A new modification of an old framework: Hofmann layers with unusual tetracyanidometallate groups

Keene, Tony D., Murphy, Michael J., Price, Jason R., Price, David J. and Kepert, Cameron J. (2011) A new modification of an old framework: Hofmann layers with unusual tetracyanidometallate groups. Dalton Transactions, 40 (43), 11621-11628. (doi:10.1039/c1dt11183c).

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 tetracyanido-metallates [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)(1/2) {MoO(CN)(4)-(bpy)(1/2)}]center dot 2H(2)O (1), [Mn(H2O)(bpy)(1/2) {MnN(CN)(4)-(bpy)(1/2)}]center dot 2H(2)O (2), [Fe(H2O)(bpy)(1/2) {MnN(CN)(4)(bpy)(1/2)}]center dot 2H(2)O (3), [Co(H2O)(bpy)(1/2) {MnN(CN)(4)(bpy)(1/2)}]center dot 2H(2)O (4) and [{Mn(H2O)(2)}(1/2) {Mn(bpa)(2)}(1/2)-{MoO(CN)(4)(bpa)(1/2)}]center dot MeOH (5), (where bpy = 4,4'-bipyridine and bpa = 4,4'-bipyridylacetylene).

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Contributors

Author: Tony D. Keene

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