Improved supercapacitors and water splitting performances of Anderson-type manganese(III)-polyoxomolybdate through assembly with Zn-MOF in a host-guest structure.

Enhancing performance through the combination of polyoxometalates (POMs) clusters with metal-organic frameworks (MOFs) that contain various transition metals is a challenging task. In this study, we synthesized a polyoxometalate-based metal-organic framework (POMOF) named HRBNU-5 using a solvothermal method. HRBNU-5 is composed of Zn[N(CH)][MnMoO{(OCH)CNH}]@Zn(CHO)·6CHNO, which includes two components: Zn[N(CH)][MnMoO{(OCH)CNH}]·3CHNO ({Zn[MnMo]}) and Zn(CHO)·3CHNO (Zn-BTC).

A host-guest compound formed by Cu[PWO] and HKUST-1 with capacitance and HO sensing properties.

Polyoxometalate-based metal-organic frameworks (POMOFs) have received wide attention in supercapacitors and HO detection due to their possession of the rich redox active sites of polyoxometalates (POMs) and the ordered structure of metal-organic frameworks (MOFs). In this study, we successfully synthesized a host-guest Cu[PWO]@HKUST-1 (HRBNU-7) compound by a grinding method. Cu[PWO] successfully entered the HKUST-1 pores as confirmed by the results of infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

Nanomaterial with Core-Shell Structure Composed of {PWO} and Cobalt Homobenzotrizoate for Supercapacitors and HO-Sensing Applications.

Designing and preparing dual-functional Dawson-type polyoxometalate-based metal-organic framework (POMOF) energy storage materials is challenging. Here, the Dawson-type POMOF nanomaterial with the molecular formula CoK[PWO]@Co(btc) (abbreviated as {PW}@Co-BTC, Hbtc = 1,3,5-benzylcarboxylic acid) was prepared using a solid-phase grinding method. XRD, SEM, TEM et al.

An inorganic-organic hybrid nanomaterial with a core-shell structure constructed by using Mn-BTC and Ag[BWO] for supercapacitors and photocatalytic dye degradation.

Creating inorganic-organic hybrids with polyoxometalates (POMs) and metal-organic frameworks (MOFs) as energy storage and dye-degradation materials remains challenging. Here, a new hybrid nanomaterial Mn-BTC@Ag[BWO] is synthesized by using Ag[BWO] and Mn(BTC)(HO) (Mn-BTC, BTC = 1,3,5-benzenetricarboxylic acid) through a plain grinding method. The structure and morphology characterization by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), and transmission electron microscopy (TEM) shows that the synthetic products have core-shell construction.

Porous {PMoO}-type Poly(oxometalate) Metal-Organic Frameworks for Improved Pseudocapacitance and Electrochemical Sensing Performance.

{PMo} poly(oxometalate) (POM) clusters have huge steric hindrance and limited active oxygen atoms, which make them difficult to combine with metal-organic units to form three-dimensional (3D) porous structures. Therefore, functionalization of such POMs has always been a bottleneck that is difficult to break through. In this study, {PMo} POM was successfully grafted on a lock-like metal-organic chain to generate a multiporous coordination polymer, [{Na(HO)(Hbtb)}{Cu(HO)(pz)Cl}{HSr⊂PMoMoO}]·3HO () (pz = pyrazine; btb = 1,4-bis(1,2,4-triazole) butane).

A hybrid borotungstate-coated metal-organic framework with supercapacitance, photocatalytic dye degradation and HO sensing properties.

The compounding of polyoxometalates (POMs) with structurally well-defined and porous metal-organic frameworks (MOFs) has become a hot research topic. Here, a core-shell type hybrid, {AgBWO}@[Ag(μ-Hbtc)(μ-Hbtc)] (called {AgBWO}@Ag-BTC-2, where BTC = 1,3,5-benzyl carboxylic acid), was successfully prepared a simple grinding method. IR, XRD, SEM, TEM, and XPS analysis was used to confirm the structure.

{BWO} Hybrids Modified by in Situ Synthesized Rigid Ligand with Supercapacitance and Photocatalytic Properties.

