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A novel supramolecular assembly built from Keggin-type polyoxometalates and [18]crown-6 ether building blocks was first applied as sulfur host in lithium–sulfur batteries to resolve remaining critical challenge of polysulfide shuttle effect.

We report here the successful synthesis and purification of asymmetrically modified Anderson clusters, and development of a robust coupling method for precision synthesis of organic–inorganic cluster oligomers.

Electrocatalysts play an important role to increase the energy conversion efficiency of electrolysis processes. In this study, a heterostructure of zinc iron oxide (ZnFe

Engineering hierarchical nanostructures with enhanced charge storage capacity and electrochemical activity are vital for the advancement of energy devices. Herein, a highly ordered mesoporous three-dimensional (3D) nano-assembly of Nickel Cobalt Sulphide/Polyaniline @Polyoxometalate/Reduced Graphene Oxide (NiCo

This study constructs a POM-based crystalline material of [(SiMo12O40)Cu6(2,2′-bipy)6(Mo6O22)] (1). The photocatalytic MB degradation and electrocatalytic nitrite reduction properties of complex 1 are systematically studied for the first time.

The iron catalyst (POM-Fe) could combine with chloride ions to form a supramolecular aggregate FeMo6·Cl, which was used in the oxidation of alcohols to carboxylic acids under mild conditions and can tolerate 40 substrates with moderate to high yield.

Metal-free radical carboselenation of terminal alkynes is developed for the synthesis of (E)-γ-seleno-substituted allyl nitriles with excellent regioselectivity and stereoselectivity.

The rate-determining step of the oxygen evolution reaction based on a semiconductor photoanode is the formation of the OO bond. Herein, polyethylene glycol (PEG)-modified BiVO

The direct esterification of alcohols with non-noble metal-based catalytic systems faces great challenges. Here, we report a new chrome-based catalyst stabilized by a single pentaerythritol decorated Anderson-type polyoxometalate, [N(C4H9)4]3[CrMo6O18(OH)3C{(OCH2)3CH2OH}], which can realize the efficient transformation from alcohols to esters by H2O2 oxidation in good yields and high selectivity without extra organic ligands. A variety of alcohols with different functionalities including some natural products and pharmaceutical intermediates are tolerated in this system. The chrome-based catalyst can be recycled several times and still keep the original configuration and catalytic activity. We also propose a reasonable catalytic mechanism and prove the potential for industrial applications.

Novel Anderson-type polyoxomanganotungstate clusters with the β-isomer structure, [{R1R2C(CH2O)2}MnIVW6O22]6-, were synthesized and monofunctionalized with derivatives of 1,3-propanediol via a one-pot strategy, and show unprecedented coordination activity as non-lacunary polyoxotungstate clusters and could have potential in the future construction of POM-frameworks.

A highly efficient method to oxidize methylarenes to their corresponding acids with a reusable Cr catalyst was developed. The reaction can be carried out in water with 1 atm oxygen and K2S2O8 as cooxidants, proceeds under green and mild conditions, and is suitable for the oxidation of both electron-deficient and electron-rich methylarenes, including heteroaryl methylarenes, even at the gram level. The excellent result, together with its simplicity of operation and the ability to continuously reuse the catalyst, makes this new methodology environmentally benign and cost-effective. The generality of this methodology gives it the potential for use on an industrial scale. Differing from the accepted oxidation mechanism of toluene, GC-MS studies and DFT calculations have revealed that the key benzyl alcohol intermediate is formed under the synergetic effect of the chromium and molybdenum in the Cr catalyst, which can be further oxidized to afford benzaldehyde and finally benzoic acid.

The carbon–carbon bond cleavage of 1,2-diols is an important chemical transformation. Although traditional stoichiometric and catalytic oxidation methods have been widely used for this transformation, an efficient and valuable method should be further explored from the views of reusable catalysts, less waste, and convenient procedures. Herein an inorganic-ligand supported iron catalyst (NH4)3[FeMo6O18(OH)6]·7H2O was described as a heterogeneous molecular catalyst in acetic acid for this transformation in which hydrogen peroxide was used as the terminal oxidant. Under the optimized reaction conditions, carbon–carbon bond cleavage of 1,2-diols could be achieved in almost all cases and carboxylic acids or ketones could be afforded with a high conversion rate and high selectivity. Furthermore, the catalytic system was used efficiently to degrade renewable biomass oleic acid. Mechanistic insights based on the observation of the possible intermediates and control experiments are presented.

