Facile and controllable preparation of carbon microsphere for electro-driven nitrogen reduction: Accommodating nitrogen doping with hierarchical porous structure.

Driven by sustainable electricity, electrochemical nitrogen fixation under ambient conditions is considered as a promising strategy to generate low-concentrated NH/NH. Under the principle of doping and porous engineering, nitrogen-doped carbon microsphere with hierarchical pores (NC-HP) is fabricated via pyrolyzing polymer microsphere. Hierarchical structure with macro-, meso- and micropores is obtained by assembling melamine/phenol-formaldehyde oligomers in Pickering droplets, with the assistance of triblock copolymer Pluronic F127.

Methyl nitrate energetic compounds based on bicyclic scaffolds of furazan-isofurazan (isoxazole): syntheses, crystal structures and detonation performances.

Two energetic bicyclic scaffolds (furazan-isoxazole and furazan-1,3,4-oxadiazole) were constructed different cyclization reactions. Based on the energetic bicyclic scaffolds, the energetic compounds, 3-(4-nitraminofurazan-3-ly)-isoxazole-5-methylnitrate 1c and 5-(4-nitraminofurazan-3-ly)-1,3,4-oxadiazole-2-methylnitrate 2c, were designed and synthesized in good yields. Because of the acidity of nitramine, the corresponding energetic ionic salts, ammonium 3-(4-nitraminofurazan-3-ly)isoxazole-5-methylnitrate 1d and ammonium 5-(4-nitraminofurazan-3-ly)-1,3,4-oxadiazole-2-methylnitrate 2e, were also obtained and well characterized, their structures were further determined by X-ray single crystal diffraction.

Regulating Electronic Structure in Bi O Architectures by Ti Mediation: A Strategy for Dual Active Sites Synergistically Promoting Photocatalytic Nitrogen Hydrogenation.

Under mild conditions, nitrogen undergoes the associative pathways to be reduced with solar energy as the driving force for fixation, avoiding the high energy consumption when undergoing dissociation. Nevertheless, this process is hindered by the high hydrogenation energy barrier. Herein, Ti was introduced as hard acid into the δ-Bi O (Ti-Bi O ) lattice to tune its local electronic structure and optimize its photo-electrochemistry performance (reduced bandgap, increased conduction band maximum, and extended carrier lifetime).

A PW/Ag functionalized mesoporous silica-coated magnetic FeO core-shell composite as an efficient and recyclable photocatalyst.

The novel composite, FeO@SiO@mSiO-PW/Ag, was successfully prepared by in situ loading Ag nanoparticles (Ag NPs) on the surface of grafted phosphotungstate (denoted as PW) FeO@SiO@mSiOvia a photoreduction deposition method. PW not only acts as a reducing agent and stabilizer for Ag NPs but also as a bridge to link Ag NPs and the SiO shell in the loading process. Its activity toward the photodegradation of methyl orange (MO) and photoreduction of CrO anions was evaluated.

Structural investigation of one- and three-dimensional lanthanide(III) coordination polymers based on functionalized terpyridine carboxylate and aromatic dicarboxylate ligands.

Three series of lanthanide coordination polymers, namely catena-poly[[lanthanide(III)-μ-(benzene-1,2-dicarboxylato)-μ-[2-(2,2':6',2''-terpyridin-4'-yl)benzoato]] monohydrate], {[Ln(CHO)(CHNO)]·HO} or {[Ln(1,2-bdc)(L)]·HO}, with lanthanide (Ln) = dysprosium (Dy, 1), holmium (Ho, 2) and erbium (Er, 3), poly[bis(μ-benzene-1,3-dicarboxylato)bis[μ-2-(2,2':6',2''-terpyridin-4'-yl)benzoato]dilanthanide(III)], [Ln(CHO)(CHNO)] or [Ln(1,3-bdc)(L)], with Ln = gadolinium (Gd, 4), Ho (5) and Er (6), and poly[(μ-benzene-1,4-dicarboxylato)[μ-2-(2,2':6',2''-terpyridin-4'-yl)benzoato]lanthanide(III)], [Ln(CHO)(CHNO)] or [Ln(1,4-bdc)(L)], with Ln = Dy (7), Ho (8), Er (9) and ytterbium (Yb, 10), were synthesized under hydrothermal conditions and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compounds 1-3 possess one-dimensional loop chains with Ln(COO) units, which are extended into three-dimensional (3D) supramolecular structures by π-π interactions. Isostructural compounds 5 and 6 show 6-connected 3D networks, with pcu topology consisting of Ln(COO) units.