Organic rigid ligand-modified polyoxometalate-based materials possess complex and diverse structures, promising electrochemical energy storage properties and outstanding photocatalytic capabilities. Hence, two new [BWO](abbreviated as {BWO})-based inorganic-organic hybrids [{Cu(en)(HO)}][{Cu(pdc)(en)}{Cu(en)}(BWO)]·2HO () and [{Cu(pz)(HO)}(BWO)] () (pdc = 2-picolinate, en = ethylenediamine, pz = pyrazine) were successfully synthesized through a hydrothermal method. Among them, pdc and pz were obtained by in situ transformation from 2,6-pyridinedicarboxylic acid (H pydc) and 2,3-pyrazinedicarboxylic acid (Hpzdc), respectively.

Cu/Ag Complex Modified Keggin-Type Coordination Polymers for Improved Electrochemical Capacitance, Dual-Function Electrocatalysis, and Sensing Performance.

Different metal-organic units were introduced into the {PMo} polyoxometalate (POM) system to yield three porous coordination polymers with distinct characteristics, {Cu(pra)}[{Cu(pra)}{PMoMoO}] (), [{Ag(pz)(HO)Cl}{PMoMoO}] (), and [{Cu(bpz)(HO)}{PMoO}] () (pra = pyrazole; pz = pyrazine; bpz = benzopyrazine), via an hydrothermal method. In comparison with the maternal Keggin cluster and most reported POM electrode materials, compounds - exhibit larger specific capacitances (672.2, 782.

{BiW O } Exerts Antitumor Effect by Triggering Pyroptosis and Upregulating Reactive Oxygen Species.

We successfully synthesized {BiW }, a 10-nuclear heteroatom cluster modified {BiW O }. At 24 h post-incubation, the IC values of {BiW } against HUVEC, MG63, RD, Hep3B, HepG2, and MCF7 cells were 895.8, 127.

Wells-Dawson Arsenotungstate Porous Derivatives for Electrochemical Supercapacitor Electrodes and Electrocatalytically Active Materials.

Two Wells-Dawson arsenotungstate coordination polymers, [{Cu(bim)}(AsWO)] () and [(CupzCl)(AsWO)] (bim = 2,2'-biimidazole; pz = pyrazine), have been assembled via a hydrothermal method and fully characterized. Compound exhibits a 2,6-connected two-dimensional hybrid layer based on asymmetrically modified {AsW} anions and {Cu(bim)} linkers, which is extended to a three-dimensional network with a special interlayer structure and a one-dimensional tunnel. Compound is a host-guest framework that consists of a Cu-pz-Cl network with 20-member square rings, 16-member irregular rings, and embedded eight-node {AsW} guest molecules.

Inhibition of Mitochondrial ATP Synthesis and Regulation of Oxidative Stress Based on {SbW O } Determined by Single-Cell Proteomics Analysis.

The 10-nuclear heteroatom cluster modified {SbW O } was successfully synthesized and exhibited inhibitory activity (IC =0.29 μM). Based on proteomics analysis, Na Ni Sb W -SbW inhibited ATP production by affecting the expression of 16 related proteins, hindering metabolic functions in vivo and cell proliferation due to reactive oxygen species (ROS) stress.

Multinuclear Transition Metal Sandwich-Type Polytungstate Derivatives for Enhanced Electrochemical Energy Storage and Bifunctional Electrocatalysis Performances.

Different transition metal (TM) units are introduced into a trivacant Keggin cluster to form three sandwich polytungstate derivatives, (Hen)[{K(HO)}{K(HO)}{Ni(HO)(en)}{Ni(HO)(PWO)}] (), [Cu(Himi){AsWO}]·5HO (), and (Hbtp)[FeFe(HO)(AsW O)]·4HO () (en = ethanediamine; imi = imidazole; btp = 1,3-bis(1, 2, 4-triazol-1-yl) propane). Compound is a 2,3,8-connected 3D network with {4}{4·6·8·6·8}{6} topology based on bisupported tetra-Ni sandwich phosphotungstate and two kinds of potassium connection units. Compound is a dense 12-connected 3D supramolecular network with {3·4·5} topology based on hexa-Cu(imi) sandwiched arsenotungstate.