A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.

Organo disulfides represent an abundant class of compounds in chemical biology, pharmaceutical fields, and industry. They are traditionally synthesized by the oxidation of mercaptan in the presence of an organic ligand supported metal catalyst or toxic oxidants under harsh conditions. Here, we disclose a highly-efficient pathway in which disulfide is synthesized by organic boric acid and Na2S2O3 using the catalyst (NH4)3[CrMo6O18(OH)6], demonstrating a high activity and excellent selectivity. Various boric acid derivatives have been successfully transformed into the corresponding disulfides. Mechanistic insights have been furnished based on the observation of intermediate and control experiments.

Two novel supramolecular assemblies built from Keggin-type polyoxometalate and [18]-crown-6 ether building blocks, (K+)4([18]-crown-6)4(CH3CN)2[SiM12O40] (M = Mo (1), W (2)), have been synthesized and characterized via single-crystal/powder X-ray diffraction and a wide range of analytical methods, including FT-IR, UV-vis, Raman, and NMR spectroscopy, thermogravimetric analysis, and density functional theory (DFT) calculations. This POM-based supramolecular architecture is the first example of a Keggin-type POM linked to four 18-crown-6 components forming unique propeller-like supramolecular host–guest structures via crown–metal–O(POM) bonds in the forms of the isostructural compounds 1 and 2. In addition, the electrochemical behaviors and electrocatalytic properties toward the reduction of sodium nitrite (NaNO2) were also investigated via cyclic voltammetry in acidic solution.

A newly prepared nano-organic–inorganic hybrid compound, videlicet [HPDCD]5[BW12O40]·3H2O (HPDCD = hydrolyzed and protonated 2-cyanoguanidine) (1), has been prepared under reflux condition and analyzed by FT-IR and 1H NMR spectroscopies, TG–DT analysis, FE-SEM, cyclic voltammetry, elemental analyses and also single-crystal and powder X-ray diffraction. Hydrogen bonding is the crucial agent in 1 hybrid structure as can be seen from the X-ray data. In this compound, 3D cage-like cavities are constructed by HPDCD counter-ions through hydrogen bonding. Four types of hydrogen bonds in compound 1 lead to the formation of cage-like cavities. [BW12O40]5− clusters are located into compound 1 cage-like cavities. Five types of HPDCD units create cage-like cavities according to which two types of BW12 clusters are placed between the cavities. Moreover, according to powder X-ray diffraction and field emission SEM analyses, the nano-size of 1 cluster has been confirmed. Furthermore, compound 1 has been considered in terms of the electrocatalytic activity and photocatalytic property.

Two novel polyoxovanadate-iodoBodipy supramolecular assemblies, named as (2I-BDP-C6)2V6 and (2I-BDP-C6)3V10, were first synthesized by the self-assembly of anionic hexavanadate and decavanadate with cationic iodoBodipy for photochemotherapy, respectively. The mechanisms for synergistic photochemotherapy of the anion-cation pairs were determined. In particular, (2I-BDP-C6)3V10 can effectively kill lung cancer cells (HepG2) by synergetic chemotherapy as well as photodynamic therapy.

Direct catalytic oxidation of alcohols to carboxylic acids is very attractive, but economical catalysis systems have not yet been well established. Here, we show that a pure inorganic ligand-supported chromium compound, (NH4)3[CrMo6O18(OH)6] (simplified as CrMo6), could be used to effectively promote this type of reaction in the presence of CO2. In almost all cases, oxidation of various alcohols (aromatic and aliphatic) could be achieved under mild conditions, and the corresponding carboxylic acids can be achieved in high yield. The chromium catalyst 1 can be reused several times with little loss of activity. Mechanism study and control reactions demonstrate that the acidification proceeds via the key oxidative immediate of aldehydes.

The first example of an inorganic-ligand supported iron(III) catalysed coupling of formic acid and amines to form formamides is reported. The pure inorganic catalyst (NH4)3[FeMo6O18(OH)6] (1), which consists of a central FeIII single-atomic core supported within a cycle-shaped inorganic ligand consisting of six MoVIO6 octahedra, shows excellent activity and selectivity, and avoids the use of complicated/commercially unavailable organic ligands. Various primary amines and secondary amines have been successfully transformed into the corresponding formamides under mild conditions, and the formylation of primary diamines has also been achieved for the first time. The Fe catalyst 1 can be reused several times without appreciable loss of activity.

