Syntheses and Crystal Structures of Two New Pentaborates Templated by Transition-Metal Complexes

Two new pentaborates [M(dap)₃][B₅O₆(OH)₄]₂·H₂O (M = Co (1) and Ni (2); dap = 1,2-diaminopropane) have been hydrothermally synthesized. Both structures were determined by single crystal X-ray diffraction and further characterized by elemental analysis, FT-IR, thermogravimetric analysis and photoluminescence spectroscopy. Two compounds are isostructural and consist of isolated pentaborate [B₅O₆(OH)₄]^? anions and [M(dap)₃]²⁺ complex cations. The anionic [B₅O₆(OH)₄]^? groups are linked by extensive hydrogen bonds to form a 3-D supramolecular framework with large channels, in which the transition-metal complex templates are located. The luminescent properties of 1 and 2 were studied, and blue luminescence occurs with an emission maximum at 405 and 408 nm upon excitation at 332 and 328 nm respectively. Crystal data: 1, monoclinic, space group P2₁/c (No. 14), a = 9.7159(5) Å, b = 29.3372(19) Å, c = 11.5121(6) Å, β = 103.286(5)°, V = 3193.6(3) ų, Z = 4; 2, monoclinic, space group P2₁/c, a = 9.7264(4) Å, b = 29.3810(16) Å, c = 11.5185(6) Å, β = 103.249(4)°, V = 3204.0(3) ų, Z = 4.     

Synthesis,Structural Characterization and Properties of Two Strontium Borates Constructed from Oxo Boron Clusters

Two strontium borates Sr₂[B₆O₉(OH)₄] (1) and Sr₂B₅O₉(OH)·H₂O (2), with acentric structures have been synthesized under hydro/solvothermal conditions. Compound 1 is reported for the first time in the strontium borates system, and it crystallizes in the monoclinic space group P2₁ with unit cell parameters a = 6.8445(5) Å, b = 8.7033(6) Å, c = 8.4632(6) Å, β = 100.581(6)°, V = 495.58(6) ų and Z = 2. Its structure consists of unusual borate layers of 3, 11-membered rings, which are interconnected via Sr–O ionic bonds and hydrogen bonds to generate a 3D supramolecular network. Compound 2 is a known strontium borate, crystallizing in the monoclinic space group C ₂ with a = 10.161 (13) Å, b = 7.965(4) Å, c = 6.393(11) Å, β = 128.0(2)°, V = 407.7(14) ų and Z = 2. Second-harmonic generation measurements on the powder samples reveal that 1 and 2 exhibits good SHG efficiency about 1.5 and 2 times that of KDP (KH₂PO₄) powder respectively.     

Metal thiolate compounds: Processable ceramic precursors

Full crystallographic characterization has been obtained for [Hg(SBz)₂]_∞ (9), ClHgSBz · TMEDA (10), [ClHgS-i-Pr]_∞ (11), [ClHg(S-neo-Pent)·0.5Py]_∞ (12), In[S-2,4,6-(i-Pr)₃C₆H₂]₃·2MeCN (13), [In(S-2-MeO,5-Me, C₆H₃)₃]₂ (14) and In(S-o-C₆H₄CH₂N(CH₃)₂)₃ (15). Relevent metal thiolate interactions, terminal and bridging, are highlighted within the realm of thermolytic conversion of these species into binary metal thiolates. Pertinent crystallographic data for these compounds include:9: C2/c,a=22.599(4)Å,b=4.334(1)Å,c=29.596(5)Å,β=106.76(1)°,V=2775.6ų,Z=8,R=3.6%;10: P $\bar 1$ ,a=8.136(2)Å,b=9.958(7)Å,c=11.834(3)Å,α=108.71(2)°,β=92.93(2)°,γ=109.05(2)°,V=845.3ų,Z=2,R=5.0%;11: C2,a=21.430(7)Å,b=4.678(2)Å,c=6.724(2)Å,β=90.43°,V=674.0ų,Z=2,R=3.9%;12: C2,a=16.732(2)Å,b=11.200(1)Å,c=11.929(2)Å,β=104.21(1)°,V=2167.1ų,Z=4,R=3.5%;13: P $\bar 1$ ,a=13.680(8)Å,b=13.815(6)Å,c=15.155(9)Å,α=77.77(4)°,β=72.57(4)°,γ=88.18(4)°,V=2669.1ų,Z=8,R=12.0%;14: C2,a=8.323(2)Å,b=24.970(4)Å,c=12.466(2)Å,β=104.32(2)°,V=2510.1ų,Z=4,R=8.2%;15: P2₁/c,a=17.587(5)Å,b=11.786(2)Å,c=13.865(2)Å,β=101.66(2)°,V=2814.6ų,Z=4,R=3.2%. The molecules-to-materials transition, from a relatively simple divalent system, to the more mechanistically complex trivalent metal system is outlined.     

