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Solvent-Controlled Synthesis of Various Anderson-type Polyoxometalate-based Metal–Organic Complexes with Excellent Capacity for Chromatographic Separation of Dyes

Abstract

Abstract: By changing solvent systems, five new Anderson-type polyoxometalates (POMs)-based metal-organic complexes, namely, {(H2PCAP’)2[CrMo6(OH)5O19]}•H2O (1), {Cu3(PCAP)2[CrMo6(OH)5O19](H2O)3(DMF)2}•4H2O•2HCHO (2), {Cu3(PCAP)2[CrMo6(OH)6O18]Cl(H2O)5}•10H2O (3), {Co3(PCAP)2[CrMo6(OH)5O19](H2O)6}•9H2O•HCHO (4), {Co3(HPCAP)2[CrMo6(OH)6O18]2(H2O)10}•7H2O•2CH3CH2OH (5) (HPCAP= 3-(2-pyridinecarboxylic acid amido)pyridine, PCAP’= 3-(pyridinecarboxylic acid)amido pyridine), were successfully synthesized and structurally characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 was obtained with H2O as solvent, which exhibits a 3D supramolecular network based on CrMo6 anions and protonated H2PCAP’ molecules via hydrogen bonds. It should be noticed that the PCAP’ was in-situ transformed from HPCAP. Complexes 2-5 were synthesized with different mixed solvents. In complex 2, the CrMo6 anions acting as the inorganic bridging ligand link the 1D [Cu3(PCAP)2]n4n+ chain to construct a 2D layer. Complexes 3 and 4 show similar 3D frameworks. Two orientations of metal-organic loops [M2(PCAP)2] (M = Cu for 3, Co for 4) can be observed, which directly extend the 1D M-CrMo6 chains into the 3D networks with a 3,3,4,4-connected {42•123•14}{42•6}2 topology. In 5, the 1D Co-CrMo6 inorganic chain, [Co2(PCAP)2] binuclear loop unit and discrete CrMo6 polyanion connect with each other by hydrogen bonding interactions to form a 1D ladder-like supramolecular dual chain. The structural diversities show that solvents play key roles in the construction of various architectures and the in-situ transformation of HPCAP. The adsorption behaviors of the title complexes for organic dyes were investigated in detail. All of the title complexes show efficient adsorption capacity for the cationic dyes gentian violet (GV) and methylene blue (MB). Especially, complex 4 can selectively separate GV from the mixture of GV&RhB and GV&MO within 5-10 min, which can be used as a chromatography column for dye removal. In addition, the electrochemical properties of the title complexes have also been studied.

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Publication details

The article was received on 12 Jun 2017, accepted on 14 Nov 2017 and first published on 14 Nov 2017


Article type: Paper
DOI: 10.1039/C7CE01092C
Citation: CrystEngComm, 2017, Accepted Manuscript
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    Solvent-Controlled Synthesis of Various Anderson-type Polyoxometalate-based Metal–Organic Complexes with Excellent Capacity for Chromatographic Separation of Dyes

    X. Wang, G. song, H. Lin, X. Wang, G. Liu and X. Rong, CrystEngComm, 2017, Accepted Manuscript , DOI: 10.1039/C7CE01092C

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