Crystal structures, electron spin resonance, and thermogravimetric analysis of three mixed-valence copper cyanide polymers

The crystal structures of three mixed-valence copper cyanide alkanolamine polymers are presented, together with thermogravimetric analysis (TGA) and electron spin resonance (ESR) data. In all three structures, a CuII moiety on a crystallographic center of symmetry is coordinated by two alkanolamines and links two CuICN chains via cyanide bridging groups to form diperiodic sheets. The sheets are linked together by cuprophilic CuI – CuI interactions to form a three-dimensional network. In poly[bis( μ -3-aminopropanolato)tetra- μ -cyanido-dicopper(I)dicopper(II)], [Cu4(CN)4(C3H8NO)2]n, 1, propanolamine bases have lost their hydroxyl H atoms and coordinate as chelates to two CuII atoms to form a dimeric CuII moiety bridged by the O atoms of the bases with CuII atoms in square-planar coordination. The ESR spectrum is very broad, indicating exchange between the two CuII centers. In poly[bis(2-aminopropanol)tetra- μ -cyanido-dicopper(I)copper(II)], [Cu3(CN)4(C3H9NO)2]n, 2, and poly[bis(2-aminoethanol)tetra- μ -cyanido-dicopper(I)copper(II)], [Cu3(CN)4(CH7NO)2]n, 3, a single CuII atom links the CuICN chains together via CN bridges. The chelating alkanolamines are not ionized, and the OH groups form rather long bonds in the axial positions of the octahedrally coordinated CuII atoms. The coordination geometries of CuII in 2 and 3 are almost identical, except that the Cu — O distances are longer in 2 than in 3, which may explain their somewhat different ESR spectra. Thermal deco...

Source: Acta Crystallographica Section C - May 3, 2024 Category: Chemistry Authors: Corfield, P.W.R. Elsayed, A. DaCunha, T. Bender, C. Tags: crystal structure mixed valence copper cyanide ethanolamine propanolamine polymeric network electron spin resonance ESR thermogravimetric analysis TGA research papers Source Type: research