Bi2(IO3)(IO6): First combination of [IO3]− and [IO6]5− anions in three-dimensional framework

A new bismuth (III) iodate periodate, Bi₂(IO₃)(IO₆) was obtained from hydrothermal reactions using Bi(NO₃)₃·5H₂O, and H₅IO₆ as starting materials. Bi₂(IO₃)(IO₆) crystallizes in the monoclinic space group P2₁/c (No. 14) with lattice parameters ɑ = 8.1119(6), b = 5.4746(4), c = 16.357(1) Å, β = 99.187(2)°, V = 717.07(9) ų, Z = 4. The structure of Bi₂(IO₃)(IO₆) features a three-dimensional framework which is a combination of [Bi(1)O₅] tetragonal pyramids, [Bi(2)O₈] bicapped trigonal prisms and [IO₃]⁻ and [IO₆]⁵⁻ anions. Thermal analysis shows that the compound is thermally stable up to about 350 °C. The solid state UV-vis-NIR diffuse reflectance spectrum indicates that Bi₂(IO₃)(IO₆) is a semiconductor with a band gap of 2.76 eV.     

The structure of the VO2F3−4 ion: Crystal structure of (NH4)3VO2F4

The VO₂F³⁻₄ ion has a cis octahedral structure, as is shown by single crystal structure analysis of the title compound. The unit cell of (NH₄)₃VO₂F₄ (space group Immm or I222, a = 912.6(2), b = 1881.8(4), c = 626.4(1) pm, Z = 6) contains two symmetrically independent anions. One is rotationally disordered. Oxo and fluoro ligands cannot be distinguished. But the second one has a distorted cis octahedral structure with the lengths 170.0(4), 186.1(4), and 202.3(4) pm for the VO, VF (axial), and VF (equatorial) bonds. Infrared and Raman spectra as well as theoretical considerations support the crystallographic results. The phase transitions at 418 and 215 K were confirmed by variable temperature X-ray powder diffraction. Above 418 K the cubic cryolite type structure is adopted with a = 902.6(2) pm. Plausible mechanisms for the phase transitions are suggested.     

1,3-Diphenyl-5-(9-phenanthryl)-2-pyrazoline (DPPhP): An Excellent Hole-Transport Material for Use in Organic Light-Emitting Diodes

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3D Organic–Inorganic Perovskite Ferroelastic Materials with Two Ferroelastic Phases: [Et3P(CH2)2F][Mn(dca)3] and [Et3P(CH2)2Cl][Mn(dca)3]

Organic–inorganic hybrid perovskite-type multiferroics have attracted considerable research interest owing to their fundamental scientific significance and promising technological applications in sensors and multiple-state memories. The recent achievements with divalent metal dicyanamide compounds revealed such malleable frameworks as a unique platform for developing novel functional materials. Herein, two 3D organic–inorganic hybrid perovskites [Et₃P(CH₂)₂F][Mn(dca)₃] ( 1 ) and [Et₃P(CH₂)₂Cl][Mn(dca)₃] ( 2 ) (dca=dicyanamide, N(CN)₂⁻) are presented. Accompanying the sequential phase transitions, they display a broad range of intriguing physical properties, including above room temperature ferroelastic behavior, switchable dielectricity, and low-temperature antiferromagnetic ordering (T_c=2.4 K for both 1 and 2 ). It is also worth noting that the spontaneous strain value of 1 is far beyond that of 2 in the first ferroelastic phase, as a result of the precise halogen substitution. From the point view of molecular design, this work should inspire further exploration of multifunctional molecular materials with desirable properties.     

Reactions of the Cluster Anion [HRu3(CO)11)]− with Dicyclohexylphosphine: Synthesis and Molecular Structure of H2Ru3(CO)8(PCy2)2 and H2Ru3(CO)6(PCy2)2(HPCy2)2

The cluster anion [HRu₃(CO)₁₁]^- (1) reacts with dicyclohexylphosphine in THF solution to give the anionic derivative [HRu₃(CO)₈(PCy₂)₂]^- (2), protonation of which yields the neutral cluster H₂Ru₃(CO)₈(PCy₂)₂ (3) and, in the presence of excess phosphine, HRu₃(CO)₇(PCy₂)₃ (4). In protic methanol as reaction medium, the reaction of 1 with HPCy₂ gives directly the neutral complex H₂Ru₃(CO)₆(PCy₂)₂(HPCy₂)₂ (5), together with 4. The single-crystal structure X-ray analysis of 3 shows a closed triangular Ru₃ framework. The electron count is in accordance with the EAN rule, but the structure analysis of 5 reveals an open, almost linear Ru₃ skeleton, which is electron-deficient with respect to the EAN rule.     

