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

Journal Article · Thu May 10 04:00:00 EDT 2012 · Dalton T.

DOI:https://doi.org/10.1039/C1DT11183C· OSTI ID:1038280

Keene, Tony D; Murphy, Michael J; Price, Jason R; Price, David J; Kepert, Cameron J ^[1]

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1. Sydney

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){sub 4}]{sup 2-} and [MnN(CN){sub 4}]{sup 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{sub 2}O)(bpy){sub 1/2}{l_brace}MoO(CN){sub 4}(bpy){sub 1/2}{r_brace}] {center_dot} 2H{sub 2}O (1), [Mn(H{sub 2}O)(bpy){sub 1/2}{l_brace}MnN(CN){sub 4}(bpy){sub 1/2}{r_brace}] {center_dot} 2H{sub 2}O (2), [Fe(H{sub 2}O)(bpy){sub 1/2}{l_brace}MnN(CN){sub 4}(bpy){sub 1/2}{r_brace}] {center_dot} 2H{sub 2}O (3), [Co(H{sub 2}O)(bpy){sub 1/2}{l_brace}MnN(CN){sub 4}(bpy){sub 1/2}{r_brace}] {center_dot} 2H{sub 2}O (4) and [{l_brace}Mn(H{sub 2}O){sub 2}{r_brace}{sub 1/2}{l_brace}Mn(bpa){sub 2}{r_brace}{sub 1/2}{l_brace}MoO(CN){sub 4}(bpa){sub 1/2}{r_brace}] {center_dot} MeOH (5), (where bpy = 4,4'-bipyridine and bpa = 4,4'-bipyridylacetylene).

• Research Organization: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
• Sponsoring Organization: FOREIGN
• OSTI ID: 1038280
• Journal Information: Dalton T., Journal Name: Dalton T. Journal Issue: (43) ; 2011 Vol. 40; ISSN 1477-9226
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

36 MATERIALS SCIENCE
FUNCTIONALS
MODIFICATIONS
POROUS MATERIALS
THERMAL EXPANSION
TRANSITION ELEMENTS