Coordination polymers based on octacyanometalates(IV,V)(M = Mo, W) and aliphatic polyamine copper(II) tectons with [N3] donor atom sets

The cyano-bridged [CuII(tetrenH2)]2[WIV(CN)8]2·5H2O (tetren = tetraethylenepentaamine)(1), [CuII(tetrenH2)][CuII(tetrenH)][WV(CN)8] [WIV(CN)8]·2.5H2O (2), [CuII(dien)]2[WIV(CN)8]·4H2O (dien = diethylenetriamine)(3) and its isomorphous molybdenum(IV) analogue (4) have been prepared and structurally characterised. 1 and 2 are built from the W2Cu2(µ-CN)4 squares extended into 1-D structure by cyano-bridges. 2-D 3 and 4 form a square grid pattern with tungsten atoms in the corners and -CN-Cu(dien)-NC- linkages on the edges of the squares. The magnetic behaviour of 1 and 3 indicates the presence of two isolated CuII spins S= 1/2 with a very weak antiferromagnetic coupling through the diamagnetic NC-WIV-CN bridges in the low temperatures. Assembly 2 exhibits a weak ferromagnetic interaction between CuII and WV isolated by diamagnetic [WIV(CN)8]4- spacer from another CuII centre within WV-CNCuII-NC-WIV-CN-CuII unit and the antiferromagnetic interaction between the CuII2WVWIV units.