1D Chain-Like Architecture in Anderson Heteropolymolybdate {[Eu(H2O)6]2(TeMo6O24)}·6H2O: Synthesis and Characterization

A new Anderson-based heteropolymolybdate {[Eu(H₂O)₆]₂(TeMo₆O₂₄)}·6H₂O (1) has been hydrothermally synthesized and characterized by elemental analyses, IR, thermal stability analysis, XRD and single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P-1, a = 9.4023(6) Å, b = 10.2530(7) Å, c = 10.6525(10) Å, α = 101.583(7)º, β = 108.024(7)º, γ = 107.150(6)º, V = 883.60(12) ų, Z = 1, R₁ = 0.0338, wR₂ = 0.0849. Compound 1 exhibits 1D chain-like structure formed by the alternative connection between Anderson type polyoxoanions [TeMo₆O₂₄]^6? and Eu³⁺ along a-axis. Compound 1 displays good fluorescent emission of the Eu³⁺ ion at room temperature.     

Synthesis, Crystal Structure and Characterization of a Mixed-Valence Keggin-Structural 12-Molybdophosphoric Acid Compound: NH4(C4N2H12)(C2N2H10)2[Mo 4 V Mo 8 VI PO40]·2H2O

A mixed-valence Keggin-structural 12-molybdophosphoric acid hydrate, NH₄(C₄N₂H₁₂)(C₂N₂H₁₀)₂ [Mo ₄ ^V Mo ₈ ^VI PO₄₀]·2H₂O (1), has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction, elemental analysis, TG, XRD, IR, Raman, UV–Vis diffuse reflection spectrum and XPS spectrum. The compound 1 crystallizes in the monoclinic system with cell parameters of a = 20.668(4) Å, b = 10.827(2) Å, c = 21.508(4) Å, β = 117.070(3)°, V = 4,285.6(14) ų, and space group C _2/c, Z = 4 at 293 K. The final full-matrix least-squares refinement converged to R ₁ = 0.029 for the observed reflections (4,721) with I > 2σ(I) and wR ₂ = 0.065 for all data (4,837) and S = 1.048. Compared with another compound, (C₄N₂H₁₂)(C₂N₂H₁₀)₂[Mo₅P₂O₂₃] (2) (Chen et al., Chin J Struct Chem 30:1178, 2011), compound 1 was obtained via only changing molar ratio of reactants and the pH value of reaction system. Meanwhile, compound 1 contains the same two kinds of organonitrogen ligands, even their molar ratio, but entirely different space architecture and distinct heteropoly blue building block, [Mo ₄ ^V Mo ₈ ^VI PO₄₀]^7?. The crystal packing of 1 presents interesting 1D Zig-zag, 2D laminated and even 3D honeycomb-like configurations.     

Synthesis and study of tetraamminecobalt hydrogen hexamolybdometalates(III)

Tetraamminecobalt hydrogen hexamolybdoferrate [Co(NH₃)₄] · H[FeMo₆O₁₈(OH)₆] · 6H₂O (I) and tetraamminecobalt hydrogen hexamolybdogallate(III) [Co(NH₃)₄] · H[GaMo₆O₁₈(OH)₆] · 6H₂O (II) were synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray diffraction. Crystals of I and II are monoclinic; a = 16.21 Å, b = 5.43 Å, c = 12.32 Å, β = 119.63°, V = 1092.11 ų, ρ_calcd = 2.21 g/cm³, and Z = 1 for I; a = 16.24 Å, b = 5.59 Å, c = 12.29 Å, β = 119.79°, V = 1064.05 ų, ρ_calcd = 2.15 g/cm³, and Z = 1 for II. Compounds I and II were used as catalysts for soft oxidation of natural gas.     

