Cluster-based networks: 1D and 2D coordination polymers based on {MnFe2(μ3-O)}-type clusters.

A straightforward approach to heterometallic Mn–Fe cluster-based coordination polymers is presented. By employing a mixed-valent μ3-oxo trinuclear manganese(II/III) pivalate cluster, isolated as [MnIIMnIII2O(O2CCMe3)6(hmta)3]·(solvent) (hmta = hexamethylenetetramine; solvent = n-propanol (1), toluene (2)) in the reaction with a μ3-oxo trinuclear iron(III) pivalate cluster compound, [Fe3O(O2CCMe3)6(H2O)3]O2CCMe3·2Me3CCO2H, three new heterometallic {MnIIFeIII2} cluster-based coordination polymers were obtained: the one-dimensional polymer chain compounds {[MnFe2O(O2CCMe3)6(hmta)2]·0.5MeCN}n (3) and {[MnFe2O(O2CCMe3)6(hmta)2]·Me3CCO2H·(n-hexane)}n (4) and the two-dimensional layer compound {[MnFe2O(O2CCMe3)6(hmta)1.5]·(toluene)}n (5). Single-crystal X-ray diffraction analysis reveals a μ3-oxo trinuclear pivalate cluster building block as the main constituent in all polymer compounds. Different M:hmta ratios in 1–5 are related to the different structural functions of the N-containing ligand. In clusters 1 and...