Syntheses, Characterization and Crystal Structures of 1D and 2D Organotin Polymers Containing 3-Methyladipic Acid Ligand

Four new organotin (IV) complexes of two types [(R₂Sn)₂(C₇H₁₀O₄)(μ₃-O)] _n (R = Me: 1; nBu: 2; and {(R₃Sn)₂[C₅H₁₀(COO)₂]} _n (R = Me: 3; nBu: 4) have been synthesized by the reaction of 3-methyladipic acid with the corresponding R₃SnCl (R = Me, nBu) under two different experimental conditions. All the complexes were characterized by elemental analysis, FT-IR, and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy. Except for 2, all of the complexes were also characterized by X-ray crystallography. The structural analyzes show that complex 1 is a 1D infinite chain polymer and forms a 2D organotin framework through intermolecular C–H···O interactions and weak Sn···O interactions. Complexes 3 and 4 are 2D network polymers in which 3-methyladipic acid acts as a tetra dentate ligand coordinated to the trialkyltin (IV) ion.     

Syntheses and Structural Characterization of Triorganotin Derivatives of Bis(carboxymethyl)trithiocarbonate: X-ray Crystal Structures of 2D Network Polymers

Six triorganotin(IV) complexes of the type {(R₃Sn)₂[C₃S₃(COO)₂]}_n (R = C₆H₅ 1; n-Bu 2; PhCH₂ 4; p-F-PhCH₂ 5; o-F-PhCH₂ 6) and {(R₃Sn)₂[C₃S₃(COO)₂]}_n·[EtOH] (R = Me 3) have been synthesized by the reaction of bis(carboxymethyl)trithiocarbonate with triorganotin(IV) chloride in the presence of sodium ethoxide. All complexes were characterized by elemental analysis IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Except for 4–6, all complexes were also characterized by X-ray crystallography. The X-ray date revealed that complexes 1–3 show two-dimensional network polymeric structure in which the geometries of tin atoms are trigonal bipyramid with the axial positions occupied by carboxylic oxygen atoms.     

Syntheses and Characterization of Diorganotin Derivatives of 2-Mercapto-5-methyl-1,3,4-thiadiazole: X-ray Crystal Structure of Polymeric (C3H3S2N2) [(n-C4H9)6Sn3O(OH)2](C3H3S2N2)

Diorganotin derivatives of 2-mercapto-5-methyl-1,3,4 -thiadiazole, (R = Me 1, n-Bu 2, Ph 3, PhCH₂ 4), have been synthesized and characterized by IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Among them, polymer 2 was also characterized by X-ray crystallography diffraction analysis. This revealed that 2 showed a unique tricyclic structure consisting of a fused five-membered Sn₂ON₂ ring and a four-membered Sn₂O₂ ring. These formed a planar N₂Sn₃O₂ skeleton, with distorted trigonal bipyramidal coordination at the two tin centers and a distorted octahedral coordination at the other tin center. The supramolecular structure of polymer 2 was a 1D zig-zag polymeric chain stabilized by intermolecular O–H...S hydrogen bonds. An erratum to this article can be found at     

Hydrothermal Synthesis and Characterization of Trimethyltin(IV) Derivatives with 2-Carboxyethylphosphonic and Benzylphosphonic acid: X-ray Crystal Structures of 2D Network Polymers

Two organotin(IV) derivatives, {[(CH₃)₃Sn]₆·[O₃P(CH₂)₂CO₂]₂·3H₂O} _n 1 and {[(CH₃)₂Sn]₄·[O₃PCH₂Ph]₄} _n 2, were synthesized by the reaction of trimethyltin(IV) chloride, 2-carboxyethylphosphonic acid and benzylphosphonic acid, respectively. Characterization of complexes 1 and 2 were achieved using elemental analysis, IR, TGA, NMR (¹H, ¹³C, ³¹P and ¹¹⁹Sn) spectroscopy and X-ray crystallography diffraction analysis. X-ray characterization show that complexes 1 and 2 are 2D network structures.     

