The reaction of sodium tungstate, sodium selenite, and cerium nitrate under reasonably acidic water solution in the presence of morpholine gives rise to a penta-CeIII-bridged polyoxotungstate, Na10(C4H10NO)10[Ce5Se4.75W34O128(OH)2(H2O)14]·21H2O (1), which is a rare example of selenotungstate featuring novel Keggin {SeW8} building blocks. This cluster is fully characterized by single crystal X-ray diffraction, elemental analyses, powder X-ray diffraction (PXRD), infrared spectrum (IR), ultraviolet–visible spectroscopy (UV/Vis), thermogravimetric/differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS) and electrospray ionization mass spectrometry (ESI-MS). Single-crystal X-ray diffraction analysis reveals that four {SeW8} are bridged by multi-Ce linkers and two equal “trans”-{WO6} centers resulting in this tetramer. The utilization of Ce cations and SeIVO32− heteroanion template as well as some determined assembly rules during the synthesis play important roles in the formation of 1. Additionally, its solution stability and electrochemical performance were also discussed in detail.

H 2 has been considered as a promising successor for traditional fossil fuels due to its sustainable and clean. In H 2 production, electrocatalytic hydrogen evolution reaction (HER) is the core step. Many noble metal free electrocatalysts for electrochemical H 2 generation have been explored in the past few years. Mo based materials, such as Mo x C (x = 1 or 2), MoP, MoS 2 and Mo x N (x = 1 or 2) have been confirmed as effective electrocatalysts in both acidic and basic conditions with small overpotential, excellent stability and nearly 100% Faradic efficiency in H 2 generation. Because of excellent solubility, controllable dimension and various components, Mo based polyoxometallates (POMs), such as [PMo 12 O 40 ] 3− , [Mo 7 O 24 ] 6− , [P 2 Mo 5 O 23 ] 6− , [Mo 6 O 19 ] 2− and [XMo 6 O 24 ] 4− (X = Co 2+ , Cu 2+ , Ni 2+ ), are ideal precursors to synthesize Mo based electrocatalyst. Here, we summarized Mo based hybrid electrocatalysts in form of Mo x C, MoP, MoS 2 and Mo x N with carbon as matrix, which derived from POM since 2013. In this review, we focus on the synthetic strategy and HER activity of these electrocatalyst. We anticipate this review can provide more insight into the structural and composition regulation of POM precursor to design and synthesis Mo based HER electrocatalyst with more excellent activity.

The title compound, poly[bis{μ 2 -4,4′-bis[(1,2,4-triazol-1-yl)methyl]biphenyl-κ 2 N 4 : N 4′ }bis(nitrato-κ O )zinc(II)], [Zn(NO 3 ) 2 (C 18 H 16 N 6 ) 2 ] n , is a two-dimensional zinc coordination polymer constructed from 4,4′-bis[(1 H -1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl units. It was synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Zn II cation is located on an inversion centre and is coordinated by two O atoms from two symmetry-related nitrate groups and four N atoms from four symmetry-related 4,4′-bis[(1 H -1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl ligands, forming a distorted octahedral {ZnN 4 O 2 } coordination geometry. The linear 4,4′-bis[(1 H -1,2,4-triazol-1-yl)methyl]-1,1′-biphenyl ligand links two Zn II cations, generating two-dimensional layers parallel to the crystallographic (132) plane. The parallel layers are connected by C—H...O, C—H...N, C—H...π and π–π stacking interactions, resulting in a three-dimensional supramolecular architecture.

Two pillared-layer MOFs as luminescent probes with multifunctional sensitivities to detect metal ions and small molecules were reported. Our results show that the luminescence intensities of 1a and 2a are highly sensitive to Fe3+ and Cd2+ ions and small molecules such as acetone and nitrobenzene.

A novel hybrid network based on octamolybdate building unit, Cu(5)(I)LBBTZ(3)H(2)O [beta-(MoMo7O26)-Mo-V-O-VI] [1, BBTZ = 1,4-bis(1,2,4-triazol-1-ylmethyl) benzene], has been synthesized under ionothermal conditions and structurally characterized by single crystal X-ray diffraction. Compound 1 is a rarely self-penetration network constructed by three dimensional(3D) poly-rings networks and (4,4) 2D layers, in which the two interpenetrating parts were united together through Cu2 and Cu1 centers. Further, the infrared (IR) spectrum, thermogravimetric(TG) analysis and photocatalytic studies were also performed to authenticate the identities of the title compound. Photocatalytic study revealed that compound 1 was active for photocatalytic 112 evolution under UV irradiation.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Four novel organic–inorganic hybrid compounds [Cu5 I(4,4′-bpy)3(2,2′-bpy)4][BW12O40] · H2O (1), [Ni0.5(2,2′-bpy)1.25][Ni(2,2′-bpy)3][Ni(2,2′-bpy)2(H2O)(SiW 11 VI WVO40)] · 0.5H2O (2), [H2bpy]2[Zn(2,2′-bpy)3]2[Si2W18O62] · 1.5H2O (3) and [CuII(2,2′-bpy)2]2[SiW12O40] · 2H2O (4) (2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, electrochemical measurements and single-crystal X-ray diffraction. Compound (1) is a novel [BW12O40]5− polyoxoanion bisupported by copper(I) coordination cations with mixed 2,2′-bpy and 4,4′-bpy ligands. Compound (2) is constructed from the [SiW 11 VI WVO40]5− polyoxoanions supported by [Ni(2,2′–bpy)2]2+. Compound (3) is composed of a novel [Si2W18O62]8− cluster and [Zn(2,2′–bpy)3]2+ complexes, which held together into a three-dimensional (3D) supramolecular network through hydrogen-bonding interactions. Compound (4) shows a 2D layer framework constructed from a bisupporting Keggin polyoxoanion cluster and [Cu(2,2′–bpy)2]2+ coordination polymer fragments, resulting in 3D networks via supramolecular interactions.