A Facile Grinding Method for the Synthesis of 3D Ag Metal-Organic Frameworks (MOFs) Containing Ag Mo O for High-Performance Supercapacitors.

Successful synthesis of three kinds of dynamically stable compounds by a simple grinding method is reported, giving Ag Mo O , Ag-BTC (Ag-MOF, BTC=benzene-1,3,5-tricarboxylic acid), and {Ag Mo O }@Ag-MOF metal-organic frameworks (MOFs). According to the electrochemical dynamic analysis, these materials have pseudocapacitor behavior and high capacitance. The unique nanorod structure of {Ag Mo O }@Ag-MOF provides more active sites, faster ion/electron transfer, and electrolyte diffusion pathways, resulting in excellent specific capacitance (971 F g ) higher than the other compounds.

The Synthesis and Biological Function of a Novel Sandwich-Type Complex Based on {SbW } and Flexible bpp Ligand.

A novel sandwich-type complex [Na(H O) ][{Na (H O) }{Mn (bpp) } (SbW O ) }]·8H O (MnSbW-bpp) (bpp = 1,3-bis(4-pyridyl) propane) is synthesized and characterized by elemental analysis, IR, thermogravimetric analysis, and single-crystal X-ray diffraction. The MnSbW-bpp compound is the first sandwich case bridged by a flexible ligand. Its biological function of MnSbW-bpp in antitumor activity is also determined in vitro and in vivo.

A Host-Guest Supercapacitor Electrode Material Based on a Mixed Hexa-Transition Metal Sandwiched Arsenotungstate Chain and Three-Dimensional Supramolecular Metal-Organic Networks with One-Dimensional Cavities.

The mixed hexa-transition metal (hexa-TM) sandwiched arsenotungstate derivative, [Cu(pz)(phen)][Cu(phen)][{Na(HO)}{(VCuO)(AsWO)}]·6HO (1) (pz = pyrazine; phen = 1,10-phenanthroline), has been hydrothermally synthesized and structurally characterized. In compound 1, two {AsWO} clusters are connected by mixed hexa-TM ring unit {VCuO} to form a sandwich-type dimer, which are further bonded in "ABAB" mode by the {Na(HO)} linker resulting in pure inorganic chains. The unique "L-shaped" trinuclear complex {Cu(phen)(pz)} is supported together via staggered π-π interactions to generate extending waveform two-dimensional supramolecular layers, which are further aggregated with their adjacent analogues by complexes {Cu(phen)} via H-bonding interaction to yield an unprecedented three-dimensional (3D) metal-organic networks with one-dimensional (1D) cavities.

Efficient and robust photocatalysts based on {PW} modified by an Ag complex.

Two novel Wells-Dawson polyoxometalate-based compounds, (Hbimb)[{Ag(bimb)}(PWO)] (1), (Hbimb)[Ag(bimb)][Ag(eim)][PWO]·HO (2) (bimb = 1,4-bis(imidazole-l-yl)butane, eim = ethyl(imidazole)), have been synthesized under hydrothermal conditions and characterized by IR, thermogravimetric, XRD and single-crystal X-ray diffraction analyses. In compound 1, two "U"-type bimb ligands are connected together viaπ interactions of Ag-C to form a ring unit. The ring unit alternately links with the "Z"-type bimb via an Ag-N bond to form an infinite Z-shaped {Ag(bimb)} chain.

Efficient visible light-driven water oxidation catalysts based on B-β-{BiWO} and unique 14-nuclear hetero-metal sandwich unit.

A sandwich tungstobismuthate with new topology based on {B-β-BiWO}-cluster and unique 14-nuclear sandwich unit is reported as a high-efficiency visible light-driven water oxidation catalyst containing extended hetero-metal oxygen layer. At optimal conditions, the turn-over number (TON) of the title compound can reach 205.5 with O yield of 32.

