铋(Ⅲ)配合物Bi(1,10-phen)[S2CN(CH3)2]2(NO3),

Three bismuth（Ⅲ） complexes Bi（1,10-phen）[S2CN（CH3）2]2（NO3） （1）, {Bi（S2COCH3）[S2CNC6Hs（CH3）]2}2 （2） and [Bi（S2CNBu2）2（CH3OH）（NO3）]∞ （3） were synthesized and characterized by elemental analysis and IR spectra. Their crystal structures were determined by X-ray single crystal diffraction analysis. Studies show that complex 1 has a monomeric structure with the central bismuth atom eight-coordinated in a capped distorted pentagonal bipyramidal geometry. The complex 2 takes centrosymmetric dimeric structure and the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry.In complex 3, the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry by bridging nitrate O atoms and the resulting structure is onedimensional infinite chain polymer.     

Coordination of Bimuth(III) to Cucurbit[8]uril. Preparation and X‐ray Structure of [{Bi(NO3)(H2O)5}2(Q8)][Bi(NO3)3(H2O)4]2[Bi(NO3)5]2·Q8·19H2O

Bi(NO₃)₃ reacts with cucurbit[8]uril, (Q8), in 3M HNO₃ to give the title complex whose structure includes three discrete Bi complexes: [{Bi(NO₃)(H₂O)₅}₂(Q8)]⁴⁺ (CN of Bi = 9, both NO₃^— and cucurbit[8]uril are bidentate), [Bi(NO₃)₅]^2— (CN of Bi = 10, all NO₃^— are bidentate), and [Bi(NO₃)₃(H₂O)₄] (CN of Bi = 10, all NO₃^— are bidentate).     

Phosphaniminato‐Komplexe von Bismut(III). Die Kristallstrukturen von [BiF2(NPEt3)(HNPEt3)]2 und [Bi2I(NPPh3)4]I3

Phosphoraneiminato Complexes of Bismuth(III). Crystal Structures of [BiF₂(NPEt₃)(HNPEt₃)]₂ and [Bi₂I(NPPh₃)₄]I₃ [BiF₂(NPEt₃)(HNPEt₃)]₂ ( 1 ) has been obtained by the reaction of BiF₃ with Me₃SiNPEt₃ at 100 °C and subsequent extraction with 1,2‐dimethoxyethane in the presence of traces of water forming pale‐yellow, moisture sensitive crystals, which were characterized by a crystal structure determination. Space group P2₁/n, Z = 4, lattice dimensions at –83 °C: a = 2105.0, b = 1195.8, c = 728.2 pm, β = 92.55°. 1  forms centrosymmetric dimeric molecules, in which the Bi atoms are linked via Bi–N bonds of varying length (213.9 and 240.1 pm) of the NPEt₃^– groups to form a Bi₂N₂ four‐membered ring. The longer one of the two Bi–N bonds is trans to one terminal F atom. [Bi₂I(NPPh₃)₄]I₃ ( 2 ) has been obtained by the reaction of bismuth with N‐iodine triphenylphosphaneimine in dichloromethane forming red crystals. Crystal structure determination of 2 · 2.5 CH₂Cl₂: Space group P2₁/n, Z = 4, lattice dimensions at –50 °C: a = 1542.6, b = 2409.1, c = 2173.5 pm, β = 105.82°. In 2 the Bi atoms are linked via two N atoms of two NPPh₃^– groups to form a non‐planar Bi₂N₂ four‐membered ring with a fold angle of 27° along the N…N connection line. The two remaining NPPh₃^– groups are terminally connected and bent in the same direction. The iodide ion caps the two Bi atoms so that a [Bi₂I(NPPh₃)₄]⁺ cation is formed.     

