A new modification of an old framework: Hofmann layers with unusual tetracyanidometallate groups†
Abstract
Cyanidometallate complexes are highly versatile building units for the generation of functional porous materials. Here we report five new pillared Hofmann layer compounds incorporating the tetracyanidometallates [MoO(CN)4]2− and [MnN(CN)4]2−. These metalloligands, which are new to this class of materials, have been combined with divalent 1st-row transition metals to produce Hofmann layers that are linked into three-dimensional frameworks by ditopic bridging dipyridyls. We report the structures and anomalous thermal expansion properties of five new materials: [Mn(H2O)(bpy)½{MoO(CN)4(bpy)½}]·2H2O (1), [Mn(H2O)(bpy)½{MnN(CN)4(bpy)½}]·2H2O (2), [Fe(H2O)(bpy)½{MnN(CN)4(bpy)½}]·2H2O (3), [Co(H2O)(bpy)½{MnN(CN)4(bpy)½}]·2H2O (4) and [{Mn(H2O)2}½{Mn(bpa)2}½{MoO(CN)4(bpa)½}]·MeOH (5), (where