A large, X-shaped polyoxometalate [AsFeMoO] assembled from [AsMoO] and [FeMoO] moieties.

A large X-shaped polyoxometalate, [As6Fe7Mo22O98]25- (1), has been synthesized and structurally characterized. The skeleton of 1 is composed of two monocapped hexavacant Keggin [AsMo7O27]9- units and two divacant Anderson [FeMo4O19]11- units fused together through a central Fe5O4 core and two μ4-As2O bridging units, resulting in a unique tetramer with C2h symmetry. The polyanion represents the largest iron-containing arsenomolybdate to date and it contains an unprecedented heptanuclear iron(iii) cluster.

Dy(iii) zig-zag chains assembled in a 3D framework with single-molecule magnet behaviour.

A new lanthanide-based framework, [Dy(STP)(1,2-bdc)]n (1), was constructed. It represents dysprosium(iii) 1D zigzag chains in a 3D framework and displays single-molecule magnet (SMM) behaviour with an energy barrier of 55.76 K under zero dc field.

Lanthanide coordination frameworks constructed from 3,3',4,4'-diphenylsulfonetetracarboxylic and 1,10-phenanthroline: synthesis, crystal structures and luminescence properties.

Two series of lanthanide coordination polymers, [Ln(Hdpstc)(HO)]·nHO (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7), Yb (8)) and [Ln(Hdpstc)(phen)(HO)]·1.5nHO (Ln = Pr (9), Nd (10), Eu (11), Tb (12)) (Hdpstc = 3,3',4,4'-diphenylsulfonetetracarboxylic acid and phen = 1,10-phenanthroline), have been hydrothermally synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction. Isostructural compounds 1-8 and 9-12 exhibit (3,6)-connected 2D layered structures with Hdpstc anions as bridges.

Synthesis, Structure, White-Light Emission, and Temperature Recognition Properties of Eu/Tb Mixed Coordination Polymers.

Two series of Eu(III)/Tb(III) coordination polymers, [LnL(glu)]n·2nH2O (Ln = Eu (1), Tb (2)) and [LnL(glu)(H2O)]n (Ln = Eu (3), Tb (4)) [HL = (2-(2-sulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline, H2glu = glutaric acid] have been hydrothermally synthesized by controlling the pH values and characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. Isomorphic compounds 1 and 2 exhibit 6-connected 3D network with the pcu topological net, containing left- and right-handed helical chains. Isomorphic compounds 3 and 4 show 3,4-connected 2D new topology with the point symbol of (4(2)·6(3)·8)(4(2)·6).

Incorporation of M(H2O)6(2+) between layers {M(H2O)2Ru2(CO3)4Cl2}n(2n-) (M = Zn, Mn): syntheses, structures and magnetic properties.

Isostructural heterometallic diruthenium carbonates KM(H2O)6[M(H2O)2Ru2(CO3)4Cl2]·4H2O [M = Zn (1) and Mn (2)] were synthesized from the reaction of the precursors [Ru2(CO3)4Cl2](5-) and transitional metal ions in aqueous solution. Complexes 1 and 2 show layered structures in which Ru2(II,III) units are linked by four octahedral environment M(H2O)2(2+) ions in a cross fashion and vice versa giving a negative bimetallic square grid layer {M(H2O)2Ru2(CO3)4Cl2}n(3n-). M(H2O)6(2+) ions, linked by K(+) forming zigzag chain {KM(H2O)6}n(3+), are located in the void spaces between the layers.

Cadmium diruthenium(II,III) carbonates showing diverse magnetism behavior arising from variety configuration of [Ru2(CO3)4]n(3n-) layer.

Two hetero-metallic carbonates, namely KCd(H2O)3Ru2(CO3)4·4H2O (1) and KCd(H2O)3Ru2(CO3)4·3.5H2O (2), have been synthesized in a neutral aqueous solution. Both of the 3D dimensional structured complexes contain mixed-valent diruthenium(II,III) carbonate paddlewheel cores of Ru2(II,III)(CO3)4(3-) that are connected to each other in trans- or cis-modes by carbonate oxygen atoms, forming rectangular square-grid and isomeric parallelogram layers [Ru2(CO3)4]n(3n-) in 1 and 2, respectively.

An unusual fan-type polyanion with a silver cation located at the axial center, [AgAsIII2(AsIIIAsVMo4O18(OH)2)3]11-.