Dimeric Structure of [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy)(η2‐NO3)2]

The synthesis and single crystal X‐ray structure determination are reported for the 2,2′ : 6′,2″‐terpyridine (= tpy) adduct of bismuth(III) nitrate. The hydroxide‐bridged dimer [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy)(η²‐NO₃)₂] with nine‐coordinate geometry about Bi was the only isolable product from all crystallization attempts in varying ratios of Bi(NO₃) : terpy.; [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy) · (η²‐NO₃)₂] is triclinic, P 1, a = 7.941(8), b = 10.732(9), c = 11.235(9) Å; α = 63.05(1), β = 85.01(1), γ = 79.26(1)°, Z = 1, dimer, R = 0.058 for N₀ = 2319.     

Dispersion interactions between neighboring Bi atoms in (BiH3)2 and Te(BiR2)2

Triggered by the observation of a short Bi⋯Bi distance and a Bi Te Bi bond angle of only 86.6° in the crystal structure of bis(diethylbismuthanyl)tellurane quantum chemical computations on interactions between neighboring Bi atoms in Te(BiR₂)₂ molecules (R = H, Me, Et) and in (BiH₃)₂ were undertaken. Bi⋯Bi distances atoms were found to significantly shorten upon inclusion of the d shells of the heavy metal atoms into the electron correlation treatment, and it was confirmed that interaction energies from spin component‐scaled second‐order Møller–Plesset theory (SCS‐MP2) agree well with coupled‐cluster singles and doubles theory including perturbative triples (CCSD(T)). Density functional theory‐based symmetry‐adapted perturbation theory (DFT‐SAPT) was used to study the anisotropy of the interplay of dispersion attraction and steric repulsion between the Bi atoms. Finally, geometries and relative stabilities of syn–syn and syn–anti conformers of Te(BiR₂)₂ (R = H, Me, Et) and interconversion barriers between them were computed. © 2018 Wiley Periodicals, Inc.     

Structural and Magnetic Properties of Bi(Fe1-xMnx)O3

Bi(Fe_1-xMnx)O₃ bulk ceramics with Mn concentration x up to 0.3 were prepared by rapid sintering using sol-gel derived fine powders. Structure transformation is found to depend on the Mn doping concentration by X-ray diffraction and Raman spectroscopy. Bi(Fe_1-xMnx)O₃ maintains the rhombohedral structure of BiFeO3 with x=0.05 and 0.1, but changes to the orthorhombic structure with x=0.3. Weak ferromagnetism is observed for Bi(Fe_1-xMnx)O₃ with x=0.05 and 0.1, but stronger paramagnetism is observed for Bi(Fe_1-xMnx)O₃ with x=0.3 indicating a magnetic phase change from antiferromagnetic to paramagnetic with the structure changing from R3c to C222. Two anomalies at 30 and 140 K are observed for Bi(Fe_1-xMnx)O₃ with x=0.05 and 0.1. The anomaly at 30 K is concluded to be related to the freezing of cluster spin glass from dc magnetic memory and relaxation measurements.     

Bismuth(III) Complexes with N,N‐Di(2‐hydroxylethyl)aminodithiocarboxylate: Synthesis and Crystal Structure of {Bi[S2CN(C2H4OH)2]2[1, 10‐Phen]2(NO3)}·3H2O and (Bi[S2CN(C2H4OH)2]3}2

Two novel one‐ and two‐dimensional network structure bismuth(III) complexes with N, N‐di(2‐hydroxylethyl)‐aminodithiocarboxylate, {Bi[S₂CN(C₂H₄OH)₂]₂[1, 10‐Phen]₂(NO₃)}·3H₂O (1) and (Bi[S₂CN(C₂H₄OH)₂]₃)₂ (2) were synthesized. Their crystal and molecular structures were determined by X‐ray single crystal diffraction analysis. The crystal 1 belongs to monoclinic system with space group C2/c, a=1.6431(7) nm, b=2.4323(10) nm, c= 1.2646(5) nm, β=126. 237(5), Z=4, V=4.076(3) nm³, D_c=1.757 Mg/m^3, μ=4.598 mm^?1, F(000)=2156, R= 0.0211, wR=0.0369. The structure shows a distorted square antiprism configuration with eight‐coordination for the central Bi atom. The one‐dimensional chain structure was formed by H‐bonding interaction between hydroxyl group of N, N‐di(2‐hydroxylethyl)aminodithiocarboxylate ligands and crystal water. The crystal 2 belongs to monoclinic system with space group p2(1)/c, a= 1.1149(4) nm, b=2.1274(8) nrn, c=2.2107(8) nm, β=98.325(8)°, 2=4, V=5. 188(3) nm³, Dc=1.920 Mg/m³, μ=7.315 mm^?1, F(000)=2944, R=0.0565, wR=0.0772. The structure shows a distorted square antiprism configuration with eight‐coordination for the central Bi atoms. The two‐dimensional network structure was formed by H‐bonding interaction between adjacent molecules.     

