An Effective Strategy To Construct Novel Polyoxometalate-Based Hybrids by Deliberately Controlling Organic Ligand Transformation In Situ

Abstract

Deliberately controlling organic ligand transformation in situ has remained a challenge for the construction of polyoxometalate (POM)-based inorganic-organic hybrids. In this work, four POM-based hybrids assembled from an in situ bifurcating organic ligand-[Cu2(DIBA)4](H3PMo12O40)·6H2O (1), [Cu2(DIBA)4](H4SiW12O40)·6H2O (2), [Ag(HDIBA)2](H2PMo12O40)·2H2O (3), [Ag3(HDIBA)2(H2O)][(P2W18O62)1/2]·4H2O (4) (DIBAH = 3,5-di(1H-imidazol-1-yl) benzoic acid)-have been designed and obtained under hydrothermal conditions. Compounds 1 and 2 are isostructural, displaying a three-dimensional (3D) 2-fold interpenetrating framework with two types of channels, and the bigger channels are occupied by Keggin polyoxoanions and crystallization water molecules, but only crystallization water molecules in the smaller ones. Compound 3 displays a 3D supramolecular structure constructed from {Ag(HDIBA)2} segments and PMo12O40(3-) polyoxoanions through hydrogen bonding interactions. Compound 4 shows a 3D 2-fold interpenetrating framework based on (3, 3, 4)-connected network, which is constructed from {Ag3(HDIBA)2}n chains and P2W18O62(6-) polyoxoanions as linkers. The DIBAH ligand was generated in situ from 3,5-di(1H-imidazol-1-yl)benzonitrile by deliberate design, which illustrates that the strategy to construct novel POM-based hybrids by controlling ligand transformation in situ is rational and feasible. In addition, the effects of the central metal and POMs on the structures of the target compounds were discussed. Finally, the electrochemical and photocatalytic properties of compounds 1-4 have been investigated in this paper.

In Situ Ligand-Transformation-Involved Synthesis of Inorganic–Organic Hybrid Polyoxovanadates as Efficient Heterogeneous Catalysts for the Selective Oxidation of Sulfides

“…In our group’s previous works, deliberately involving in situ ligand transformation in the reaction system has been considered to be a feasible pathway for the synthesis of POM-based hybrids, − where not only were the N-bidentate ligands containing nitrile groups [3,5-di­(1 H -imidazol-1-yl)­benzonitrile (DICN), 3,5-di­[1,2,4]­triazol-1-yl-benzonitrile (DTCN), and 3,5-di­(benzimidazolyl-1-yl)­benzonitrile] hydrolyzed in situ into new N-bidentate ligands containing carboxylic acid in the final structures (Scheme ), but also the generated ligands can participate in the formation of POM-based hybrids, together with various structural features. Inspired by the above results, in situ ligand transformation was intentionally introduced into the reaction system based on POVs that may be a hopeful pathway for the preparation of POV-based inorganic–organic hybrids with innovative architectures and catalytic properties.…”

Diversity of Polyoxometalate‐Based Copper Compounds Obtained from the Same Reaction System

“…In recent decades, much attention has been devoted to the purification of water containing organic dyes with POM‐based compounds. In most studies, it is emphasized that the photocatalytic degradation activity occurred as the main process , . However, there are only a few reports of the adsorption of the pollutants on hybrid materials , .…”

Two rare {M2(MoO4)2}n chain-containing molybdate-based metal–organic complexes with a bis-pyrazole-bis-amide ligand: fluorescent sensing and photocatalysis performance

“…S2, † the PXRD spectra of both the experimental diffraction peaks of complex 1 aer being used as photocatalyst and the simulated one are consistent, indicating that complex 1 is stable in photocatalytic experiments. 49 That is to say, complex 1 has excellent photocatalytic effect for the degradation of cationic dyes MB and NR under UV light, which may be good photocatalyst for degradation of the pollutants containing MB and NR.…”