New topology of CN-bridged clusters: dodecanuclear face-sharing defective cubes based on octacyanometallates(IV) and nickel(II) with diimine ligands

摘要

New dodecanuclear bimetallic Ni8M4 clusters were obtained in the reaction between octacyanometallates( IV), nickel(II) cations and diimine ligands. {[Ni(LL)(H2O)](2)[Ni(LL)(H2O)(2)](6)[M(CN)(8)](4)} assemblies, where LL = 1,10-phenanthroline M = Mo, (1) or LL = 2,2'-bipyridine M = W (2) or Mo (3), are among the largest octacyanometallate-based clusters. They show the same compact topology of the cluster core, which can be described as defective face-sharing cubes with corners defined by alternating metal centres. The structures are stabilised by p-p interactions between aromatic rings of diimine ligands and hydrogen bonds connecting terminal CN groups and coordinated H2O molecules through a crystallisation solvent. Different decorating ligands cause different arrangements of clusters in the crystal structure. 1 crystallises in the triclinic system space group P (1) over bar, while 2 and 3 crystallise in the monoclinic system space group P2(1). The clusters show paramagnetic behaviour with weak antiferromagnetic interactions between the Ni-II centres through diamagnetic NC-M-IV-CN linkages.