Zicheng Xiao

Synthesis, crystal structure and spectroscopic studies of a series of hexavanadate hybrids with multiple functional groups

Three new derivatives of hexavanadate with remote methacryl, phthalyl and tetrahydrophthalyl groups, respectively, were synthesized by esterification of pentaerythritol-derivatized hexavanadate. These new compounds were characterized by FT-IR, 1H NMR, UV-vis, elemental analysis and single-crystal X-ray diffraction. Their thermal stabilities were also tested by TGA analyses. Through such syntheses, we have successfully introduced the carbon–carbon double bond and/or carboxylic groups into the polyoxovanadates which could be utilized to build more complex structures. We also discuss the influence of anhydrides with different functional groups on the esterification of the pentaerythritol derivatized hexavanadate.

Crystal Structures of Three New Hexavanadate Hybrids with Aromatic Carboxylate Ligands

AbstractThree novel hexavanadate hybrids: (Bu4N)2[V6O13{(OCH2)3CCH2OOCC6H4Br-p}2] (compound 1), (Bu4N)2[V6O13{(OCH2)3CCH2OOCC6H4NO2-m}2] (compound 2) and (Bu4N)2[V6O13{(OCH2)3CCH2OOCC4H3S}2] (compound 3) have been synthesized and structurally characterized by means of single-crystal X-ray diffraction. All three compounds crystallize in the monoclinic space group in P21/c with the respective cell parameters: a = 11.806 (2) Å, b = 16.926 (3) Å, c = 17.836 (4) Å, β = 98.42 (3) Å for compound 1, a = 11.471 (2) Å, b = 16.796 (3) Å, c = 18.136 (4) Å, β = 98.22 (3) Å for compound 2 and a = 11.3299 (2) Å, b = 15.8742 (3) Å, c = 18.6637(3) Å, β = 97.7462 (14) Å for compound 3. The influences of these organic conjugated systems to the structures of hexavanadate hybrids have also been discussed.Graphical AbstractThree new hexavanadate hybrids with aromatic carboxylate ligands were synthesized by means of post-functionalization strategy. In the structures of these compounds, the organic ligands are rigid and the atoms are almost coplanar on account of the conjugated effect of the aromatic rings, forming wings of a spacecraft-like structure.

Stepwise syntheses and supramolecular assemblies of a series of polyoxovanadate hybrids with various architectures

By controlling the terminal organic ligands, various fascinating supramolecular assemblies originating from hydrogen bonding interactions in different dimensions in a series of hexavanadate hybrids were synthesized via step-by-step organic modification. These hybrids were characterized, and their structures were determined by single-crystal X-ray diffraction. Moreover, the introduction of a rigid bridging ligand has a positive influence on the assembly of supramolecular architectures, providing a new vision for the design and synthesis of advanced inorganic–organic materials.

Improved peroxidase-mimic property: Sustainable, high-efficiency interfacial catalysis with H2O2 on the surface of vesicles of hexavanadate-organic hybrid surfactants

An emerging method for effectively improving the catalytic activity of metal oxide hybrids involves the creation of metal oxide interfaces for facilitating the activation of reagents. Here, we demonstrate that bilayer vesicles formed from a hexavanadate cluster functionalized with two alkyl chains are highly efficient catalysts for the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) with H2O2 at room temperature, a widely used model reaction mimicking the activity of peroxidase in biological catalytic oxidation processes. Driven by hydrophobic interactions, the double-tailed hexavanadate-headed amphiphiles can self-assemble into bilayer vesicles and create hydrophobic domains that segregate the TMB chromogenic substrate. The reaction of TMB with H2O2 takes place at the interface of the hydrophilic and hydrophobic domains, where the reagents also make contact with the catalytic hexavanadate clusters, and it is approximately two times more efficient compared with the reactions carried out with the corresponding unassembled systems. Moreover, the assembled vesicular system possesses affinity for TMB comparable to that of reported noble metal mimic nanomaterials, as well as a higher maximum reaction rate.

Spectroscopic Studies of a Novel Inorganic–Organic Hybrid Based on Polyoxovanadates Under a Wide Range of Wavelengths

In this paper, we reported the synthesis of a new polyoxovanadate hybrid with chlorobenzoyl ligand, which was characterized by a series of spectroscopic technologies radiated with the wavelengths from nanoscale to decimetre including X-ray diffraction, Ultraviolet–Visible spectrometer, Fourier Transform Infrared spectrometer, Raman spectrometer and Nuclear Magnetic Resonance. The electrochemical behaviour and thermal stability were also investigated through cyclic voltammetries and thermogravimetric analyses, respectively. The spectroscopic studies in this work could give a cornerstone to explore the polyoxovanadate hybrids on molecular scale.

Crystal structure of bis(3-(3-ethylureido)-N,N-dimethylpropan-1-aminium) bis (μ3-2-(hydroxymethyl)-2-(oxidomethyl)propane-1,3-bis(olato))-(μ6-oxo)-hexakis(μ2-oxo)-hexaoxo-hexavanadium(V) – dichloromethane (1/1), C27H60Cl2N6O23V6

Abstract C27H60Cl2N6O23V6, C2/c (no. 15), a = 26.1482(12) Å, b = 10.6096(4) Å, c = 17.4426(6) Å, β = 90.932(4)°, V = 4838.3(3) Å3, Z = 4, Rgt(F) = 0.0565, wRref(F2) = 0.1477, T = 106 K.