A new type of polyoxomolybdate containing mixed-valence arsenic, [AgAs(III)(2)(As(III)As(V)Mo(4)O(18)(OH)(2))(3)](11-) (1), has been synthesized. Single-crystal X-ray analysis was carried out on (NH(4))(5)(C(2)H(9)N(2))(4.5)H(1.

Single-molecule magnet based on a C-type polyoxomolybdate with an S = 11 ground state: [Fe5CoMo22As2O85(H2O)]15-.

A C-type polyoxomolybdate containing a mixed-transition metal cluster Fe(5)Co has been prepared as an ammonium salt, (NH(4))(15)[Fe(5)CoMo(22)As(2)O(85)(H(2)O)]·15H(2)O (1). Interestingly, the magnetism measurements show that the compound exhibits not only an overall ferromagnetic cluster with a large spin ground state of S = 11 but also the behavior of single-molecule magnets.

A diruthenium soft ferromagnet showing T(c) = 3.0 K: Mn4(H2O)16H[Ru2(CO3)4]2[Ru2(CO3)4(H2O)2]·11H2O.

A three-dimensional CO(3)(2-)-bridged Mn(II)-Ru(2)(II,III) complex, Mn(4)(H(2)O)(16)H[Ru(2)(CO(3))(4)](2)[Ru(2)(CO(3))(4)(H(2)O)(2)]·11H(2)O (1), was synthesized by self-assembling Ru(2)(CO(3))(4)(3-) paddle-wheel precursors and Mn(2+) cations. It contains an unprecedented layer [Ru(2)(CO(3))(4)](n)(3n-) with (4,4) network. The ferromagnetic coupling between spin centers results in ordering below 3.

Double sandwich polyoxometalate and its Fe(III) substituted derivative, [As2Fe5Mo21O82]17– and [As2Fe6Mo20O80(H2O)2]16–.

A double sandwich polyoxometalate and its Fe(III) substituted derivative, [As(2)Fe(5)Mo(21)O(82)](17-) (1) and [As(2)Fe(6)Mo(20)O(80)(H(2)O)(2)](16-) (2), were synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, fluorescent spectroscopy, UV spectra, thermogravimetry-differential scanning calorimetry analyses, electrospray ionization mass spectrometry, and magnetism measurements. The polyoxoanion is composed of a central fragment FeMo(7)O(28) for 1 (Fe(2)Mo(6)O(26)(H(2)O)(2) for 2) and two external AsMo(7)O(27) fragments linked together by two distinct edge-sharing dimeric clusters Fe(2)O(10) to lead to a C(2v) molecular symmetry. The central FeMo(7)O(28) fragment and external AsMo(7)O(27) fragment have a similar structure, and both of them can be viewed as a monocapped hexavacant α-Keggin subunit with a central FeO(4) group or a central AsO(3) group.

Combined DFT and BS study on the exchange coupling of dinuclear sandwich-type POM: comparison of different functionals and reliability of structure modeling.

The exchange coupling of a group of three dinuclear sandwich-type polyoxomolybdates [MM'(AsMo7O27)2](12-) with MM' = CrCr, FeFe, FeCr are theoretically predicted from combined DFT and broken-symmetry (BS) approach. Eight different XC functionals are utilized to calculate the exchange-coupling constant J from both the full crystalline structures and model structures of smaller size. The comparison between theoretical values and accurate experimental results supports the applicability of DFT-BS method in this new type of sandwich-type dinuclear polyoxomolybdates.

Three banana-shaped arsenomolybdates encapsulating a hexanuclear transition-metal central magnetic cluster: [As(III)2Fe(III)5MMo22O85(H2O)]n- (M = Fe3+, n = 14; M = Ni2+ and Mn2+, n = 15).

Three polyoxometalates encapsulating high-nuclearity magnetic clusters MFe(5), [As(2)MFe(5)Mo(22)O(85)(H(2)O)](n-) (M = Fe(3+), n = 14; M = Ni(2+) and Mn(2+), n = 15), were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis, and magnetism measurements. The polyanion [As(2)MFe(5)Mo(22)O(85)(H(2)O)](n-) consists of a central MMo(7)O(28) (M = Fe(3+), Ni(2+), and Mn(2+)) fragment and two AsMo(7)O(27) fragments linked together by two trimeric clusters, Fe(2)MoO(μ(2)-O)(2) and Fe(3)(H(2)O), to form a banana-shaped structure with C(1) symmetry. The MMo(7)O(28) and AsMo(7)O(27) units have a similar structure and can be considered as a monocapped hexavacant α-B-Keggin subunit with a central MO(4) group or a central As(III)O(3) group.

