title: 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(H(2)O)(bpy)(½){MoO(CN)(4)(bpy)(½)}]·2H(2)O (1), [Mn(H(2)O)(bpy)(½){MnN(CN)(4)(bpy)(½)}]·2H(2)O (2), [Fe(H(2)O)(bpy)(½){MnN(CN)(4)(bpy)(½)}]·2H(2)O (3), [Co(H(2)O)(bpy)(½){MnN(CN)(4)(bpy)(½)}]·2H(2)O (4) and [{Mn(H(2)O)(2)}(½){Mn(bpa)(2)}(½){MoO(CN)(4)(bpa)(½)}]·MeOH (5), (where bpy = 4,4'-bipyridine and bpa = 4,4'-bipyridylacetylene).
authors.affiliation: School of Chemistry, The University of Sydney, NSW, 2006, Australia.
authors.forename: Tony D
authors.initials: TD
authors.lastname: Keene
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Murphy
authors.forename: Jason R
authors.initials: JR
authors.lastname: Price
authors.forename: David J
authors.initials: DJ
authors.lastname: Price
authors.forename: Cameron J
authors.initials: CJ
authors.lastname: Kepert