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

The cyano-bridged [Cu-II(tetrenH(2))](2)[W-IV(CN)(8)](2).5H(2)O (tetren = tetraethylenepentaamine) (1), [Cu-II(tetrenH(2))][Cu-II(tetrenH)][W-V(CN)(8)][W-IV(CN)(8)].2.5H(2)O (2), [Cu-II(dien)](2)[W-IV(CN)(8)].4H(2)O (dien = diethylenetriamine) (3) and its isomorphous molybdenum(iv) analogue (4) have been prepared and structurally characterised. I and 2 are built from the W2Cu2(mu-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 Cu-II spins S = 1/2 with a very weak antiferromagnetic coupling through the diamagnetic NC-W-IV CN bridges in the low temperatures. Assembly 2 exhibits a weak ferromagnetic interaction between Cu-II and W-v isolated by diamagnetic [W-IV(CN)(8)](4-) spacer from another Cu-II centre within W-v-CN-Cu-II-NC-W-IV-CN-Cu-II unit and the antiferromagnetic interaction between the (CuIIWWIV)-W-2-W-v units.