A cagelike polyanion with a Ag+ enwrapped, [AgAs2Mo15O54]11-.

The polyanion [AgAs(2)Mo(15)O(54)](11-) has an unusual cage-like structure composed of [AsMo(6)O(27)](15-) and [AsMo(6)O(24)](9-) subunits connected by three MoO(4) tetrahedra, and a Ag(+) cation is inclosed at the center of the cage and coordinated by two As atoms with a As-Ag-As bond angle of 180° along with three μ(3)-oxo groups from MoO(4) tetrahedra to lead to a trigonal-pyramidal coordination geometry. The compound was also characterized by IR, X-ray photoelectron spectroscopy, fluorescent spectroscopy, and thermogravimetry-differential scanning calorimetry. The stability of [AgAs(2)Mo(15)O(54)](11-) in aqueous solution was investigated by using electronic absorbance spectroscopy and electrospray ionization mass spectrometry.

AsMo7O27-bridged dinuclear sandwich-type heteropolymolybdates of Cr(III) and Fe(III): magnetism of [MM'(AsMo7O27)2]12- with MM' = FeFe, CrFe, and CrCr.

Two new dinuclear sandwich-type heteropolymolybdates based on the mulitidendate inorganic fragment [AsMo(7)O(27)] and Cr(III) and Fe(III) ions, namely, the homometallic sandwich polyoxometalate (POM) (NH(4))(12)[Fe(2)(AsMo(7)O(27))(2)] x 12 H(2)O (1) and the first example of the "symmetrical" heterometallic Cr(III)-Fe(III) sandwich POM, (NH(4))(12)[FeCr(AsMo(7)O(27))(2)] x 13 H(2)O (2), were simultaneously synthesized in high yield. Their magnetic properties are thoroughly investigated together with the homometallic sandwich POM (NH(4))(12)[Cr(2)(AsMo(7)O(27))(2)] x 11 H(2)O (3). The chi(M)T values for compounds 1-3 at 300 K correspond well to the calculated spin-only values for Fe(III) (S = 5/2) and Cr(III) (S = 3/2) with g(Fe) = g(Cr) = 2.

Two sandwich arsenomolybdates based on the new building block As(iii)Mo(7)O(27)(9-): [Cr(2)(AsMo(7)O(27))(2)](12-) and [Cu(2)(AsMo(7)O(27))(2)](14-).

The polyanions [Cr(2)(AsMo(7)O(27))(2)](12-) () or [Cu(2)(AsMo(7)O(27))(2)](14-) () have sandwich-like structures wrapping two transition metals between two [As(iii)Mo(7)O(27)](9-) fragments, and the fragment is unprecedented and can be viewed as a mono-capped hexavacant B-alpha-Keggin subunit with a central AsO(3) group.

An unusual asymmetric polyoxomolybdate containing mixed-valence antimony and its derivatives: [Sb4VSb2IIIMo18O73(H2O)2]12- and {M(H2O)2[Sb4VSb2IIIMo18O73(H2O)2]2}22- (M = MnII, FeII, CuII or CoII).

A new type of heteropolyanion containing mixed-valence antimony, [Sb4(V)Sb2(III)Mo18O73(H2O)2](12-) (1a), and its four derivatives, {M(H2O)2[Sb4(V)Sb2(III)Mo18O73(H2O)2]2}(22-) (M = Mn(II), Fe(II), Cu(II), or Co(II)) (2a-5a), have been isolated as ammonium salt, and their structures were determined by single-crystal X-ray diffraction. The framework of the polyanion 1a displays a curious asymmetric structure, and there exist six types of Sb coordination environments and seven types of {MoO6} octahedra. The title compounds were also characterized by elemental analyses, IR, UV-vis, Raman spectra, and cyclic voltammogramms.

The novel sandwich-type heteropolyoxotungstates [M2Bi2(beta-B-MW9O34)2]14- (M = Co(II), Zn(II)): beta-type dimeric heteropolyanions with a transition metal as the central heteroatom and Bi(III) and M as linking atoms.

Two new sandwich-type heteropolyoxometalates, Na(14)[Co(2)Bi(2)(beta-B-CoW(9)O(34))(2)].48H(2)O (1) and Na(14)[beta-B-Zn(2)Bi(2)(ZnW(9)O(34))(2)].51H(2)O (2), have been synthesized at pH = 7.