A one-dimensional chain of polyoxometalate polymer bridged by dinuclear copper coordination units with 4-(5-phenylpyridin-2-yl)pyridine

A new Keggin polyoxometalate-based polymer, formulated as (Hppy)₂Cu₂(ppy)₄[SiMo₁₂O₄₀] (1) ppy = 4-(5-phenylpyridin-2-yl)pyridine, had been synthesized under hydrothermal conditions. Complex 1 exhibits a one-dimensional polyoxometalate-based chain constructed from Keggin anions of [SiMo₁₂O₄₀]^4? weakly connected by dinuclear [Cu(ppy)₂] groups. This complex crystallizes in the triclinic space group P-1, a = 12.621(3) Å, b = 13.168(3) Å, c = 17.467(4) Å, α = 86.09(3)°, β = 85.35(3)°, γ = 64.10(3)°, V = 2601.1(9) Å³, Z = 1. The elemental analyses, FT-IR, TG-DTA for this compound were also determined.     

Three types of heterometallic structural motifs based on [Mo(CN)8]3−/4− anion and MnII cation as building blocks

The reaction between K₃[Mo(CN)₈] · H₂O and MnCl₂ · 4H₂O in different reaction conditions have obtained three new bimetallic cyanide-bridged compounds, namely, {(tetrenH₂)_0.5[Mn(H₂O)₂][Mo^V(CN)₈] · 2H₂O} _n (1) (where, tetren is tetraethylenepentamine), {[Mn₂(H₂O)₄][Mo^IV(CN)₈] · 3H₂O} _n (2), and {[Mn₂(H₂O)₄][Mo^IV(CN)₈] · 4H₂O} _n (3). Compound 1 crystallizes in the orthorhombic system with space group Cmc21 and unit cell constants a = 7.8234(15), b = 26.013(5), c = 10.021(2) Å, β = 90°, and Z = 4. Compound 2 crystallizes in the monoclinic system with space group P21/n and unit cell constants a = 7.3329(11), b = 14.372(2), c = 18.070(3) Å, β = 90.869(2)°, and Z = 4. Compound 3 crystallizes in the tetragonal system with space group I4/m and unit cell constants a = b = 11.9371(8), c = 13.2930(18) Å, β = 90°, and Z = 4. X-ray single-crystal structures reveal that the Mo centers adopt a distorted square antiprism coordination environment for 1 and 3, while 2 closed to a bicapped trigonal prism. For these complexes, all the Mn^II centers in the extended structure adopt distorted octahedron geometry. For 1, each Mo^V coordinated via four cyanide groups to four Mn^II ions, and the other four cyanide groups are terminal, forming a two-dimensional framework. For 2, the Mo^IV center of structural unit coordinated via four cyanide groups to four Mn(1), and the other four cyanide groups coordinated to four Mn(2), forming a three-dimensional framework. For 3, each [Mo^IV(CN)₈]^4? building block is linked to Mn^II ions through its eight CN ligands, and each Mn^II center is connected to four Mo units forming a three-dimensional framework. In addition, magnetic studies of these complexes have also been presented.     

Synthesis and crystal structure of diferrocenylmethoxyethylamine

The reaction of diethanolamine with diferrocenylmethyl carbonium (2) that was generated by diferrocenylmethanol (1) treated with BF₃ in CH₂Cl₂ provided the synthesis of title compound diferrocenylmethoxyethylamine (3). The structure of 3 was determined by the X-ray diffraction (XRD) with crystal data: monoclinic P2₁/n space group and a=5.8419(14) Å, b=13.572(3) Å, c=23.839(6) Å, α=90°, β=91.827(5)°, γ=90°, V=1889.2(8) Å³, Z=4, D _c =1.558 mg·m^?3, μ=1.548 mm^?1, F(000)=920. The intra- and inter-molecular H bonding modes in 3 were demonstrated both in molecular crystal structure and IR spectral characterization.     

