Assembly of Hybrid Inorganic−Organic Materials from Octahedral Nb6 Clusters and Metal Complexes

Abstract

The octahedral edge-bridged niobium cyano-chloride cluster [Nb6Cl12(CN)6]4- and the [Mn(salen)]+ metal complex have been used as building units to prepare solid-state materials with extended frameworks at room temperature through self-assembly processes. Three materials with different dimensionalities were prepared and characterized: (Me4N)4[Nb6Cl12(CN)6]·2MeOH (1) (0D), (Me4N)2[Mn(salen)]2[Nb6Cl12(CN)6] (2) (2D), and (Et4N)2[Mn(salen)(MeOH)]2[Nb6Cl12(CN)6]·2MeOH (3) (1D). 1 was used as cluster precursor for the preparation of 2 and 3. The framework dimensionality seems to be affected by the size of the template-counterion used. Single-crystal X-ray analysis revealed that 1 is based on discrete [Nb6Cl12(CN)6]4- separated by (Me4N)+ and MeOH molecules. 2 has a two-dimensional framework, in which each layer is formed by [Nb6Cl12(CN)6]4- clusters connected through four cyanide ligands to four different [Mn(salen)]+. Each manganese complex connects two clusters through Nb−CN−Mn−NC−Nb bridges, leading to the ...