A new inorganic (carbon-free) chelate ring: SnO2N2. Eight-coordinated tin(IV) in Sn(O2N2Ph)4 and a self-assembled 20-membered macrocycle in [Me3Sn(O2N2Ph)]4

The reaction of cupferron (NH₄L, L=PhN(O)NO⁻) with tin(IV) and trimethyltin(IV) halides yields cupferronato complexes SnL₄ (1) and [Me₃SnL]₄ (2) which were characterised by FT-IR and FT-Raman spectroscopy. The first X-ray diffraction analysis of the complexes reveals a slightly distorted dodecahedral and trigonal-bipyramidal coordination of the central metal atoms in 1 and 2, respectively. The N-nitroso-N-phenylhydroxylaminato [PhN(O)NO⁻] ligand behaves as chelating in 1 and bridging in 2 leading to a novel five-membered chelate ring, SnO₂N₂ in 1 and an unprecedented 20-membered inorganic metallomacrocycle, Sn₄O₈N₈ in 2.     

Cu(II) and Zn(II)-Pyridine-2,3-Dicarboxylate Complexes with 2-Methylimidazole: Syntheses, Crystal Structures, Spectroscopic and Thermal Analyses

Two new Cu(II) and Zn(II)-pyridine-2,3-dicarboxylate (pydc) complexes with 2-methylimidazole (2-Meim), [Cu(pydc)(2-Meim)₃]·H₂O (1) and {[Zn(μ-pydc)(H₂O)(2-Meim)]·H₂O}_n (2) have been synthesized and characterized by elemental, spectral (IR and UV–Vis.) and thermal analyses. The molecular structures of mononuclear (1) and polynuclear (2) complexes have been determined by the single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic P ? 1 space group, while compound 2 crystallizes in the monoclinic P2₁/c space group. The pyridine-2,3-dicarboxylate ligand acts in two different coordination modes; namely, bidentate-(N,O) for 1 and μ-tridentate-(N,O,O) for 2, the latter displaying a 1D polynuclear structure. The crystal packing of the complexes exhibit 3D supramolecular frameworks including channels by C–H···π, π···π, and N–H···O interactions. Water molecules occupy the channels by O–H···O hydrogen bonds.     

Tin(IV) Polymers: Part 1. Synthesis of Diorganotin Esters of Thiosalicylic Acid: X-ray Crystal Structure of Polymeric Thiosalicylatodiorganotin

Thiosalicylatodiorganotin, [R₂Sn(O₂CC₆H₄S)]_n, (R=Me (1), n-Bu (2), Ph (3), 3-Cl–PhCH₂ (4)), are prepared from thiosalicylic acid and diorganotin chlorides. All the compounds, 1–4, are characterized by elemental analysis as well as IR and ¹H-NMR spectroscopy. X-ray crystallographic analysis of the 2 and 4 shows that the structures are polymeric with neighboring diorganotin centers being linked by one O-atom of the carboxylate ligands. The carboxylate moiety is involved in coordination to one Sn atom via one O-atom while the other O-atom coordinates to the neighboring Sn atom. The mercaptotropone sulfur atom is bonded to the central Sn atom thereby establishing that Sn is five-coordinate and exists in a trigonal bipyramidal geometry.     

Interesting Copper(I) and Mercury(II) 1D Coordination Polymers Based on 3,6-Bis(2-pyridylthio)pyridazine Ligand: Syntheses,Structures and Properties

Two interesting d¹⁰ metal complexes of 3,6-bis(2-pyridylthio)pyridazine ligand (PTP), [Cu₃I₃(PTP)] _n (1) and [HgI₂(PTP)] _n (2), have been synthesized and characterized by IR, elemental analysis, UV–Vis–NIR spectra, thermal analysis and single crystal X-ray diffraction analysis. Single-crystal X-ray analyses show that two complexes are both 1D chain coordination polymer. Complex 1 is a linear chain structure which is constructed from trinuclear Cu₃I₃ butterfly-shaped units by means of Cu–I bonds. Complex 2 is one-dimensional helical chain structure. In complex 2, two helical single chains form a double helix structure, and these double helix structures are further assembled to form a quasi 2D network by C–H⋯I hydrogen bonds. Optical diffuse-reflection spectra results suggest complex 1 has the property of the semiconductor.     