Synthese und Kristallstruktur von [(Me3Si)2BiCu(PMe3)3], dem ersten Komplex mit einer Bismut—Kupfer‐Bindung

Synthesis and Crystal Structure of [(Me₃Si)₂BiCu(PMe₃)₃] — the First Complex with a Bismuth—Copper Bond The reaction of CuO^t Bu with PMe₃ and Bi(SiMe₃)₃ in hexane yields the phosphine‐stabilized complex [(Me₃Si)₂Bi‐Cu( PMe₃)₃]. This synthesis gave rise to the first binuclear Bi—Cu compound to be structurally characterized by X‐ray crystallography.     

Crystallographic report: Bi(S2CNC5H10)2(NO3)(1,10‐phenanthroline)

The structure of Bi(S₂CNC₅H₁₀)₂(NO₃)(1,10‐Phen) features an eight‐coordinated distorted square antiprismatic geometry around bismuth, defined by an N₂O₂S₄ donor set, with Bi? S distances ranging from 2.641(2) to 2.824(2) Å. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis of 3‐substituted indoles promoted by pulverization‐activation method catalyzed by Bi(NO3)3·5H2O

A new, facile, efficient, “green” and chemoselective procedure for the synthesis of indole derivatives has been developed with pulverization‐activation method catalyzed by Bi(NO₃)₃·5H₂O (PAMC‐ Bi(NO₃)₃·5H₂O) through grinding of indoles with aldehydes or Michael acceptors in the presence of catalytic amounts of Bi(NO₃)₃·5H₂O under solvent‐free conditions.     

Bi(IO3)F2: The First Metal Iodate Fluoride with a Very Strong Second Harmonic Generation Effect

The first metal iodate fluoride, Bi(IO₃)F₂, with a strong second harmonic generation (SHG) effect has been prepared. Bi(IO₃)F₂ crystallizes in the polar space group C2 and features a three‐dimensional [BiF₂]⁺ cationic framework with IO₃ groups capping the inner walls of the one‐dimensional tunnels. This [BiF₂]⁺ cationic framework acts as a template for the assembly of the polar IO₃ units in a favorable superposed fashion, which leads to the polar structure of the material. Bi(IO₃)F₂ displays a rather wide transmittance window (0.3–11 μm) and exhibits a very strong SHG response that is about 11.5 times larger than that of KH₂PO₄ (KDP) under 1064 nm laser radiation and the same as that of KTiOPO₄ (KTP) under 2.05 μm laser radiation. Preliminary investigations indicate that Bi(IO₃)F₂ is a promising nonlinear optical material in the visible and mid‐IR region.     

Transition Metal Substitutions Induce Ferromagnetism in Bi2Te3

The possibilities of magnetism induced by transition-metal atoms substitution in Bi₂Te₃ system are investigated by ab initio calculations. The calculated results indicate that a transition-metal atom substitution for a Bi atom produces magnetic moments, which are due to the spin-polarization of transition-metal 3d electrons. The values of magnetic moments are 0.92, 1.97, 2.97, 4.04, and 4.98 μ_B for 4% Ti-, V-, Cr-, Mn-, and Fe-doped Bi₂Te₃ respectively. When substituting two transition-metal atoms, the characteristics of exchanging couple depend upon the distributions of the Bi atoms substituted. When two transitionmetal atoms substituting for Bi atoms locate at the sites of Bi1 and Bi5, with the distance of 11.52 Å, the Bi_1.84TM_0.16Te₃ system is energetically most stable and exhibits ferromagnetic coupling.     