Synthesis and photo-/electro-catalytic properties of a 3D POMOF material based on an interpenetrated copper coordination polymer linked by in situ dual ligands and Dawson-type phosphotungstates.

A novel 3D polyoxometalate metal organic framework (POMOF), [{CuCu (HO)(pzc)(pz)}{PWO}]·4HO (1) (Hpzc = pyrazine-2-carboxylic acid, pz = pyrazine) has been hydrothermally synthesized and characterized by IR, TG, XRD, UV-vis and elemental analyses. In compound 1, the pzc and pz ligands are generated through in situ transformation from pyrazine-2,3-dicarboxylic acid (pzdc) to remove one or two CO molecules. The ligands with four coordination modes connect nine crystallographically independent Cu atoms to form a super-big circle unit.

Nonclassical Phosphomolybdates with Different Degrees of Reduction: Syntheses and Structural and Photo/Electrocatalytic Properties.

Four nonclassical phosphomolybdates, formulated as (H2pytty)8[{Mn(H2pytty)(H2O)3}{Sr⊂P6Mo6(V) Mo12(VI)O73}]2·16H2O (1), [{Mn(H3pytty)(H2O)3}2{Sr⊂P6Mo4(V)Mo14(VI)O73}]·18H2O (2), (H3pytp) (H2pytty)2[{Fe(H2O)4}{Sr⊂P6Mo3(V)Mo15(VI)O73}]·5H2O (3), and (H2pytty)2[{Cd(H2O)4}{Cd(H2O)3 (H3pytty)}{Sr⊂P6Mo5(V)Mo13(VI)O73}]·9H2O (4) (pytty = 3-(pyrazin-2-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl; pytp = 4'-(4″-pyridyl)-2,4':6',4″-terpyridine) were hydrothermally synthesized and fully characterized. The penta- and hexa-reduced basket clusters represent the highest reduced level of basket-based polyoxometalate so far. In addition, transition metal complexes as bridge units were introduced to basket system for the first time to induce rare two-dimensional inorganic-organic hybrid layer.

Organic-Inorganic Hybrid Materials Based on Basket-like {Ca⊂P6Mo18O73} Cages.

Four basket-like organic-inorganic hybrids, formulated as [{Cu(II)(H2O)2}{Ca4(H2O)4(HO0.5)3(en)2}{Ca⊂P6Mo4(V)Mo14(VI)O73}]·7H2O (1), (H4bth)[{Fe(II)(H2O)}{Ca⊂P6Mo18(VI)O73}]·4H2O (2), (H2bih)3[{Cu(II)(H2O)2}{Ca⊂P6Mo2(V)Mo16(VI)O73}]·2H2O (3), (H2bib)3[{Fe(II)(H2O)2}{Ca⊂P6Mo2(V) Mo16(VI)O73}]·4H2O (4), (bth = 1,6-bis(triazole)hexane; bih = 1,6-bis(imidazol)hexane; bib = 1,4-bis(imidazole)butane) have been hydrothermally synthesized and fully characterized. Compounds 1-4 contain polyoxoanion [Ca⊂P6Mon(V)Mo18-n(VI)O73]((6+n)-) (n = 0, 2, or 4) (abbreviated as {P6Mo18O73}) as a basic building block, which is composed of a "basket body" {P2Mo14} unit and a "handle"-liked {P4Mo4} fragment encasing an alkaline-earth metal Ca(2+) cation in the cage.

Assembly of a basket-like {Sr ⊂ P6Mo18O73} cage from 0D dimmer to 2D network and its photo-/electro-catalytic properties.

A series of basket-like heteropoly blues, formulated as (H4bth)[{Cu(H2O)}2{Sr ⊂ P6MoV2MoVI16O73}]·4H2O (1), {H2bih}3[{FeII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (2), (H2bih)3[{CoII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (3), (H2bih)3[{NiII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (4), (H2bih)2(H2bip)[{Zn (H2O)0.5}{Sr ⊂ P6MoV2MoVI16O73}]·5.5H2O (5), (bth = 1,6-bis(triazole)hexane; bih = 1,6-bis(imidazol)hexane; bip = 1,5-bis(imidazol)pentane) have been synthesized hydrothermally and fully characterized.

pH and ligand dependent assembly of Well-Dawson arsenomolybdate capped architectures.

