Synthesis and Characterisation of the First Three-Dimensional Mixed-Metal-Center Inorganic-Organic Hybrid Framework with N-(Phosphonomethyl)iminodiacetate
✍ Scribed by Filipe A. Almeida Paz; Fa-Nian Shi; Jacek Klinowski; João Rocha; Tito Trindade
- Publisher
- John Wiley and Sons
- Year
- 2004
- Tongue
- English
- Weight
- 361 KB
- Volume
- 2004
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
Using crystal engineering concepts, the first three‐dimensional (3D) mixed‐metal‐centre inorganic‐organic hybrid frameworks incorporating N‐(phosphonomethyl)iminodiacetate (pmida^4−^) were synthesised under mild hydrothermal conditions (100 °C) and characterised structurally. The crystal structures, obtained by the displacement of the coordinated water molecules in [Co~2~V~2~O~2~(pmida)~2~(H~2~O)~10~]·2(H~2~O) (1) [__P__2~1~/c monoclinic space group, Z = 2, a = 9.996(2) Å, b = 14.854(3) Å, c = 10.781(2) Å, β = 110.90(3)° and V = 1495.5(5) Å^3^] by the rod‐like bridging 4,4′‐bipyridine (4,4′‐bpy) ligand — [CdVO(pmida)(4,4′‐bpy)(H~2~O)~2~]·(4,4′‐bpy)~0.5~·H~2~O (2) and [CoVO(pmida)(4,4′‐bpy)(H~2~O)~2~]·(4,4′‐bpy)~0.5~ (3) — are isostructural and were also determined in the __P__2~1~/c monoclinic space group (Z = 4) by single‐crystal X‐ray diffraction studies at low temperature (180 K): for 2, a = 9.1267(18) Å, b = 17.610(4) Å, c = 15.361(3) Å, β = 93.06(3)° and V = 2465.3(9) Å^3^; for 3, a = 8.7734(18) Å, b = 17.264(4) Å, c = 15.507(3) Å, β = 93.94(3)° and V = 2343.2(8) Å^3^. All the crystal structures contain centrosymmetric dimeric [V~2~O~2~(pmida)~2~]^4−^ units connected to neighbouring M^2+^ cations (Cd^2+^ for 2, and Co^2+^ for 1 and 3) through the phosphonate group. In 2 and 3, extended two‐dimensional [MVO(pmida)(H~2~O)~2~]~n~ layers are formed, with the 4,4′‐bpy molecules acting as pillars between adjacent layers, leading to porous 3D supramolecular structures, [MVO(pmida)(4,4′‐bpy)(H~2~O)~2~]~∞~, with a topology resembling that of the NbO net. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)