Two new compounds [Hbpy]2[Ce(Hbpy)(DMF)5(H2O)2][H2W12O40] · 0.5H2O (1) and [La(DMF)7(H2O)][PMo12O40] · DMF · (CH3)2NH (2) (DMF = N,N-dimethylformamide, bpy=4,4′-bipyridine) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectra, TG analysis and electrochemical analysis. In 1, the [Ce(Hbpy)(DMF)5(H2O)2]4+ unit is supported on the α-Keggin polyoxoanion [H2W12O40]6− via bridging oxygen atoms, and further extended into 2-D supramolecular networks by hydrogen-bonding and π–π interactions. There exist one-dimensional channels surrounded by supramolecular interactions, in which 4,4′-bipy ligands reside. Compounds constructed from Ln(III) and [H2W12O40]6− polyoxoanions are rare. For 2, the [La(DMF)7(H2O)]3+ is supported by [PMo12O40]3− units via the surface bridging oxygens, and further extended into 2-D supramolecular networks through hydrogen bonds. As for 1, a one-dimensional channel exists in 2, in which DMF resides. To our surprise, (CH3)2NH molecules exist in the structure of 2, from hydrolysis of DMF under catalysis of 12-molybophosphate. The electrochemistry of 1 is investigated.

A new compound [Zn(phen)(2)](2)[(PMo8V4V2O42)-V-VI-V-V-O-IV][Zn(phen)(2)(H2O)](2)[(PMo8V4V2O42)-V-VI-V-V-O-IV] center dot 7H(2)O (phen =phenanthroline) has been synthesized under hydrothermal conditions and characterized by IR, TG analysis and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P2(1)/C, a = 21.609(4) angstrom, b =16.537(3) angstrom, c =21.279(4) angstrom, alpha = 90 degrees, beta = 100.25(3)degrees, gamma = 90 degrees, V = 7483(3) angstrom(3), Z = 2. The basic building unit in 1 is the [PMo8V6O42] cluster. The most remarkable structural feature of 1 is that there exist two distinct [PMo8V6O42] clusters. One is covalently linked by [Zn(phen)(2)] complexes to form a 2D covalent layer, the other supports two [Zn(phen)(2)(H2O)] complexes forming a discrete bisupporting structure. It is interesting that discrete bisupporting clusters locate in the space of two adjacent covalently layers to form a 3D supramolecular framework.

Two new coordination polymers [Ni(C6H10O4)(C10H8N2)] n (1) and [Zn3(C6H10O4)3(C12N2H8)2] n (2) have been synthesized under hydrothermal conditions. Complex (1) exhibits an interesting three-dimensional interpenetrating network, whereas complex (2) has a two-dimensional network. The IR and TG properties of these two complexes are studied. Furthermore, complex (2) exhibits photoluminescence.

A novel compound [Zn(2,2'-bipy)2]2[PMoⅥ11 MoⅤO40] has been synthesized.It is decorated by transition-metal complex bisupporting Keggin-type molybdenum phosphate under mild hydrothermal conditions and structurally characterized by IR,elemental analyses and single-crystal X-ray diffraction.The result indicates that the structure of the compound consists of one [PMoⅥ11 MoⅤO40]4-heteropolyoxoanion and two [Zn(2,2'-bipy)2]2+ fragments.Different basic building subunits formed the 1D chainlike supramolecular architectures via hydrogen bonds.Then the 1D chains extended to 2D layers with the same weak interactions.The compound crystallized in the monoclinic space group P21/n with a=1.358 7(3) nm,b=1.207 3(2) nm,c=1.893 2(4) nm,α= 90.00°,β=93.15(3)°,γ=90.00°,V=3.100(9) nm3,Z=2,R1=0.065 8,wR2=0.202 3.

A new dimeric polyoxotungstate, based on the monovacant anion [SiW11O39] connected by a hexa-metal cluster (CeCs5)-Cs-III, is synthesized and characterized by single-crystal X-ray diffraction, IR, TG and electrochemistry. The polyoxoanions are connected to 3D structures by additional alkali metal ions.

In this article, two compounds [H2bpy][Ln(DMF)4(H2O)3(Hbpy)][H2W12O40] (Ln = La,Ce; DMF = N,N-dimethylformamide, bpy = 4,4′-bipyridine) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectra, and TG analysis. X-Ray analysis showed that the [Ln(DMF)4(H2O)3(Hbpy)]4+ unit is supported on the α-Keggin polyoxoanion [H2W12O40]6− via the surface bridging oxygen atom. The [H2bpy][Ln(DMF)4(H2O)3(Hbpy)][H2W12O40] entity is further extended into 2D supramolecular networks with 1-D channels by hydrogen-bonding interactions, in which 4,4′-bipy ligands reside. To the best of our knowledge, these complexes represent the first examples of rare earth metal-organic complex-decorated α-metatungstate clusters. Furthermore, the electrochemical properties of these compounds have been studied via the method of bulk-modified carbon paste electrodes.

An unprecedented rare-earth molybdenum phosphate supramolecular compound(H3O)3[Nd(DMF)4(H2O)5][P2Mo18O62]·DMF(DMFN,N′-dimethylformamide) was synthesized under room temperature with water and organic mixed solution,and the crystal structure was determined.The compound crystallized in the monoclinic space group C2/c with a2.220 8(4) nm,b1.624 2(3) nm,c3.037 5(6) nm,α90.00°,β110.17(3)°,γ90.00°,V10.284(4) nm3,Z8,R10.041 5,wR20.092 7.