Supramolecular Heteropentamers As Building Blocks for Metal Organic Materials: Synthesis and Characterization of 1D and 2D 2-Fold Interpenetrated Frameworks

Reactions between (Me4N)4[Nb6Cl12(CN)6], [Mn(ACEN)Cl] (ACEN2- = bis(acetylacetonato)ethylenediamine), and dpyo (dpyo = 4,4′-dipyridyl-N,N′-dioxide) in different ratios led to the crystallization of two cluster-based metal-organic materials (CMOMs): {[Mn(ACEN)]2[Mn(ACEN)(MeOH)]2(Nb6Cl12(CN)6)(dpyo)}·2MeCN (1) and {[Mn(ACEN)]4(Nb6Cl12(CN)6)(dpyo)2}·MeCN·2MeOH·3.5H2O (2). Their crystal structures were determined by single-crystal X-ray diffraction. Both materials are built of neutral heteropentamers {[Mn(ACEN)]4[Nb6Cl12(CN)6]} in which the edge-bridged hexacyano octahedral metal cluster [Nb6Cl12(CN)6]4- is functionalized by four [Mn(III)(ACEN)]+ complexes. The supramolecular assemblies are connected to each other by the ditopic ligand, dpyo. In 1, each heteropentamer is trans-bridged by two dpyo linkers to give a neutral chain. Hydrogen bonds between nonbridging cyanides and coordinated methanol ligands further connect the chains into layers which are separated by solvent molecules. In 2 each heteropentamer ...