Crystal Structure, Thermal and Magnetic Behavior of Inorganic–Organic Hybrid [VIV 4O10 VV 2O4] (C6H14N2)·H2O Polymeric Framework

Summary The inorganic–organic hybrid [V^IV ₄O₁₀V^V ₂O₄] (C₆H₁₄N₂)·H₂O polymeric framework was prepared under mild hydrothermal conditions from a mixture of DABCO and V₂O₅ in deionized water with a 1:1:450 mole ratio, at neutral pH. The reaction was carried out at 180 °C for 3 days under autogenous pressure yielding phase pure crystals product. The crystal structure was studied using both powder and single crystal X-ray crystallography, revealing the structure to be of the ({UuDd}:T*)α′ type in the SP+T class and Z-T subclass. The presence of the organic cation was confirmed by FT-IR spectrum and chemical composition analysis. The structure was thermally stable up to over 400 °C, and showed ferromagnetic character at room temperature with the maximum molar susceptibility of 8.26 × 10⁻³ emu/mol⁻¹ at zero applied field.     

(Sn_(1-x),Ni_(2x))O_2纳米颗粒膜的制备及半导体性能

为提高SnO2的半导体性能,以分析纯SnCl2.2H2O和NiCl2.6H2O为主要原料,控制不同n(Ni2+)/n(Sn2+),利用溶胶凝胶-浸渍提拉法制备了(Sn1-x,Ni2x)O2纳米颗粒膜及半导体元件。用XRD、AFM对样品的结构、形貌进行了分析,并测试了(Sn1-x,Ni2x)O2元件的半导体性能。结果表明,(Sn1-x,Ni2x)O2纳米颗粒膜表面椭球形颗粒排列致密,尺寸约30 nm,(Sn1-x,Ni2x)O2为金红石型结构,但Ni2+代替了SnO2晶格中的部分Sn4+,使其晶胞参数a轴长平均减小0.000 4 nm,c轴长平均减小0.000 3 nm;随n(Ni2+)/n(Sn2+)由0.006增大到0.03,(Sn1-x,Ni2x)O2的晶粒尺寸由约45 nm减小至约18 nm;随温度由30℃上升至150℃,n型(Sn1-x,Ni2x)O2半导体元件的电阻约减小至其10%,而纯净SnO2元件的电阻仅约减小至其15%;随n(Ni2+)/n(Sn2+)的增大,离子化杂质散射增强,(Sn1-x,Ni2x)O2内部载流子迁移率下降,元件在150℃左右的电阻也由4.8 kΩ增大至12.1 MΩ,提高了元件的半导体性能。     

Interesting Copper(I) Coordination Polymers of Heterocyclic Monothioether Ligand Containing Long S-Hexadecyl Chain: Syntheses,Structures and Properties

Two structurally related heterocyclic monothioether ligands containing long S-alkyl(hexadecyl) chain, 2-methyl-5-(1-n-hexadecylsulfanyl)-1,3,4-thiadiazole (L ¹ ) and 2-(1-n-hexadecylsulfanyl) pyridine (L ² ), have been designed, and two CuI complexes with these ligands, [Cu₄I₄(L¹)₂] _n (1) and [Cu₄I₄(L²)₂] _n (2), have been synthesized and characterized by IR, elemental analysis, UV–vis spectra, thermal analysis and X-ray diffraction analysis. Single-crystal X-ray analyses show that two complexes are all 1-D coordination polymer with a double-stranded stair CuI-chain. Optical diffuse-reflection spectra results complex 1 and 2 have the properties of the semiconductor.     

氢键配合物[Mn(H_2O)_2(HNic)_2]晶体的合成及结构表征

用3d金属离子锰与2-羟基-3-吡啶羧酸配体合成出新的水杨酸式螯合具有三维网络结构的Mn(H_2O)_2(HNic)_2配合物。均三苯甲酸苯环上一、三、五位置上的羧基都有脱质子化进行各种不同的结合,利用这点水溶液合成氢键配合物Mn(H_2O)_2(HNic)。我们采用常规分析方法即元素分析谱等,对配合物进行了表征.利用X-射线衍射晶体结构分析,结果显示该配合物属于单斜晶系,空间群为P2(1)/c,每一各晶胞包含两个Mn(H_2O)_2(HNic)_2分子,一个2-羟基-3-吡啶羧酸分子,通过N原子质子化的H原子与临近2-羟基-3-吡啶羧酸分子上的羟基上O原子又形成了一个八元环的氢键结构,该配合物具有复杂的氢键结构。     

