Asymmetric Hybrid Polyoxometalates: A Platform for Multifunctional Redox‐Active Nanomaterials

Abstract

Access to asymmetrically functionalized polyoxometalates is a grand challenge as it could lead to new molecular nanomaterials with multiple or modular functionality. Now, a simple one‐pot synthetic approach to the isolation of an asymmetrically functionalized organic–inorganic hybrid Wells–Dawson polyoxometalate in good yield is presented. The cluster bears two organophosphonate moieties with contrasting physical properties: a chelating metal‐binding group, and a long aliphatic chain that facilitates solvent‐dependent self‐assembly into soft nanostructures. The orthogonal properties of the modular system are effectively demonstrated by controlled assembly of POM‐based redox‐active nanoparticles. This simple, high‐yielding synthetic method is a promising new approach to the preparation of multi‐functional hybrid metal oxide clusters, supermolecular systems, and soft‐nanomaterials.

Inhibition of Mitochondrial ATP Synthesis and Regulation of Oxidative Stress Based on {SbW8O30} Determined by Single‐Cell Proteomics Analysis

“…Polyoxometalates (POMs) are considered as promising drug candidates that have high redox, [1] nucleophilic [2] and surface charge distribution, [3] which enhance the target recognition of biological macromolecules,a nd an adjustable molecular structure, [4] high solubility,a nd stability in aw ide range of pH. [5] Some representative studies on POM compounds with anticancer activity are described in Figure 1a; [6] all POMs exhibiting antiproliferative activity on cancer cells are summarized in Table S1;a nd as eries of possible mechanisms and potential targets of antitumor cell proliferation is shown in Figure 1b.…”

“…Protozoa are used in cancer research because they are single-cell organisms with many similarities to cancer cells. [17,18] Of these, Tetrahymena thermophila (T. thermophila) [19] is commonly used in molecular studies because: (1) it is widespread in nature and harmless to humans;( 2) its culture method is simple and inexpensive;( 3) it has dual characteristics of animals and cells;( 4) it is au nicellular animal, and thus,many life activities are different from those of multicellular animals but with essential similarities;( 5) it contains 58 genes related to diseases and has ahigh degree of conserved gene function in humans;a nd (6) the sequence of the T. thermophila gene is complete.T herefore, T. thermophila is considered amodel protozoan and used for determining the drug mechanisms and toxicity in higher organisms.…”

Synthesis of CdS-loaded (CuC10H26N6)3(PW12O40)2 for enhanced photocatalytic degradation of tetracycline under simulated solar light irradiation

“…Polyoxometalates (POMs) belong to an emerging group of semiconductor photocatalysts. They are endowed with unique magnetic, 26 redox, 27 and catalytic properties 28,29 thanks to fast electron-hole pair separation processes. However, lack of visible-light adsorption and easy aqueous dissolution limit its photocatalytic applications in practical ambiences.…”

Transition metal decorated soft nanomaterials through modular self-assembly of an asymmetric hybrid polyoxometalate

“…))(P(O)OC 24 H 41 )]ÁnDMF (Pt-1), was prepared from the asymmetric hybrid POM, 1, which was synthesised according to our previously reported procedure. 11 [Pt(COD)Cl 2 ] (COD = cyclooctadiene) was stirred briefly with two equivalents of AgBF 4 in acetone to labilise the Pt 2+ complex. The resultant AgCl was removed by filtration and the Ptcontaining solution was added to a solution of 1 in DMF-CH 3 CN (1 : 1 v/v) and stirred at room temperature for 72 h. This resulted in a yellow/orange coloured reaction mixture, which is characteristic of many {Pt(TPY)L} complexes.…”

“…6 The spherical assemblies formed by Pt-1 also differ significantly from the randomly shaped aggregates observed in our previous work as a result of the solvent-driven self-assembly of the POM-Fe II -POM dimer derived from 1. 11 The micelle-favouring 'headtail' polarity of 1 is retained upon platinum(II) coordination. In contrast, formation of the dimeric iron(II) complex leads to molecules of ill-defined polarity with restricted capacity to form regular assemblies.…”