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

Tony D Keene; Michael J Murphy; Jason R Price; David J Price; Cameron J Kepert

doi:10.1039/c1dt11183c

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

Dalton Trans. 2011 Nov 21;40(43):11621-8. doi: 10.1039/c1dt11183c. Epub 2011 Sep 30.

Authors

Tony D Keene¹, Michael J Murphy, Jason R Price, David J Price, Cameron J Kepert

Affiliation

¹ School of Chemistry, The University of Sydney, NSW, 2006, Australia.

PMID: 21960042
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 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).