 (2); L = 2,2′-bipyridine, A = [Au(CN)4]–, x = 2, y = 0 (3) and 2 (4); L = N,N,N′,N′-teteramethylethylenediamine, A = [Pt(SCN)4]2–, x = 1, y = 0 (5)) have been prepared and have been characterized by elemental analysis, IR and Raman spectroscopy, X-ray crystallography, and SQUID magnetometry. Complexes 1 and 2 consist of five-coordinate Cu(II) hydroxo-bridged dinuclear units bound to two NCS– anions in the apical positions, 3 and 4 are pseudo-polymorphs of a Cu(II) hydroxo-bridged dimer core with [Au(CN)4]– counteranions, and 5 is a coordination polymer of Cu(II) hydroxo-bridged dimers with trans-bridging [Pt(SCN)4]2– anions coordinated in the apical position of the five-coordinate Cu(II) centres. The magnetic susceptibility versus temperature for each system was measured, fit to obtain J-coupling values (which range from –0.37 to 17.8 cm−1), and qualitatively compared to known magnetostructural correlation parameters.