Solvothermal Syntheses and Crystal Structures of Two Novel Borates: [(CH3)3NH][B5O6(OH)4] and Na2[H2TMED][B7O9(OH)5]2

Two novel borates [(CH₃)₃NH][B₅O₆(OH)₄] (I) and Na₂[H₂TMED][B₇O₉(OH)₅]₂ (II) have been synthesized under solvothermal conditions, and characterized by elemental analyses, FT-IR spectroscopy, and single crystal X-ray diffraction. Crystal data for I: monoclinic, P2₁/c, a = 9.3693(11) Å, b = 14.0375(17) Å, c = 10.0495(9) Å, β = 91.815(9)°, Z = 4. Crystal data for II: monoclinic, P2₁/c, a = 11.6329(2) Å, b = 11.9246(3) Å, c = 10.2528(2) Å, β = 100.178(2)°, Z = 4. Their crystal structures both have 3D supramolecular framework with large channels constructed by O–H···O hydrogen-bonding among the polyanions of [B₅O₆(OH)₄]^? or [B₇O₉(OH)₅]^2? clusters. The templating organic amines cations in I and II are both located in the channels of 3D supramolecular frameworks, respectively, and interact with the polyborate frameworks both electrostatically and via hydrogen bonds of N–H···O. Na₂[H₂TMED][B₇O₉(OH)₅]₂ is the first example of heptaborate co-templated by alkali metal and organic base, which is also rare in borates. The photoluminescence property of the synthetic sample of Na₂[H₂TMED][B₇O₉(OH)₅]₂ in the solid state at room temperature was also investigated by fluorescence spectrophotometer.     

Synthesis, Crystal Structure and Magnetic Property of a New Two-Dimensional Polymers with 4-Connected sql Topology

A new polymer [Mn₃(OAc)₆(H₂O)₁₂] _n (1) based on trinuclear manganese clusters has been synthesized under hydrothermal condition and structurally characterized by single-crystal X-ray diffraction analysis. The compound crystallizes in monoclinic system, space group P2₁/c, with a = 10.401(5), b = 17.527(7), c = 9.073(4) Å, α = 90, β = 110.943(7), γ = 90°, V = 1544.8(12) Å³, Z = 2. Compound 1 is a two-dimensional (2D) structure with 4-connected sql topology, and is further extended to a 3D supramolecular framework by hydrogen bonds. Variable temperature magnetic susceptibility measurements indicate antiferromagnetic couplings between Mn²⁺ ions. Furthermore, elemental analyses and powder X-ray diffraction properties of 1 are also investigated.     

Dicopper(II) Assembly Containing the Tetrameric Cluster of Water Constructed from Terephthalate Dianion and Copper(II) Macrocyclic Fragment

To utilized a mononuclear fragment of [Cu(L)Cl]ClO₄ (1) and TPHA bridged-ligand as building block by self-assembly technology, a new dinuclear copper(II) compound [(CuL)₂(μ-TPHA)](ClO₄)₂ · 4H₂O (2), where L = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1^6,9]octadecane, TPHA = terephthalate dianion, has been constructed and structurally characterized by X-ray crystallography. Crystal analyses denotes that crystal water molecules interact with each other give rise to a tetrameric cluster of water, which by sharing dinuclear units result in a 1D chain structure. Complex 2 crystallizes in monoclinic, space group P2₁/c, with a = 11.1586(14), b = 13.2240(16), c = 16.241(2) Å and β = 105.636(2)°. Magnetic measurements confirm that 2 present an antiferromagnetic interaction between the paramagnetic ions.     

Synthesis and Characterization of a Novel 3D Organic–Inorganic Hybrid Framwork Templated by Keggin Anions

A novel 3D compound, {K₃H₂[Cu(Gly)₂]₃BW₁₂O₄₀}·10H₂O 1 (Gly = glycine), has been synthesized and characterized by elemental analyses, IR, TG analyses, cyclic voltammetry, and single-crystal X-ray diffraction. Compound 1 contains square-grid layers constructed by potassium cations and copper-glycine coordination complexes, the [BW₁₂O₄₀]^4? anions as templates are accommodated in the square grids by connecting with the K atoms. The K atoms link [BW₁₂O₄₀]^4? anions from different layers together to yield a 3D novel structure. The crystal data for compounds 1: monoclinic, space group p2(1)/n, a = 18.832(4) Å, b = 16.488(3) Å, c = 20.570(4) Å, β = 106.21(3)°, V = 6133(2) Å³, Z = 4.     

