Rare tetranuclear mixed-valent [Mn(II)2Mn(IV)2] clusters as building blocks for extended networks.

We report the synthesis of a series of mixed valence Mn(II/IV) tetranuclear clusters [Mn(II)2Mn(IV)2O2(heed)2(EtOH)6Br2]Br2 (1), [Mn(II)2Mn(IV)2O2(heed)2(H2O)2Cl4].2EtOH.H2O (2.2EtOH.H2O), [Mn(II)2Mn(IV)2O2(heed)2(heedH2)2](ClO4)4 (3), [Mn(II)2Mn(IV)2O2(heed)2(MeCN)2(H2O)2(bpy)2](ClO4)4 (4) and [Mn(II)2Mn(IV)2O2(heed)2(bpy)2Br4].2MeOH (5.2MeOH). Clusters 1-5 are constructed from the tripodal ligand N,N-bis(2-hydroxyethyl)ethylene diamine (heedH2) and represent rare examples of tetranuclear Mn clusters possessing the linear trans zig-zag topology, being the first Mn(II/IV) mixed-valent clusters of this type. The molecular clusters can then be used as building blocks in tandem with the (linear) linker dicyanamide ([N(CN)2]-, dca-) for the formation of a novel extended network {[Mn(II)2Mn(IV)2O2(heed)2(H2O)2(MeOH)2(dca)2]Br2}n (6), which exhibits a rare form of the 2D herring bone topology.