Five Well-Dawson-type arsenomolybdates, formulated as [Cu(2,2'-bpy)2][{Cu(2,2'-bpy)}3{As2(V)Mo2(V)Mo16(VI)O62}]·4H2O (1), [H2(4,4'-bpy)]2.5[As(III)(As2(V)Mo2(V)Mo16(VI)O62)]·5H2O (2), (pyr)(imi)(Himi)3[As2(III)(As2(V)Mo3(V)Mo15(VI)O62)]·3H2O (3), [As3(III)(As2(V)Mo3(V)Mo15(VI)O62)]·4H2O (4), and (H2btp)3[As2(V)Mo18(VI)O62]·6H2O (5) (bpy = bipyridine, pyr = pyrazine, imi = imidazole, btp = 1,5-bis(triazol)pentane), have been hydrothermally synthesized and structurally characterized by the elemental analysis, TG, IR, UV-vis-NIR, XPS, XRD, and single-crystal X-ray diffraction. The structural analysis indicates that compounds 1-4 contain rare reduced Dawson {As2Mo18O62} (abbreviated as {As2Mo18}) anions as parent cluster unit, which are capped by a certain number of Cu(II) or As(III) species on different coordination positions via altering pH values and organic ligand of the reaction system.

An organic-inorganic hybrid semiconductor material based on Lindqvist polyoxomolybdate and a tetra-nuclear copper complex containing two different ligands.

A 3D organic-inorganic hybrid compound based on the Lindqvist-type polyoxometalate, [{Cu(phen)}3{Cu(μ2-ox)3}{Mo6O19}] (1) (phen = 1,10-phenanthroline, ox = oxalate), has been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR, TG, PXRD, XPS, UV-vis, and single-crystal X-ray diffraction. In compound 1, three C2O4(2-) ligands bridge one Cu atom and three Cu(phen) fragments to form a tetra-nuclear copper(II) coordination complex [{Cu(phen)}3{Cu(μ2-ox)3}](2+) unit. The six-node [Mo6O19](2-) clusters are interweaved by the 6-connected tetranuclear copper(II) complex units into an intricate 3D network structure, exhibiting a 4(12)·6(3)-nbo (sodium chloride-type) topology.

The inhibitory effects of a new cobalt-based polyoxometalate on the growth of human cancer cells.

A new cobalt-based polyoxometalate, (Himi)2[Bi(2)W2(0)O(66)(OH)(4)Co2(H2O)(6)Na(4) (H2O)14] · 17H2O (imi = iminazole) (BWCN) has been synthesized and structurally characterized. The inhibitory activities against selected human cancer lines were also determined in this study. The cell viability and chemoresistance of BWCN on human colon carcinoma HT-29 cells were assessed by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazoliumbromide), cell morphology changes, a comet assay and western blot analysis.

Novel antitumor agent, trilacunary Keggin-type tungstobismuthate, inhibits proliferation and induces apoptosis in human gastric cancer SGC-7901 cells.

A new one-dimensional chain-like compound of tungstobismuthate, [(W(OH)2)2 (Mn(H2O)3)2(Na3(H2O)14)(BiW9O33)2](Himi)2·16H2O (1) (imi = iminazole), has been synthesized in aqueous solution. The structure of 1 was identified by elemental analysis, IR, thermogravimetry (TG), X-ray photoelectron spectroscopy (XPS), (183)W-NMR, and single crystal X-ray diffraction. To investigate the inhibitory effect of 1 on human gastric adenocarcinoma SGC-7901 cells, cell proliferation and apoptosis initiation were examined by MTT assay (MTT = 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazoliumbromide), flow cytometry, nuclear staining, transmission electron microscopy, single cell gel electrophoresis, DNA fragmentation, and Western blotting.