| Abstract |
The new one-dimensional (1D) mixed-valence copper(I/II) coordination polymer [Cu-3(mu-HCOO)(2)(HCOO)(3)(mu-PTA)(3)(PTA)](n)center dot nH(2)O (1) has been obtained from copper(II) formate, copper(0) powder, and 1,3,5-triaza-7-phosphaadamantane (PTA) in MeCN medium. It has been characterized by IR, H-1, and P-31\H\ NMR and EPR spectroscopy, and elemental, differential thermal, powder, and single-crystal X-ray diffraction analysis. The latter features the intricate bitubular 1D chains composed of the novel tetracopper(II) \Cu-4(mu-HCOO)(4)(HCOO)(6)\(2-) blocks that are multiply assembled by copper(I) \mu(3)-Cu(PTA)(4)\(+) units. The topological analysis of 1 discloses a binodal 3,3-connected network with the unprecedented topology described by the point symbol of (4.6.8)(2)(4(2).6). The magnetic susceptibility of 1 has been studied and described by a model that considers independent contributions of tetracopper(II) \Cu-4(mu-HCOO)(4)(HCOO)(6)\(2-) blocks, with global antiferromagnetic exchange between the outer (J = -23(2) cm(-1)) and inner (J = -112(3) cm(-1)) pairs of copper atoms. Compound 1 widens the still limited family of PTA-driven coordination polymers, also representing the first homometallic mixed-valence derivative bearing this cagelike aminophosphine building block. |