Ring and Cluster Structures of {Li[C(NtBu)2(HNtBu)]}2·(THF) and {Li2[C(NtBu)3]}2, Containing the Novel Anions [C(NtBu)2(HNtBu)]−- and [C(NtBu)3]2−

The reaction of tert.-butyl carbodiimide with one equivalent of LiNH^tBu in tetrahydrofuran at-78 °C produces {Li[C(N^tBu)₂(HN^tBu)]}₂-(THF) (1), which is an eight-membered Li₂C₂N₄ ring; the deprotonation of (1) with two equivalents of n-BuLi in tetrahydrofuran at -78 °C and recrystallisation of the product from n-pentane yielded the unsolvated dimer {Li₂[C(N^tBu)₃]}₂ (2), which adopts the structure of a distorted hexagonal prism.     

Thermal and calorimetric studies of M(IO3)2·6H2O and M(IO3)2·6D2O forM 2+=Ca2+ and Sr2+

Thermal and calorimetric studies were carried out on M(IO₃)₂·6H₂O and M(IO₃)₂·6D₂O forM ²⁺=Ca²⁺ and Sr²⁺, using DTA and DSC methods. The thermal behaviour of the ordinary and deuterated hydrates is outlined and the differences observed between them are discussed. The enthalpies of the phase transitions were determined. The H _f ^o for Ca(IO₃)₂·6H₂O, Ca(IO₃)₂·6H₂O(D₂O) and Sr(IO₃)₂·6H₂O(D₂O) were calculated from the H _deh data and comments are made on the isotope effect observed.

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Zusammenfassung Mittels DTA- und DSC-Methoden wurden Me(IO₃)₂·6H₂O und Me(IO₃)₂·6D₂O (mitMe ²⁺=Ca²⁺ und Sr²⁺) thermisch und kalorimetrisch untersucht. Es wird ein Überblick über das thermische Verhalten ordentlicher und deuterierter Hydrate gegeben, in dem auch die Unterschiede zwischen beiden diskutiert werden. Die Enthalpien der untersuchten Phasenumwandlungen wurden bestimmt. Aus den Daten für H_deh wurde H_f von Ca(IO₃)₂·6H₂O, Ca(IO₃)₂H₂O(D₂O) und Sr(IO₃)₂·6H₂O(D₂O) berechnet und Bemerkungen zum beobachteten Isotopeneffektes gemacht.

     

Synthesis, characterisation and thermal properties of [Cu(VO)2(C2O4)3(4,4′-bpy)2·2H2O]A 2D polymer

The heterometallic complex [Cu(VO)₂(C₁₀H₈N₂)₂(C₂O₄)₃·2H₂O] has been prepared and characterised by electronic and IR spectra, molecular electrical conductivity and thermal behaviour. A polymeric structure is proposed with oxalate and 4,4′-dipyridine acting as bridging ligands and VO(IV) of C_4v symmetry and Cu(II) in octahedral surrounding the oxalate anion V_4h.     

Synthesis and Crystal Structure of an Unprecedented Supramolecular Complex [Co(μ2-ClO4)2(H2O)2]•2MA

利用水热法合成了一个结构新颖的超分子化合物[Co(μ2-ClO4)2(H2O)2]·2MA (1),晶体结构表明化合物1是靠氢键和p - p相互作用形成的独特的有机-无机杂化型三维超分子配合物。结构中存在两种不同的超分子构件：a)一维无机链通过氢键形成二维(4,4)拓扑网状构筑单元[Co(μ2-ClO4)2(H2O)2];b)三嗪环之间靠p - p相互作用形成的zigzag链状构筑单元。二者之间通过丰富的氢键和p-p相互作用最终形成了一个三维超分子结构。     

Mixed Amidohalotantalates [Ta(NMe2)3X3]– (X = F,Cl)

Russian Journal of Coordination Chemistry - The anionic tantalum complex (ItBuH)[Ta(NMe2)3Cl3] (I) is synthesized by the reaction of [Ta(NMe2)3Cl2]2 with N-heterocyclic carbene ItBu and is isolated...     