A New 2D Cd(II) Grid-like Structure Based on Hetero-Chiral Helical Chains: Synthesis, Crystal Structure, Thermal and Luminescent Properties

A new 2D Cd(II) coordination polymer, [Cd(BBI)₄Cl₂] _n (BBI = 1,1′-(1,4-butanediyl)bis (imidazole)) (1), was synthesized under hydrothermal conditions, and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction crystallography. For complex 1, each Cd(II) ion crystallizes in a [CdN₄Cl₂] six-coordinated slightly distorted octahedral geometry, coordinating to four BBI ligands by Cd–N bonds, completed by two terminal Cl⁻ anions. The characteristic of 2D grid-like layers, from the central Cd(II) ions as knots and BBI ligands as spacers, is the hetero-chiral helical chains of left- and right-hand helixes. Two kinds of π interactions assemble 2D layers into 3D supramolecular architecture in an ···ABC··· packing arrangement. The fluorescent properties were studied in the solid state for its luminescent applications.     

New catalyst systems for polymerization of substituted acetylenes: W(NO)2(O2CR)2-MCl4(M=Ti, Sn)

Summary W(NO)₂(O₂CR)₂ - Lewis acid (LA) catalysts (LA=TiCl₄, SnCl₄; R=-CH(C₂H₅)(CH₂)₃CH₃) induce substituted acetylenes (phenylacetylene, propargyl ether, 1,6-heptadiyne, diphenylacetylene) to polymerize or oligomerize. Their catalytic ability strongly depends on the Lewis acid and solvent. The polymerization reactions of phenylacetylene always accompany the cycolotrimerization reactions. In the system with TiCl₄ in CH₂Cl₂ the yield of polymer equals to 56% at 80% conversion of a monomer. However, in the system with SnCl₄ in benzene, 42% cyclotrimers arise at 57% conversion of phenylacetylene. The mechanism of these reactions as well as the structure of the obtained polymers were determined. Received: 14 December 1998/Revised version: 25 July 1999/Accepted: 5 September 1999     

含吡咯亚胺铜配合物的合成、表征及晶体结构

合成了一种新型含吡咯亚胺铜配合物,用元素分析、红外光谱及X射线单晶衍射对其进行了表征。结构解析表明,每个铜配合物分子含有两个吡咯亚胺配体,每个配体用两个氮原子与中心金属铜离子螯合,每个铜离子均采取平面四边形构型与配体中的四个氮原子配位。     

Single-layer XBi2Se4 (X = Sn Pb) with multi-valley band structures and excellent thermoelectric performance

Using the first-principle simulations and the Boltzmann transport equation, our study investigated the properties of single-layer SnBi₂Se₄ and PbBi₂Se₄, including stability, elasticity, electronic and thermoelectric transport properties. We discovered that both 2D materials have acceptable cleavage energies ranging from 0.27 to 0.28 J/m² and that they are indirect semiconductors with narrow band gaps of 0.68 eV and 0.94 eV, respectively. Interestingly, the valence band maximum exhibits ‘multi-valley’ energy dispersion. Furthermore, SnBi₂Se₄ and PbBi₂Se₄ have comparable electron and hole mobility of about ∼10² cm²/Vs and ∼10³ cm²/Vs, respectively resulting in high conductivity and a high thermoelectric power factor. Owing to low group velocities and strong phonon–phonon scattering rates, the materials exhibit low lattice thermal conductivities of 2.59 W/mK (SnBi2Se₄) and 1.73 W/mK (PbBi₂Se₄). Thus, they demonstrate high thermoelectric figures of merit, namely 0.31 (SnBi2Se₄) and 0.37 (PbBi₂Se₄) at 300 K, which rise further to 1.22 and 1.82, respectively, at 700 K. Our results suggest that these two single-layer materials are promising candidates for use in nanoelectronics and thermoelectric appliances.