Ionic complexes comprising single/double chain cationic surfactant and Lindqvist-type polyoxomolybdate anionic cluster were used for controlled self-assembly in organic solutions. In the solvent with low dielectric constant the complexes self-assembled into flat ribbon like lamellar aggregations with an inverse bilayer substructure where the cluster located at the middle. Under the condition of increased dielectric constant, the solvent triggered the formation of helical self-assemblies, which finally transformed from helical ribbons to the flower-like assemblies due to the bilayer becoming excessively twisted. The self-assembled morphology and the substructure were characterized by SEM, TEM, and XRD. The solvent dielectricity-controlled morphologic transformations modulated by the variation of electrostatic interactions between organic cations and inorganic polyanions were demonstrated by 1H NMR and IR spectra. The strategy in this work represents an effective route in targeting the chirality-directed functionalization of inorganic clusters by combining controllable and helical assemblies of achiral polyoxometalate complexes in one system.
Jialin Yu,Qi Gao,Lijuan Zhang,Yunshan Zhou,Yuxu Zhong,Jianbo Yin,Yuanyuan Zhou,Fangsheng Tao,Yong'an Wang
ε-[Al13O4(OH)24(H2O)12]7+, which shares similarity with the phosphotriesterase active site ZnII–OH–ZnII, was specially chosen to interact with the cluster α-PMo10V2O405− to form a new three-dimensional intercluster, which crystallized in the monoclinic space group P21/m with Z = 2, for the decontamination of chemical warfare agents. The experimental results showed that 50 mg of the compound decontaminated 96.4% (within 120 min) and 99.5% (within 40 min) of sulfur mustard (HD) (4 μL) and soman (GD) (4 μL), respectively, in ambient conditions. The decontamination processes followed first-order reaction kinetics with a rate constant and half-life of 0.01234 min−1 and 56.15 min for HD and 0.1198 min−1 and 5.78 min for GD, respectively. It was concluded that the α-PMo10V2O405− moiety was responsible for the catalytic oxidation of HD into non-toxic sulfoxide, while the ε-[Al13O4(OH)24(H2O)12]7+ moiety was responsible for the catalytic hydrolysis of HD and GD into nontoxic hydrolysates. Besides, the compound showed notable efficacy for the decontamination of HD on guinea pig skin and of GD on Kunming mouse skin, indicating high potential for use in human skin protection and treatment.
Jing Yan,Huiya Huang,Zhiliang Miao,Qiuyu Zhang,Yi Yan
To enrich the building blocks and functions of supramolecular polymer, functioned inorganic polyoxometalate clusters were introduced through a novel and efficient orthogonal self-assembly strategy. The design principle is based on the organic modification of polyoxometalates (POMs) with coordination groups and electrostatic interaction of POMs with surfactants capped by photo-cross-linkable groups. Because of the relatively independent nature of these two interactions, it is possible to prepare POMs-based supramolecular cross-linked network through coordination–photo-cross-linking and vice versa, leading to the formation of main-chain-type POMs-based supramolecular polymer networks and gels. The responsiveness of these two interactions also endows the resulted supramolecular polymer with different responsiveness to light and coordination. Therefore, orthogonal self-assembly supramolecular polymerization of POMs provides a facile strategy to improve the processability of inorganic clusters, paving a new avenue toward cluster-based materials and electronic devices.
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