Polyoxometalate-Based Metal−Organic Frameworks Assembled under the Ionothermal Conditions

• Published in: Crystal growth & design Vol. 11; no. 2; pp. 458 - 465
• Main Authors: Fu, Hai, Li, Yangguang, Lu, Ying, Chen, Weilin, Wu, Qiong, Meng, Jingxin, Wang, Xiaolan, Zhang, Zhiming, Wang, Enbo
• Format: Journal Article
• Language: English
• Published: Washington,DC American Chemical Society 02.02.2011
• Subjects: Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Diffusion and ionic conduction in liquids; Exact sciences and technology; Ionic conduction; Materials science; Organic compounds; Other materials; Physics; Specific materials; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Transport properties of condensed matter (nonelectronic); Metal organic framework; Metallates; Imidazole derivatives; Organometallic compounds; XRD; Topology; Cadmium sulfide; Ionic liquid; Monocrystals; Lamellar structure; Imidazoles; Benzene; Supramolecular structure; Ligands; Copper
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/cg101224r

One new polyoxometalate compound H3(Tea)(Bmim)3[P2W18O62]·3H2O (Tea = triethylamine, Bmim = 1-methyl-3-ethylimidazole) (1) and three new polyoxometalate-based metal−organic frameworks (PMOFs) CuII(Bbi)1.5(H2Bbi)2[P2W18O62] (Bbi = 1,1-(1,4-butanediyl)-bis(imidazole)) (2), CuII 2.5(Mimin)(HMimin)(Bbi)3[P2W18O62]·3H2O (Mimin = methylimidazol) (3), and CuII(Bbtz)(H2Bbi)(H2Btp)[P2W18O62] (Bbtz = 1,4-bis(triazol-1-ylmethyl)benzene, Btp = 1,3-Bis(1,2,4-triazol-1-yl)propane) (4) have been synthesized under ionothermal conditions using an ionic liquid (IL) [Bmim]Br (Bmim = 1-ethyl-3-methylimidazole) as solvent. Their structures were determined by single crystal X-ray diffraction. Compound 1 possesses a one-dimensional (1D) supramolecular chain-like structure constructed from [P2W18O62]6− anions, Bmim, Tea, and water molecules. Compound 2 has a two-dimensional (2D) (6,3)-layer structure built by [P2W18O62]6− anions, copper ions, and Bbi ligands. Compounds 3 and 4 are three-dimensional (3D) PMOFs with novel (6.8.10)(4.6.83.10)(4.6.83.12) and classic (65.8)(65.8)-cds topologies, respectively. Compounds 2−4 represent the first examples of PMOFs synthesized by the ionothermal method. The successful synthesis of compounds 2−4 suggests that ionothermal synthesis will be a very promising synthetic technique for assembling new PMOFs. Additionally, the properties of the four compounds have been studied in detail.