Structure, and magnetic and transport behavior of twinned Ce2Rh3(Pb,Bi)5

Single crystals of a new compound, Ce₂Rh₃(Pb,Bi)₅, have been grown via a flux-growth technique using molten Pb as a solvent. The compound has been characterized by single crystal X-ray diffraction and found to be of the orthorhombic Y₂Rh₃Sn₅ structure type [Cmc2₁ (No. 36), Z=4] with lattice parameters a=4.5980(2), b=27.1000(17) and c=7.4310(4) Å, with V=925.95(9) Å³. Ce₂Rh₃(Pb,Bi)₅ has a complex crystal structure containing Ce atoms encased in Rh-X (X=Pb/Bi) pentagonal and octagonal channels in [100], with polyanions similar to those found in Ce₂Au₃In₅ and Yb₂Pt₃Sn₅. Magnetization measurements find that Ce₂Rh₃(Pb,Bi)₅ is a quasi-two-dimensional system, where the Ce moments are spatially well-localized. Heat capacity measurements show a transition at the Néel temperature of 1.5 K. Evidence for Fermi surface nesting is found in electrical resistivity measurements, and we argue that Ce₂Rh₃(Pb,Bi)₅ is very near a metal-insulator transition in zero field.     

Bi12Rh3Br2: a subbromide from the oxidation of the intermetallic compound Bi4Rh

Bi₁₂Rh₃Br₂ was synthesized from the elements using niobium bromides as auxiliaries to modify the partial pressures in the course of the reaction. The orthorhombic crystal structure (space group Fddd (no. 70); a=717.12(3) pm, b=1680.37(6) pm, c=3187.1(1) pm) consists of a three-dimensional framework of [RhBi₈] cubes and square antiprisms, which share common edges. Bromide ions fill the chiral pores of the framework. The crystal structure of Bi₁₂Rh₃Br₂=(Bi₄Rh)₃Br₂ is closely related to that of the intermetallic compound α-Bi₄Rh. The oxidation of Bi₄Rh to Bi₁₂Rh₃Br₂ is accompanied by an emptying of BiBi and BiRh antibonding states near the Fermi level, leading to a strengthening of bonding in the intermetallic part of the structure. Despite the partial oxidation the metallic conductivity is retained.     

ZnO-B2O3∶Tb3+长余辉玻璃的发光性质

通过还原方法制备了Tb³⁺离子掺杂的硼酸锌玻璃，并观察到在254 nm紫外光激发后有明亮的绿色长余辉发光现象，余辉时间达6 h。通过激发与发射光谱、余辉光谱、余辉衰减曲线、热释光谱、热释光释出速率衰减曲线等得到的信息，研究了Tb³⁺离子掺杂的硼酸锌玻璃的发光性质。     

Dimethylarsenazid (CH3)2AsN3, Dimethylwismutazid (CH3)2BiN3 und Dimethylthalliumzid (CH3)2TiN3

The reaction of (CH₃)₂AsJ and AgN₃ yields (CH₃)₂AsN₃; a colourless liquid (b. p. 136°C) which dissolves as a monomeric in benzene. (CH₃)₂BiN₃ is precipitated in form of colourless needles (dec. temp. 150°C) from an etherical solution of Bi(CH₃)₃ and HN₃. According to its vibrational and mass spectra the molecules are not associated although the (CH₃)₂BiN₃ is not soluble; dipole association of this polar molecules is assumed for the crystal structure. (CH₃)₂TlN₃ can be obtained from TI(CH₃)₃ and ClN₃ as well as from (CH₃)₂TlOH and HN₃ in form of colourless needles and leaves (dec. temp. 245°C). According to its vibrational spectra it has an ionic structure, (CH₃? Tl? CH₃)⁺N^?₃.     

