一种具有一维链状结构的4f-3d双核配合物[Eu(DMSO)3(H2O)3Cr(CN)6]·H2O(DMSO=二甲亚砜)的合成、晶体结构和磁性研究(英)

A new cyano-bridged complex [Eu(DMSO)₃(H₂O)₃Cr(CN)₆]·H₂O with one-dimensional chain molecular structure was synthesized and characterized. The crystal data for the title complex: orthorhombic, P2₁2₁2₁, a=0.972 2(3) nm, b=1.489 5(4) nm, c=1.748 6(5)nm, Z=4, μ=3.171 mm^-1, final R₁=0.020 4, wR₂=0.043 4. From magnetic susceptibility measurements the complex was found to exhibit a weak ferromagnetic interaction between the Eu (Ⅲ)and Cr(Ⅲ)atoms. CCDC: 272212.     

两个3d-4f杂核配合物[Fe(phen)3]2[FeLn(H2O)(tiron)3]·6H2O的合成、晶体结构和磁性(Ln=HoⅢ, YbⅢ)

Ln₂O₃、硝酸铁、邻菲罗啉和钛铁试剂(tiron)通过水热法自组装合成了2个异质同晶的3d-4f杂核配合物[Fe(phen)₃]₂[FeLn(H₂O)(tiron)₃]·6H₂O, 其中, Ln=Ho^Ⅲ (1)和Yb^Ⅲ (2)。X-射线单晶衍射分析表明, 晶体属立方晶系, P2₁3空间群。3个tiron^4-配体利用酚氧桥联Ln³⁺和Fe³⁺形成具有C₃对称性的[FeLn(H₂O)(tiron)₃]^6-异双核配位单元, 其中七配位的Ln³⁺呈现一种畸变的单帽反三棱柱配位构型。配阳离子[Fe(phen)₃]³⁺通过phen-phen之间的π-π相互作用和与配阴离子间的静电引力等作用组装成三维的超分子。在2~300 K温度范围内测试了配合物的变温磁化率, 结果表明, Ln(Ⅲ)-Fe(Ⅲ)之间存在反铁磁性相互作用。     

一维双核锌配合物[Zn2(SHSH)2(2-Me-py)2]的合成、晶体结构及理论研究

The crystal of one-dimensional binuclear zinc complex [Zn₂(SHSH)₂(2-Me-py)₂] was obtained in DMF and 2-methylpyridine, where SHSH is salicylaldehyde salicylhydrazone. It has been characterized by IR, UV, element analysis and X-ray diffraction analysis. The crystallographic data were as follows: monoclinic system, space group P2₁/c, a=1.144 49 nm, b=1.206 69 nm, c=1.379 39 nm, β=97.039°, Z=2, V=1.890 6 nm³, M_r=825.47, D_c=1.450 g·cm^-3, μ=1.324 mm-1, F(000)=848 and the final R=0.033 6 and wR=0.094 7 for 3 752 observed reflections with I≥2σ(I). The theoretical investigation of title complex as a structure unit was carried out at B3LYP/6-31G and HF/6-31G levels with Guassian 03W program, and the atomic charges, natural bond orbital analysis and bond energies were also discussed. CCDC: 260920.     

配合物[Mn(NPA)2(Phen)(H2O)2]的合成、晶体结构及热稳定性

合成了一个Mn(Ⅱ)的配合物[Mn(NPA)₂(Phen)(H₂O)₂](NPA=N-苯基代邻氨基苯甲酸，Phen=邻菲咯啉)，经红外光谱、紫外光谱、元素分析、差热，X射线单晶衍射等表征，其晶体结构为单斜晶系，C2/c空间群。标题配合物中的Mn原子与2个N-苯基代邻氨基苯甲酸的2个氧原子、1个Phen的2个N原子，2个水分子的氧原子形成六配位八面体结构。     

