Side-Chain Coordination Polymers Containing Redox-Active Pendants: Complexation of Ferrocene-Based Bidentate Ligands with M(hfac)2 (hfac=1,1,1,5,5,5-Hexafluoroacetylacetonate, M = Mn, Ni, Cu, Zn) and CuX (X = I, Br)
Coordination polymers with redox active pendants, {5-ferrocenylpyrimidine.M(hfac)(2)}(n) [M=Mn (1a), Ni (1b), Cu (1c), Zn (1d)] and {5-ferrocenylpyrimidine.CuX}(n) [X=I (2a), Br (2b)], have been prepared and characterized. In complex 1c, the Cu(II) ions are linked by the bridging ligands to form one-dimensional chains. This complex was shown to exhibit an antiferromagnetic intra-chain interaction, which was analyzed by the Bonner-Fisher model (2J/k(B) = -6.3 K). Complex 2a shows a two-dimensional sheet-like structure, in which one-dimensional chains, consisting of the Cu(I) ions and the ligands, are further bridged by iodide anions. These compounds show quasi-reversible redox processes of the ferrocenyl groups in the solid state.
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