Standard molar enthalpy of formation of [(C12H8N2)2Bi(O2NO)3] and its biological activity on Schizosaccharomyces pombe

The title complex [(C₁₂H₈N₂)₂Bi(O₂NO)₃] was synthesized by reaction of 1,10-phenanthroline (phen) and Bi(NO₃)₃·5H₂O. The structure of the complex was characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. An advanced solution-reaction isoperibol microcalorimeter was applied to determine the standard molar enthalpies of formation at 298.15 K of the complex and Bi(NO₃)₃·5H₂O, giving –(798.92 ± 5.99) and –(1986.87 ± 0.20) kJ mol⁻¹, respectively. The biological effect of the complex was evaluated by microcalorimetry on the growth of Schizosaccharomyces pombe (S. pombe). According to thermogenic curves, the corresponding thermokinetics and thermodynamic parameters were derived. The complex had good bioactivity on the growth metabolism of S. pombe, with the value of IC₅₀ being 2.8 × 10⁻⁵ mol L⁻¹.

     

Bismuth(III) dimethyldithioarsinate,Bi(S2AsMe2)3: A new dimer formed through Bi … S secondary bonding

The crystal and molecular structures of bismuth(III) dimethyldithioarsinate, Bi(S₂AsMe₂)₂, were investigated by X-ray diffraction. The compound is a centrosymmetric dimer in which pentagonal-bipyramidal monomeric units are associated through secondary Bi–S interactions. The structure is compared with that of the analogous dithiophosphinate, Bi(S₂PMe₂)₂. © 1997 John Wiley & Sons, Inc.     

A spectroscopic and ab initio study on Bi(III) complex formation with 3-mercaptopropanesulfonic acid

This article deals with complex formation of Bi(III) with 3-mercaptopropanesulfonic acid (H₂MPS) in aqueous perchloric acid solutions, with synthesis and characterization of a solid 3-mercaptopropanesulfonate complex of bismuth(III). The stoichiometry and structures of Bi-MPS species in aqueous solution and of a solid complex have been studied by UV–Vis, ¹H-NMR, ICP-AES, Raman, and EXAFS spectroscopic methods; the structures have also been simulated with DFT/PBE0 calculations. The Bi(III) L_III-edge EXAFS oscillation for a solid compound with the empirical formula [Bi(HMPS)₂(ClO₄)]⁰ was simulated with two Bi–S interatomic distances at 2.50 ± 0.01 Å, two Bi–O distances at 2.56 ± 0.02 Å and two Bi–O distances at 2.75 ± 0.02 Å. Implementation of the same approach for aqueous solutions on the assumption of S₃BiO₃ coordination at the H₂MPS?:?Bi(III) mole ratio ≥ 3.0 revealed three Bi–S bonds at 2.53 ± 0.02 Å and three Bi–O bonds at 2.68 ± 0.02 Å, respectively. Optimized geometries, electronic structures of Bi(HMPS)₃ and [Bi(HMPS)₂ClO₄]⁰, vibrational properties of [Bi(HMPS)₂ClO₄]⁰, and electronic absorption spectrum of Bi(HMPS)₃ species obtained by DFT and TD–DFT modeling are consistent with empirical parameters. In the UV–Vis spectrum of Bi(HMPS)₃ the LMCT and MLCT S^2? ? Bi³⁺ band appears at 268 nm.     

Superconductivity Induced by Oxygen Doping in Y2O2Bi

When doped with oxygen, the layered Y₂O₂Bi phase becomes a superconductor. This finding raises questions about the sites for doped oxygen, the mechanism of superconductivity, and practical guidelines for discovering new superconductors. We probed these questions in terms of first‐principles calculations for undoped and O‐doped Y₂O₂Bi. The preferred sites for doped O atoms are the centers of Bi₄ squares in the Bi square net. Several Bi 6p x /y bands of Y₂O₂Bi are raised in energy by oxygen doping because the 2p x /y orbitals of the doped oxygen make antibonding possible with the 6p x /y orbitals of surrounding Bi atoms. Consequently, the condition necessary for the “flat/steep” band model for superconductivity is satisfied in O‐doped Y₂O₂Bi.