[Pt2(P2O4H2)4]4-和[Pt2(P2O4CH4)4]4-基态和激发态性质的理论研究

采用从头计算MP2和CIS方法分别优化等电子双核d⁸配合物[Pt₂(P₂O₄H₂)₄]^4-和[Pt₂(P₂O₄CH₄)₄]^4-的基态和激发态结构。结果表明基态Pt-Pt距离分别为0.290 5和0.298 7 nm，与实验的0.292 5和0.298 0 nm符合。NBO计算的Pt-Pt键级以及Pt原子间伸缩振动说明Pt-Pt相互作用具有吸引本质。CIS计算揭示电子激发到Pt-Pt的σ(p_z)成键轨道使得相互作用增强。保持激发态几何，含时密度泛函理论(TD-DFT)计算的溶液发射分别为449和475 nm，与实验值512和510 nm接近。     

配合物(BenzMeIm)2[PtCl4]的合成与表征

通过离子液体氯化1-苄基-3-甲基咪唑（BenzMeIm-Cl）与PtCl₂的反应,合成了配合物（BenzMeIm）₂[PtCl₄],并用元素分析、红外光谱、紫外-可见光谱、¹H NMR、¹³C NMR和单晶X射线衍射对其进行了表征。单晶X射线分析表明,配合物结构属于P2₁/c空间群,晶胞参数和结构解析参数为：a=0.981 80（5）nm,b=0.861 47（3）nm,c=0.144 332（7）nm,β=92.480（2）°,V=121.96（1）nm³,R₁=0.014 4,wR₂=0.038 8。     

配合物(BenzMeIm)2[PtCl4]的合成与表征

通过离子液体氯化1-苄基-3-甲基咪唑（BenzMeIm-Cl）与PtCl₂的反应,合成了配合物（BenzMeIm）₂[PtCl₄],并用元素分析、红外光谱、紫外-可见光谱、¹H NMR、¹³C NMR和单晶X射线衍射对其进行了表征。单晶X射线分析表明,配合物结构属于P2₁/c空间群,晶胞参数和结构解析参数为：a=0.981 80（5）nm,b=0.861 47（3）nm,c=0.144 332（7）nm,β=92.480（2）°,V=121.96（1）nm³,R₁=0.014 4,wR₂=0.038 8。     

配合物[Cu(NPA)2(Im)2(H2O)]·H2O的合成、晶体结构及电化学性质

A novel copper(II) complex [Cu(NPA)₂(Im)₂(H₂O)]·H₂O has been synthesized (NPA=N-phenylanthranilic acid and Im=imidazole) and characterized by IR, elemental analysis and X-ray single crystal diffraction methods. It Crystallizes in Triclinic system, space group P1 with a=0.987 9(2) nm, b=1.075 7(3) nm, c=1.559 7(5) nm, α=104.18(10)°, β=108.14(10)°, γ=92.69(10)°, V=1.513 39(7) nm³, Z=2, D_c=1.447 g·cm^-3, F(000)=684, R₁=0.028 0, wR=0.083 1. The Cu(II) ion in the title complex is coordinated with two oxygen atoms from two N-phenylanthranilic acid in monodenate mode, two nitrogen atoms form two imidazole, and one oxygen atom from water, forming a distorted square-pyramid coordination geometry. CCDC: 638653.     

[Zn(en)3]SO4配合物大尺寸单晶的水热法生长和表征

Large size single crystals of [Zn(en)₃]SO₄ have been successfully grown by a hydrothermal process at 160℃ for 24h， using CuSO₄·5H₂O， ethylene diamine and reductive Zn powder as reactants. The diameters of the single crystals are range from 0.5mm to 1mm， and lengths reach up to 20mm. The single crystals were characterized by XRD analysis， FTIR and UV-Vis spectrum absorption measurements. The single crystal was confirmed to be [Zn(en)₃]SO₄ by performing powder diffraction of the single crystal. X-ray diffraction of the single crystals shows (100)-face to be cleavage face. The diffraction peaks are sharp and rocking curve for 200 diffraction has a narrow FWHM (the full width at half maximum)， which indicate the single crystal of [Zn(en)₃]SO₄ is perfect with less lattice distortion and defects. The single crystal appears transparent，and has constant weak absorption in UV-Vis spectrum region，which could be used as a novel optical crystal material.     