Polyoxometalates (POMs) are a class of discrete molecular inorganic metal-oxide clusters with reversible multielectron redox capability. Taking advantage of their redox properties, POMs are thus expected to be directly involved in the lithium-sulfur batteries (Li-S, LSBs) system as a bidirectional molecular catalyst. Herein, we design a three-dimensional porous structure of reduced graphene-carbon nanotube skeleton supported POM catalyst as a high-conductive and high-stability host material. Based on various spectroscopic techniques and in situ electrochemical studies together with computational methods, the catalytic mechanism of POM clusters in Li-S battery was systematically clarified at the molecular level. The constructed POM-based sulfur cathode delivers a reversible capacity 1110 mAh g-1 at 1.0 C and cycling stability up to 1000 cycles at 3.0 C. Furthermore, Li-S pouch/beaker batteries with a POM-based cathode were successfully demonstrated. This work provides essential inputs to promote molecular catalyst design and its application in LSBs.

Novel Anderson-type polyoxomanganotungstate clusters with the β-isomer structure, [{R

One halide ion (X- ) can bind on the surface of nanoscale Anderson-type polyoxometalate (POMs) clusters [(n-C4 H9 )4 N]3 {AlMo6 O18 (OH)3 [(OCH2 )3 CCH3 ]}, and form stable complexes in solution with binding constant K=1.53×103 . Single-crystal structural analysis showed that this binding behavior occurs through multiple hydrogen bonding between X- and three hydroxy groups on the uncapped side of the cluster. This supramolecular interaction in the cluster systems means that their catalytic activities, evaluated from the oxidation of alcohols to aldehydes, can be switched upon the introduction of halide ions and water molecules. The halide ions work as inhibitors by blocking the active sites of the clusters while they can be re-activated by the addition of water.

An efficient oxidation and functionalization of C–H bonds with an inorganic-ligand supported iron catalyst and hydrogen peroxide to prepare the corresponding ketones was achieved using the bromide ion as a promoter. Preliminary mechanistic investigations indicated that the bromide ion can bind to FeMo6 to form a supramolecular species (FeMo6·2Br), which can effectively catalyze the reaction.

Polyoxometalates (POMs), an exceptional family of coordination clusters consisting of Mo, W, V, etc. early transition metal ions in their highest oxidation states, have received significant attention over recent years due to their structural versatility and unique and diverse chemical and physical properties. The functionalization of POMs with organic ligands provides a novel strategy to precisely incorporate POMs with advanced functional organic moieties on their surfaces and enhance their compatibility in organic media. Among the various organically functionalized synthetic strategies for POM-based organic–inorganic hybrid materials, alkoxylation of POMs stands for one of the hottest topics during the past decades, since the diverse and tunable alkoxyl ligands are able to anchor on the surface of many POMs clusters, forming novel and flexible organically functionalized POM clusters, which can be further exploited as building blocks to design various functionalized POM-based hybrids with charming catalytic properties, and biomedicine, energy, or functional materials applications. In this review, recent advances in alkoxylation chemistry of POMs from synthetic strategies, structural overviews to their functional applications have been discussed.

The oxidation of alcohols to aldehydes or ketones is a highly relevant conversion for the pharmaceutical and fine-chemical industries, and for biomass conversion, and is commonly performed using stoichiometric amounts of highly hazardous oxidants. The aerobic oxidation of alcohols with transition metal complex catalysts previously required complicated organic ligands and/or nitroxyl radicals as co-catalysts. Herein, we report an efficient and eco-friendly method to promote the aerobic oxidation of alcohols using an inorganic-ligand supported copper catalyst 1, (NH4)4[CuMo6O18(OH)6], with O2 (1 atm) as the sole oxidant. Catalyst 1 is synthesized directly from cheap and commonly available (NH4)6Mo7O24·4H2O and CuSO4, which consists of a pure inorganic framework built from a central CuII core supported by six MoVIO6 inorganic scaffolds. The copper catalyst 1 exhibits excellent selectivity and activity towards a wide range of substrates in the catalytic oxidation of alcohols, and can avoid the use of toxic oxidants, nitroxyl radicals, and potentially air/moisture sensitive and complicated organic ligands that are not commercially available. Owing to its robust inorganic framework, catalyst 1 shows good stability and reusability, and the catalytic oxidation of alcohols with catalyst 1 could be readily scaled up to gram scale with little loss of catalytic activity, demonstrating great potential of the inorganic-ligand supported Cu catalysts in catalytic chemical transformations.