Oxidation of coordinated ethylenediamine in platinum(IV) complexes with bromine. Crystal structures of [Pt(en)Py2Br2]Br2 · H2O, [Pt(HN-C(O)-C(O)-NH)Py2Br2] · H2O, and [Pt(en)PyBr3]NO3

Heating of an aqueous solution of [Pt(en)Py₂Cl₂]Cl₂ · 2H₂O (I) with KBr excess leads to the formation of [Pt(en)Py₂Br₂]Br₂ · H₂O (II). The interaction of a solution of II with bromine water results in the precipitation of polybromide ([Pt(en)Py₂Br₂]Br₂ · Br₂), which within a few days in the reaction solution partly transforms into oximide platinum(IV) complex, [Pt(HN-C(O)-C(O)-NH)Py₂Br₂] · H₂O (III). Complex [Pt(en)PyBr₃]Br · H₂O (IV) with an impurity of II was prepared by reacting KBr excess and the product of [Pt(en)Py₂]Cl₂ oxidation with chlorine in 0.05 N HCl. The action of HNO₃ on the solution of IV produced a nitrate derivative ([Pt(en)PyBr₃]NO₃, V). Complex IV, unlike II, does not react with bromine. The IR spectra of all the obtained compounds were recorded. Complexes II, III, and V were studied by X-ray crystallography. The crystals of II are monoclinic, space group P2₁/c, a = 15.640(2) Å, b = 9.345(1) Å, c = 14.167(2) Å, β = 102.63(1)°, V = 2020.5(5) ų, Z = 4, R _hkl = 0.033. The crystals of III are triclinic, space group P $\bar 1$ , a = 7.108(1) Å, b = 10.946(1) Å, c = 11.020(2) Å, α = 83.63(1)°, β = 80.31(1)°, γ = 75.02(1)°, V = 814.4(2) ų, Z = 2, R _hkl = 0.033. In the near-planar five-membered chelate ring (torsion angle NCCN is 7°), the C-O distances (1.23(1) Å) correspond to double bonds; the C-C (1.53(1) Å) and C-N (1.31(1) Å), distances correspond to ordinary bonds. The crystals of V are monoclinic, space group P2₁/c, a = 8.306(2) Å, b = 8.995(2) Å, c = 20.231(4) Å, β = 97.48(2)°, V = 1498.6(6) ų, Z = 4, R _hkl = 0.037.     

Diethyltin-Containing Tungstoarsenate(V), [{Sn(C2H5)2}3(H2O)6(A–α–AsVW9O34)]3−

Reaction of (C₂H₅)₂SnCl₂ with the trilacunary 9-tungstoarsenate(V) [A–α–AsW₉O₃₄]^9? in aqueous pH 5 medium resulted in the diethyltin-containing polyanion [{Sn(C₂H₅)₂}₃(H₂O)₆(A–α–As^VW₉O₃₄)]^3? (1), which crystallized as a hydrated guanidinium salt, [C(NH₂)₃]₃[{Sn(C₂H₅)₂}₃(H₂O)₄(A–α–As^VW₉O₃₄)]·9H₂O (1a). Polyanion 1 represents the first example of a diethyltin-containing polyanion. The diethyltin groups are bound to the trilacunary Keggin units via two Sn–O(W) bonds involving edge-shared WO₆ octahedra. Each Sn atom also has two terminal, cis-related water ligands, and two terminal, trans-related ethyl groups. Multinuclear (¹H, ¹³C, ¹¹⁹Sn, ¹⁸³W) NMR spectrometry indicated that polyanion 1 is stable in solution. Compound 1a was structurally characterized in the solid state by single-crystal XRD, FT-IR, as well as thermogravimetric and elemental analyses. Single-crystal X-ray analysis showed that 1a crystallizes in the orthorhombic system, space group P _nma , with a = 23.5280(10) Å, b = 15.5435(6) Å, c = 18.6191(9) Å, V = 6809.1(5) ų and Z = 4. The structure of 1a is an extended 2D assembly of individual polyanion units 1 linked via Sn–O(W) bridges.     

