The syntheses, structures and characterizations of a series of frameworks constructed from polyoxometalates, metals and organic units

Wang, Yan; Wang, Lamei; Li, Zhifang; Hu, Yangyang; Li, Guanghua; Xiao, Li‐Na; Wang, Tie‐Gang; Dong, Zheng; Cui, Xiao‐Bing; Xu, Ji‐Qing

doi:10.1039/c2ce26477c

Cited by 16 publications

(2 citation statements)

References 63 publications

(14 reference statements)

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“…Chiral polyoxometalates (POMs) have received much attention, not only owing to their intriguing topologies and architectures, but also because of their significant potential applications in nonlinear optics, enantioselective catalysis, chiroptical switching, and medicine. − The syntheses of chiral POMs can be realized either by enantioselective synthesis using enantiomerically pure chiral organic species and chiral metal–organic fragments, − or by spontaneous resolution using achiral materials, generating a conglomerate (mixture of chiral crystals). − Compared with the approach using expensive chiral auxiliary, spontaneous resolution upon crystallization is more appealing as an economical and convenient method. However, the laws of physics determining the processes have not yet been fully understood because of the unpredictability of crystal structures, and most POM clusters possess high symmetry, thus spontaneous resolution is still a relatively scarce phenomenon, confronting more difficulties and challenges.…”

Section: Introductionmentioning

confidence: 99%

Spontaneous Resolution of Evans–Showell-Type Polyoxometalates in Constructing Chiral Inorganic–Organic Hybrid Architectures

Wang

et al. 2015

Inorg. Chem.

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Six new hybrid compounds based on [Co2Mo10H4O38](6-) polyoxoanion, (4-H2pya)6Co2Mo10H4O38·10H2O 1 (4-Hpya =3-(4-pyridyl)acrylic acid) and (4-H2pya)4[M(H2O)6][Co2Mo10H4O38]·5H2O (M = Co 2, Ni 3, Cu 4, Zn 5, Cd 6), were synthesized and characterized by elemental analysis, IR spectroscopy, TG analysis, solid diffuse reflective spectrum, powder X-ray diffraction, and single crystal X-ray diffraction. Compound 1 crystallizes in the centrosymmetric space group P-1, which is built up of protonated 4-H2pya molecules and isolated [Co2Mo10H4O38](6-) polyoxoanions. Isostructural compounds 2-6 crystallize in the chiral space group P1 by spontaneous resolution, as a conglomerate of two enantiomerically pure crystals, which were obtained by adding different metal cations to the reaction system of compound 1. The structures of 2-6 comprise chiral [Co2Mo10H4O38](6-) anions, cationic [M(H2O)6](2+) units, and protonated 4-H2pya ligands. The chiral [Co2Mo10H4O38](6-) polyoxoanions can be connected up together by directional hydrogen-bonding interactions among terminal oxygen atoms of anions, coordinated water molecules and organic ligands to construct a 3D supramolecular chiral framework in 2-6. The absolute configuration of 2-6 was determined from the Flack parameter by X-ray crystallography and solid state circular dichroism spectroscopy. As far as we know, compounds 2-6 represent the first examples of chiral inroganic-organic hybrid species based on Evans-Showell-type polyoxometalates. Furthermore, the second harmonic generation (SHG) activities for 2 and 4 were measured, showing an SHG efficiency of approximately 0.9 × KH2PO4.

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Section: Introductionmentioning

confidence: 99%

Spontaneous Resolution of Evans–Showell-Type Polyoxometalates in Constructing Chiral Inorganic–Organic Hybrid Architectures

Wang

et al. 2015

Inorg. Chem.

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“…The UV-vis spectra have shown an intense absorption band at 255 nm and a broad band at 284 nm of 1 , a sharp absorption peak at 253 nm and a broad peak at 286 nm of 2 . Both of them are all due to pπ(O(t)/O(b)/O(c))-dπ* (Mo/V) nuclear transitions in Mo/V-O bonds [ 31 , 63 ].…”

Section: Resultsmentioning

confidence: 99%

Two New Compounds Based on Bi-Capped Keggin Polyoxoanions and Cu-Bpy Cations Contain Both CuII and CuI Complexes: Synthesis, Characterization and Properties

et al. 2023

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Two inorganic–organic hybrid complexes based on bi-capped Keggin-type cluster, {([CuII(2,2′-bpy)2]2[PMoVI8VV2VIV2O40(VIVO)2])[CuI(2,2′-bpy)]}∙2H2O (1) and {[CuII(2,2′-bpy)2]2[SiMoVI8.5MoV2.5VIVO40(VIVO)2]}[CuI0.5(2,2′-bpy)(H2O)0.5] (2) (bpy = bipyridine), had been hydrothermally synthesized and structurally characterized by elemental analysis, FT-IR, TGA, PXRD and X-ray single-crystal diffraction analysis. Compound 1 consists of a novel 1-D chain structure constructed from [CuI(2,2′-bpy)]+ unit linking bi-supported POMs anion {[CuII(2,2′-bpy)2]2[PMoVI8VV2VIV2O40(VIVO)2]}−. Compound 2 is a bi-capped Keggin cluster bi-supported Cu-bpy complex. The main highlights of the two compounds are that Cu-bpy cations contain both CuI and CuII complexes. Furthermore, the fluorescence properties, the catalytic properties, and the photocatalytic performance of compounds 1 and 2 have been assessed, and the results show that both compounds are active for styrene epoxidation and degradation and adsorption of Methylene blue (MB), Rhodamine B (RhB) and mixed aqueous solutions.

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Supramolecular Assembly Based on Octamolybdate and Triazole Derivative: Crystal Structure and Catalytic Application in Olefin Epoxidation

Gao

et al. 2014

J Clust Sci

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The syntheses, structures and characterizations of a series of frameworks constructed from polyoxometalates, metals and organic units

Abstract: The syntheses, structures and characterizations of a series of frameworks constructed from polyoxometalates, metals and organic units3

Cited by 16 publications

References 63 publications

Spontaneous Resolution of Evans–Showell-Type Polyoxometalates in Constructing Chiral Inorganic–Organic Hybrid Architectures

Spontaneous Resolution of Evans–Showell-Type Polyoxometalates in Constructing Chiral Inorganic–Organic Hybrid Architectures

Two New Compounds Based on Bi-Capped Keggin Polyoxoanions and Cu-Bpy Cations Contain Both CuII and CuI Complexes: Synthesis, Characterization and Properties

Supramolecular Assembly Based on Octamolybdate and Triazole Derivative: Crystal Structure and Catalytic Application in Olefin Epoxidation

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