配合物[Cu(H2biim)2]Br2的合成和晶体结构

The complex [Cu(H₂biim)₂]Br₂ (H₂biim=2,2′-biimdazole) has been synthesized and structurally charac-terized. It crystallizes in the Monoclinic system, space group C2/c with a=1.422 5(4) nm, b=0.931 2(2) nm, c=1.343 1(3) nm, β=116.227(4)°, V=1.595 9(7) nm^-3, R₁=0.060 2, wR₂=0.152 8 and Z=4. The copper ion has a sligh-tly distorted square planar coordination configuration with four nitrogen atoms from two H₂biim ligands. The complex has a one-dimensional chain structure, which is formed by hydrogen bonds and semi-coordinate bonds. CCDC: 624679.     

Theoretical studies on structures and spectroscopic properties of bis-cyclometalated iridium complexes [Ir(ppy)2X2]

The electronic structures and spectroscopic properties of a series of mixed bis-cyclometalated iridium(III) complexes [Ir(ppy)₂X₂]⁻ (X = CN, 1; X = NCS, 2; X = NCO, 3; ppy = 2-phenylpyridl) were investigated at the B3LYP/LANL2DZ and CIS/LANL2DZ levels. The calculated geometry parameters in the ground state are well consistent with the corresponding experimental values. The HOMO of 1 is dominantly localized on Ir atom and ppy ligand, but the HOMO of 2 and 3 have significant X ligand composition. Under the TD-DFT level with PCM model, the absorption and phosphorescence in CH₂Cl₂ media were calculated based on the optimized geometries in the ground and excited states, respectively. The lowest-lying absorption of 1 at 403 nm is attributed to {[d_x²-y²(Ir)+d_xy(Ir)+π(ppy)]→[π^∗(ppy)]} transition with metal-to-ligand and intraligand charge transfer (MLCT/ILCT) transition characters, whereas those of 2 (449 nm) and 3 (475 nm) are related to {[d_x²-y²(Ir)+d_xy(Ir)+π(ppy)+π(NCS/NCO)]→[π^∗(ppy)]} transition with MLCT/ILCT and ligand-to-ligand charge transfer (LLCT) transition characters. The phosphorescence of 1 at 466 nm can be described as originating from ³{[d_x²-y²(Ir)+d_xy(Ir)+π(ppy)][π^∗(ppy)]} excited state, while those of 2 (487 nm) and 3 (516 nm) originate from ³{[d_x²-y²(Ir)+d_xy(Ir)+π(ppy)+π(NCS/NCO)][π^∗(ppy)]} excited states. The calculated results showed that the transition character of the absorption and emission can be changed by adjusting the π electron-accepting abilities of the X ligands and the phosphorescent color can be tuned by altering the X ligands.     

Na2O-P2O5系晶体微结构形态的拉曼光谱研究及其ab initio计算

本文采用激光拉曼光谱仪测量了磷酸钠二元系(1-x)Na₂O·xP₂O₅(x=0.25,0.33,0.50,1.0)几种晶体的拉曼光谱,比较并解释了随化学组成而变化微结构单元的拉曼振动模。同时用Gaussian 98W量子化学软件从头计算了这几种化合物的拉曼光谱。实验和计算均表明,磷酸盐晶体的基本结构单元为磷氧四面体[PO₄],并且晶体中磷氧四面体的伸缩模振动频率与连接中心磷原子的桥氧数密切相关,随桥氧数增加而升高。此外还解释了模拟图谱与实验谱差异的原因。     

Spectroscopic properties of guanidinium zinc sulphate [C(NH2)3]2Zn(SO4)2 and ab initio calculations of [C(NH2)3]2 and HC(NH2)3

Raman and FTIR spectra of guanidinium zinc sulphate [C(NH₂)₃]₂Zn(SO₄)₂ are recorded and the spectral bands assignment is carried out in terms of the fundamental modes of vibration of the guanidinium cations and sulphate anions. The analysis of the spectrum reveals distorted SO₄²⁻ tetrahedra with distinct S–O bonds. The distortion of the sulphate tetrahedra is attributed to Zn–O–S–O–Zn bridging in the structure as well as hydrogen bonding. The CN₃ group is planar which is expressed in the twofold symmetry along the C–N (1) vector. Spectral studies also reveal the presence of hydrogen bonds in the sample. The vibrational frequencies of [C(NH₂)₃]₂ and HC(NH₂)₃ are computed using Gaussian 03 with HF/6-31G* as basis set.     