Two New One-Dimensional Chain-Like Compounds Constructed from the Sandwich-Type Polyoxotungstate Clusters

Two new one-dimensional chain-like compounds, K₄Na₄[Mn₂(H₂O)₈Mn₄(H₂O)₂(GeW₉O₃₄)₂] · 20.5H₂O (1) and K₂Na₄Cu₂(H₂O)₁₂[Cu(H₂O)₂Cu₄(H₂O)₂(SiW₉O₃₄)₂] · 15H₂O (2), constructed from the sandwich-type clusters, have been obtained by the routine synthetic reactions in aqueous solutions, and their structures were determined by X-ray single crystal diffraction analysis. The crystal data is following: for 1, space group, monoclinic, P _21/n, a = 16.693(3) Å, b = 14.935(3) Å, c = 20.090(4) Å, β = 92.23(3)°, V = 5004.7(17) ų, Z = 2; For 2, space group, triclinic, P _?1, a = 11.744(2) Å, b = 13.415(3) Å, c = 17.609(4) Å, α = 73.08(3)°, β = 82.68(3)°, γ = 65.18(3)°, V = 2409.1(8) ų, Z = 1. The crystal structure of 1 shows a 1D ladder-like chain, built up of the sandwich anions [Mn₄(H₂O)₂(GeW₉O₃₄)₂]^12? and the Mn²⁺ ions. Compound 2 is a polymeric chain, composed of the Cu-substituted sandwich-type anions [Cu₄(H₂O)₂(SiW₉O₃₄)₂]^12? linked by the Cu(H₂O)₄ clusters. These extended materials based on the sandwich-type polyoxoanions are rarely reported in the POM chemistry.     

Copper(I) halide complexes with N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L2+). Synthesis and crystal structures of the complexes [L0.5CuCl2], [L0.5CuCl0.72Br1.28], and [L0.5CuBr2]

The Eschweiler-Clarke reaction of ethylenediamine with formaldehyde and formic acid yielded N,N,N′,N′-tetramethylethylenediamine, which was alkylated with allyl chloride or allyl bromide to give the corresponding N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L²⁺) dihalides. In methanolic solutions of copper(II) halide and an appropriate ligand, ac electrochemical synthesis with copper wire electrodes afforded single crystals of Cu(I) complexes with L²⁺: [L_0.5CuCl₂] (I), [L_0.5CuCl_0.72Br_1.28] (II), and [L_0.5CuBr₂] (III). The crystal structures of complexes I–III were determined by X-ray diffraction study. The isostructural crystals of I and II are monoclinic, space group P2₁/n, Z = 4. For I: a = 7.632(4) Å, b = 11.318(5) Å, c = 10.635(5) Å, β = 98.551(7)°, V = 908.4(7) ų. For II: a = 7.7415(7) Å, b = 11.4652(9) Å, c = 10.7267(10) Å, β = 98.351(4)°, V = 942.0(2) ų. The organic cation L²⁺ acts as a bridge linking a pair of separate cuprous halide fragments Cu₂X₄. Although being isostoichiometric with I and II, complex III has a different structure. The crystals of III are monoclinic, space group P2₁/c, a = 6.519(2) Å, b = 9.060(3) Å, c = 16.284(6) Å, β = 97.219(4)°, V = 954.2(6) ų, Z = 4. In structure III, the inorganic fragment forms infinite polymer chains (CuBr ₂ ^? ) _n . The organic and inorganic parts are held together only by electrostatic interactions. Structures I–III are stabilized by hydrogen bonds (C)H…X (2.6–2.9 Å).     