Synthesis and Crystal Structure of a Novel 1D Coordination Polymer: [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)]

The novel coordination polymer [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)] (BYBAH = 2-benzoylbenzoic acid) was yielded by hydrothermal synthesis, determined by single-crystal X-ray diffraction, and characterized by FT-IR and UV-Vis spectra. The crystal crystallizes in the triclinic system, space group P with a = 9.112(3), b = 14.644(5), c = 27.076(11) (A), α = 84.223(3), β = 87.816(4), γ = 88.902(4)o, V = 3592(2) (A)3, C84H60O21Pr2, Mr = 1687.14, Z = 2, F(000) = 1700, Dc = 1.560 g/cm3, μ = 1.419 mm-1, the final R = 0.0485 and wR = 0.1258 for 13035 observed reflections with I＞2((I). The compound contains two different building units, [Pr2(BYBA)6(H2O)4] and [Pr2(BYBA)6(H2O)2]. It is noticeable that [Pr2(BYBA)6(H2O)4] is an isolated binuclear building block, in which the Pr3 ion centers are both located in an eight-coordinated environment. However, in [Pr2(BYBA)6(H2O)2] the Pr3 ion centers are located in a nine-coordinated environment and connected by BYBA ligands to form 1D chains.     

Theoretical study of the V(4F)?+?NO(2��r)?��?VO(4��?)?+?N(4S��) reaction compared with the Sc(2D) and Ti(3F) cases

To understand the title reaction, the MRCI, CCSD, CCSD(T), and DFT calculations have been done. A large domain of the ground-state potential energy surface has been explored including the activation energy barrier to form the triatomic complex, two stable intermediate complexes, V[NO] and NVO, the transition state connecting these two conformers, and the detachment of the nitrogen atom. We compared this reaction with the similar ones involving the Sc and Ti atoms. The activation barrier to form the VNO complex made from the ionic-covalent coupling decreases to approach the experimental data when the electron correlation effect is better included as in the Sc and Ti systems. The transition state connecting the two conformers was calculated to be higher than in the Sc and Ti cases probably due to larger number of nonbonding valence electrons and is probably too high with respect to the reactant energy level to allow the interconversion between the two conformers in the VNO. The direct concerted substitution (abstraction) reaction is improbable because this process will have to overcome a too high potential barrier. We have also found the transition state connecting two conformers of ScNO.     

Synthesis and Crystal Structure of an Octa-nuclear V-Cu-S Cluster:[VS_3O(CuPBu_3)_2(CuSPBu_3)]_2

11NTRODUCTIONThetetrathiometalateanions[MS'j"-(M=Mo,W,V,Reetc.)havebeenshowntoactasligandstoawidevarietyofmetalions[li.Thechemistryof[MoS'j'-and[WS'j'-isbyfarthemosthighlydevelopedbecausesomeofthecubane-typeMoFe3S4clustersarerelevanttothenitrogenase"'andMo-Cuantagonismexistsinruminantst3i.However,[VS'j'hasnotbeendeeplyinvestigatedbecauseitissensi-tivetoairandmoisture.Evenso,theextensivevanadiumbiologicalfunctionhasim-pelledmoreandmorescientiststoprobeintothechemistryofthevanadiumco…     

Synthesis and characterization of glycol-modified vanadium(V) oxoisopropoxide and their oximato derivatives: sol–gel transformations of [VO(OPr i )3], [VO{OCH2CH2OCH2CH2O}{OPr i }] and [VO{OCH2CH2OCH2CH2O}{ON=C(CH3)(C4H3S-2)}] to vanadia

Reaction of [VO(OPr ⁱ )₃] (1) with [O(CH₂CH₂OH)₂] in 1:1 molar ratio in anhydrous benzene yield glycol-modified precursor, [VO{OCH₂CH₂OCH₂CH₂O}{OPr ⁱ }] (2). Further reactions of (2) with internally functionalized oximes in anhydrous benzene yield heteroleptic complexes of the type [VO{OCH₂CH₂OCH₂CH₂O}{ON=C(R)(Ar)}] (3–8) {where R=CH₃, Ar=C₄H₃O-2 (3), C₄H₃S-2 (4), C₅H₄N-2 (5); and when R=H, Ar=C₄H₃O-2 (6), C₄H₃S-2 (7), C₅H₄N-2 (8)}. All these derivatives have been characterized by elemental analyses, molecular weight measurements and spectroscopic techniques. The crysoscopic molecular weight measurement as well as FAB mass study suggests dimeric nature of (2). However, FAB mass spectrum of (4), and the crysoscopic molecular weight measurements of (3), (4), (5) and (6) indicate the monomeric behavior of the oximato derivatives (3–8). Hexa-coordination around vanadium(V) has been proposed for both monomeric and dimeric derivatives. Sol–gel transformations of (1), (2) or (4) to vanadia [(a), (b) or (c), respectively] have been carried out at low sintering temperature (600 °C). The XRD patterns of (a), (b) or (c) indicate formation of a single orthorhombic phase in all the three cases. The SEM images suggest grain like [for (a) and (b)] and rod like [for (c)] morphology of the crystallites. IR, Raman spectra as well as EDX analyses indicate formation of pure vanadia. Absorption spectra of the vanadia (b) and (c) suggest energy band gaps of 2.53 and 2.65 eV, respectively.     