[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究

The two symmetrical isomers in [Co(amp)₂Cl₂]₂[ZnCl₄](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me₂SO-d₆ with the central peak of the CD₃ septet as the reference ( ₁₃C,δ 39.37; ₁H,δ 2.49 relative to SiMe₄). Cation exchange media used was Dowex 50Wx 2(H⁺ form, 200～400mesh; Biorad).     

四(对-硝基苯基)卟啉配合物的红外和拉曼光谱

本文研究了四(对-硝基苯基)卟啉及其Cr(Ⅲ)、Mn(Ⅲ)、Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)配合物的3500～220cm~(-1)的红外光谱和1700～100cm~(-1)的拉曼光谱.谱带归属表明,～250cm~(-1)谱带是M—N伸缩振动和卟啉环变形振动的复合振动.金属敏感带出现在～1600、～1582、～1547、～1284、～1190、～355和～245cm~(-1)处,其中二价金属配合物金属敏感带频率按Ni>Co>Cu>Zn顺序递减.用金属半径和d_x~2 y~2电子排斥作用解释了金属敏感带变化规律.     

Chelate complex Ni(S2C2H2)2 as a molecular model of the hydrodesulfurization active center

Electronic states of Ni atom in a square-planar complex Ni(S₂C₂H₂)₂ and its molecular adduct with H₂S were studied by means ofab initio molecular orbital calculations. H₂S adsorption stabilizes the Ni(IV) state (d⁶) in the complex with the Ni atom shifted from the plane by 0.35 ?.     

[Zn(py)2SHSH]的合成、晶体结构及理论研究

The crystal of zinc complex with salicylaldehyde salicylhydrazone(SHSH) was obtained in DMF and pyridine. It has been characterized by IR, UV, element analysis and X-ray diffraction analysis. The crystallographic data were as follows: monoclinic system, space group Pn, a=1.094 6 nm, b=0.884 0 nm, c=1.161 0 nm, β=101.350°, Z=2, V=1.101 0 nm³, D_c=1.441 g·cm^-3, μ=1.148 mm^-1, F(000)=492 and the final R=0.029 5 and wR=0.068 5 for 2 642 observed reflections with I≥2σ(I). The X-ray crystal structure analysis revealed that the center zinc(Ⅱ) is bonded to two oxygen atoms and one nitrogen atoms from a tridentate ligand(SHSH) and two nitrogen atoms from two solvent pyridine molecules to form a five-coordinate distorted trigonal bipyramid. The full-optimized molecular geometries of title complex was calculated at B3LYP/6-31G and HF/6-31G levels with Guassian 98W program. CCDC: 252832.     

Vibrational spectra of the peroxotantalates (NH4)3[Ta(O2)4], K3[Ta(O2)4], Rb3[Ta(O2)4] and Cs3[Ta(O2)4] and the crystal structure of Rb3[Ta(O2)4]

The compounds (NH₄)₃[Ta(O₂)₄], K₃[Ta(O₂)₄], Rb₃[Ta(O₂)₄] and Cs₃[Ta(O₂)₄] have been prepared and investigated by X-ray powder methods as well as Raman- and IR-spectroscopy. In the case of Rb₃[Ta(O₂)₄] the structure has been solved from single crystal data. It is shown that all these compounds are isotypic and crystallize in the K₃[Cr(O₂)₄] type (SG , No. 121). The infrared- and Raman spectra (recorded on powdered samples) are discussed with respect to the internal vibrations of the peroxo-group and the dodecahedral [Ta(O₂)₄]³⁻ ion. Symmetry coordinates for the [Ta(O₂)₄]³⁻ ion are given from which the vibrational modes of the O-O stretching vibrations of the O₂²⁻ groups, the Ta-O stretching vibrations and the Ta-O bending vibrations are deduced.