Amino Acid Functionalization of {Ni6PW9}-Based Clusters Under Hydrothermal Conditions

Two novel hexa-nickel(II)-substituted Keggin-type {Ni₆PW₉}-based tungstophosphates [Ni₆(μ ₃-Tris)(en)₃(Pr)(damp)(H₂O)₂(B-α-PW₉O₃₄)]·10H₂O (1) and [Ni₆(μ ₃-Tris)(en)₃(damp)₂(H₂O)₂(B-α-PW₉O₃₄)]·7H₂O (2) (en = ethylenediamine, Pr = CH₃CH₂COO^?, damp = 2-aminoisobutyrate, Tris = pentaerythritol) were hydrothermally synthesized and characterized by IR spectra, elemental analyses, powder X-ray diffraction, thermogravimetric analyses, and single-crystal X-ray diffraction. Crystal data for 1: orthorhombic, Pca2₁, a = 21.6962(7) Å, b = 20.6398(5) Å, c = 14.7825(4) Å, β = 90º, V = 6619.7(3) Å³, Z = 4; for 2: orthorhombic, Pca2₁, a = 21.6978(9) Å, b = 20.6658(7) Å, c = 14.7767(4) Å, β = 90º, V = 6625.9(4) Å³, Z = 4. 1 consists of a {Ni₆(μ ₃-Tris)(en)₃(Pr)(damp)(H₂O)₂}⁹⁺ core and a [B-α-PW₉O₃₄]^9? (PW₉) unit and is covalently functionalized by one Pr and one damp, as well as en and Tris ligands. The structure of 2 is the same to 1 except that the Pr anion in 1 is substituted by the other damp ligand. Most interestingly, 1 contains four kinds of organic ligands, while 2 includes three kinds of organic ligands, which are first observed in polyoxometalate chemistry.     

Two Hexa-Ni-Substituted AsW9O34 Clusters Functionalized by Organic Ligands

Hydrothermal reactions of trilacunary precursor A-α-AsW₉O₃₄ ^9? polyoxoanions and nickel ions in the presence of ethylenediamine (en = ethylenediamine) led to two new hexa-Ni-substituted Keggin-type tungstoarsenates [Ni₆(μ ₃-OH)₃(en)₃(H₂O)₆(B-α-AsW₉O₃₄)]·6H₂O (1) and [Ni₆(μ ₃-OH)₃(en)₃(H₂O)₆(B-α-AsW₉O₃₄)]·10H₂O (2), which have been characterized by elemental analyses, IR spectra, powder X-ray diffraction, thermogravimetric analyses and single-crystal X-ray diffraction. Crystal data for 1: hexagonal, R3c, a = b = 20.4379(5) Å, c = 21.5062(6) Å, β = 120º, V = 7779.8 (3) Å³ and Z = 6; for 2: momoclinic, P2₁/c, a = 13.4200(3) Å, b = 19.1428(5) Å, c = 22.8845(9) Å, β = 112.403(3)º, V = 5435.2(3) Å³ and Z = 4. Structural analyses reveal that the [Ni₆(μ ₃-OH)₃(B-α-AsW₉O₃₄)] clusters in 1 and 2 are covalently functionalized by neutral en ligands, in which two similar {Ni₆(μ ₃-OH)₃(en)₃(H₂O)₆}⁹⁺ cores have been observed by our lab. Notably, 1 and 2 represent the highest number of substituted transition metal ions in all known lacunary Keggin-type polyoxotungstoarsenate monomers.     

Two new organic borates with the large [B14O20(OH)6]4− oxoboron clusters

Two new borate clusters, [NH₃(CH₂)₃NH₃]₂[B₁₄O₂₀(OH)₆] (1) and [NH₃(CH₂)₆NH₃]₂[B₁₄O₂₀(OH)₆] (2), have been made under solvothermal conditions and characterized by single-crystal X-ray structural analysis. Also their IR and UV–Vis spectroscopy, thermogravimetric analysis, and elemental analysis have been investigated, respectively. Crystal data for 1: triclinic, P-1, a = 8.8049(4) Å, b = 9.1585(5) Å, c = 10.1912(5) Å, α = 74.925(4)°, β = 80.987(4)°, γ = 67.495(5)°, Z = 1. Crystal data for 2: triclinic, P-1, a = 9.2010(4) Å, b = 9.8663(4) Å, c = 11.4191(4) Å, α = 107.014(4)°, β = 92.514(3)°, γ = 107.265(4)°, Z = 1. The structures consist of isolated 8-membered boron ring made of the [B₇O₁₀(OH)₃]^2?cluster subunits. UV–Vis spectral investigation indicates that they are wide-band-gap semiconductors. Fluorescence spectroscopy indicates that they are potential blue light materials.