Carbonate complexes [C(NH2)3]6[An(CO3)5] · nH2O (An = Th, U, Np, and Pu; n = 3 and 4): Synthesis and structures

Two series of isostructural double An(IV) and guanidinium carbonates were obtained as single crystals of the formula [C(NH₂)₃]₆[An(CO₃)₅] · nH₂O (An = Th, U, Np, and Pu; n = 3 (I) and 4 (II)) and examined by X-ray diffraction. For the Pu(IV) complexes, a = 10.490(2) Å, b = 33.798(5) Å, c = 10.519(2) Å, β = 119.414(7)°, space group P2₁/c, Z = 4, R = 0.0369 (I) and a = 16.0895(18) Å, b = 13.1458(14) Å, c = 16.6951(18) Å, β = 108.116(6)°, space group C2/c, Z = 4, R = 0.0171 (II). Both series of complexes contain the anions [An(CO₃)₅]^6?, in which the An atom is coordinated to five chelating bidenate carbonate ions. The coordination polyhedra of the An atoms are distorted bicapped square antiprisms. Within both the series, the An-O bond lengths decrease monotonically only for the sequence Th-U-Np. The average Np-O and Pu-O bond lengths in both tri- and tetrahydrates are virtually equal. The IR and electronic absorption spectra of the complexes obtained were studied. The absorption bands due to the f-f transitions experience bathochromic shifts in the spectra of the U⁴⁺ and Pu⁴⁺ carbonate complexes and hypsochromic shifts in the spectra of the Np⁴⁺ complexes.     

Reaction of [Pt(NH3)4]Cl2 with NH4VO3 in an Alkaline Solution at 190°C in Autoclave

Russian Journal of General Chemistry - The reaction of [Pt(NH3)4]Cl2 with NH4VO3 in alkaline solution in an autoclave at 190°C was studied. The solid autoclave thermolysis product was...     

Uranyl orthovanadate of composition (UO2)3(VO4)2 · 4H2O: Synthesis and characterization

Uranyl orthovanadate of composition (UO₂)₃(VO₄)₂ · 4H₂O was prepared by heating uranovanadic acid HVUO₆ · 2H₂O under hydrothermal conditions at 200°C. X-ray fluorescence analysis, high-temperature X-ray diffraction, scanning calorimetry, and IR spectroscopy served to study dehydration and to determine the structure, X-ray diffraction, and spectroscopic characteristics of dehydration products.     

A Corrugated 2D Mn(Ⅱ) Network:[Mn_3(μ-oxalate)_3(μ-4,4'-bpy)_2(4,4'-bpy)_2]_n

1 INTRODUCTION It is well known that the bi-functional 4,4?-bi- pyridine (4,4?-bpy) has the ability to act as a rigid, rod-like organic building block in the self-assembly of coordination frameworks. Many researches have also been done on the metal oxalate compounds. The remarkable coordination abilities of oxalate and 4,4?- bpy ligands are applied to design and synthesize new polymeric coordination complexes[1～4] containing mixed bridging ligands. Manganese is one of the several first-r…     

An Unprecedented 1D Zigzag Chain Alkaline Earth Metal Derivative {[Ba(DMF)_3(H_2O)_2][Ba(DMF)_4]_2(P_2W_(18)O_(62))}_n Containing Dawson Heteropolyanion

Most of the polyoxometalates have discrete structures of definite sizes and shapes belonging to well-known structural types, such as the Lindquist, Keggin, Dawson, Strandberg, or Anderson1–2. Linking these discrete entities to build solid-state materials…