[Co (C5O2H8)2]·H3COH的 水热合成和晶体结构

合成了[Co (C5O2H8)2]·H3COH金属配合物,通过X射线衍射仪测得配合物[Co(C5O2HD2]·H3COH的晶体结构.晶体属于单斜晶系,空间群为P2 (1)/c,其晶胞参数为a=0.93325(16)nm,b=1.15015(16)nm,c=1.30029(16)nm,α=90.00°,γ=90.00°,...     

配合物[Co(PBSP)2(H2O)2]·CH3OH的合成、晶体结构和热重分析

由对氨基苯磺酸、吡啶-2-甲醛、KOH和Co(Ac)2.4H2O在甲醇和水的混合溶剂中反应得到了标题配合物[Co(PBSP)2(H2O)2]·CH3OH(KPBSP=对氨基苯磺酸缩吡啶-2-甲醛席夫碱的钾盐),并进行了元素分析、红外光谱、X-射线衍射和热重分析等表征.结果表明:标题配合物属三斜晶系,空间群为P-1,晶体学参数为:a=1.0188(4)nm,b=1.1079(5)nm,c=1.3243(5)nm,α=98.371(5)°,β=102.324(5)°,γ=106.419(4)°,V=1.3664 (10)nm3,Z=2.配合物中的金属钴离子位于非对称中心,分别与两分子脱质子的PBSP-配体中的吡啶氮原子、亚氨基氮原子及两个水分子的O原子配位,形成变形的八面体结构.     

{[K(18-C-6)][K(H2O)2]}[Cd(CN)4]的合成与结构分析

合成了配合物 { [K(18- C- 6 ) ][K(H2 O) 2 ]} [Cd(CN) 4 ](1) ,并通过元素分析、红外光谱、单晶 X-射线衍射进行了结构分析。配合物属单斜晶系 ,空间群 P2 (1) / n。晶体学数据 :a=0 .936 5 3(18) nm,b=1.6 178(3) nm,c=1.74 81(3) nm,β=91.332 (3)°,V=2 .6 479(9) nm3 ,Z=4 ,Dcalcd=1.4 5 3g/ cm3 ,F(0 0 0 ) =12 0 8,R1=0 .0 317,w R2 =0 .0 5 6 7。配合物中 [K(18- C- 6 ) ],[K(H2 O) 2 ]和 [Cd(CN) 4 ]基团通过 K N键和 K —π相互作用形成三维网状结构     

{[K(18-C-6)][K(H_2O)_2]}[Cd(CN)_4]的合成与结构分析

合成了配合物 { [K(18- C- 6 ) ][K(H2 O) 2 ]} [Cd(CN) 4 ](1) ,并通过元素分析、红外光谱、单晶 X-射线衍射进行了结构分析。配合物属单斜晶系 ,空间群 P2 (1) / n。晶体学数据 :a=0 .936 5 3(18) nm,b=1.6 178(3) nm,c=1.74 81(3) nm,β=91.332 (3)°,V=2 .6 479(9) nm3 ,Z=4 ,Dcalcd=1.4 5 3g/ cm3 ,F(0 0 0 ) =12 0 8,R1=0 .0 317,w R2 =0 .0 5 6 7。配合物中 [K(18- C- 6 ) ],[K(H2 O) 2 ]和 [Cd(CN) 4 ]基团通过 K N键和 K —π相互作用形成三维网状结构     

希夫碱配合物M3L6(NO3)6(H2O)2的合成与光谱性质

以4-氨基-1,2,4-三氮唑与对二甲氨基苯甲醛为原料,在冰醋酸催化下合成了配体4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛(L).然后利用L与过渡金属硝酸盐[M(NO3)2·xH2O(M=Cu,C0,Zn,Cd;x=3～6)]在无水乙醇中反应,制得固态配合物M3L6(NO3)6(H2O)2.通过元素分析、红外光谱、紫外光谱、荧光光谱等手段对合成的配体及配合物进行了表征.实验结果表明,该物质是一种多晶粉末状的发光材料,在紫外光的激发下,在乙醇溶液体系中的荧光发射峰在416 nm处,为蓝色荧光,色纯度高,荧光量子效率高,而配合物M3L6(NO3)6(H2O)2的荧光发射峰则红移至445 nm左右,同时荧光强度显著增强.M3L6(NO3)6(H2O)z中与M(Ⅱ)发生配位作用的基团是配体中三氮唑环上的氮原子.     

糖精钴水合物[Co(C7H4NO3S)2(H2O)4]·2H2O的合成及晶体结构

以糖精钠(sac-Na)、丙氨酸和硝酸钴为原料合成得到糖精钴琥珀色块状晶体,采用红外、X射线单晶衍射对配合物进行了表征,该晶体属单斜晶系,空间群为P21/c,晶胞参数为:a=0.79269(5)nm,b=1.61407(10)nm,c=0.77026 (5) nm,α=90°,β=99.695(7)°,Ⅴ=0.97145 (11) nm3,Z=2,Dc=1.817g/cm3,F(000)=546,R=0.0278.结构分析表明,中心Co离子与4个O原子和两个N原子配位,处于四角双锥八面体配位环境中,4个水分子在赤道平面上与Co离子配位,晶胞中还包含有2个游离的结晶水,形成了含6个水分子的结晶物.     

配合物[Zn(DMF)2(H2O)4]·C8Cl4O4的合成及其结构的研究

采用溶剂挥发扩散法合成了配合物单晶[Zn(DMF)2(H2O)4]·C8Cl4O4,其中DMF为N,N'-二甲基甲酰胺.配合物为三斜晶系,P-1空间群,其晶胞参数为a=0.57680(10)nm,b=0.85991(14)nm,c=1.2030(2)nm,α=95.781(3)°,β=102.074(3)°,γ=98.594(2)°,V=0.57154nm3,Z=1.Mr=585.51,Dc=1.701g/cm3,F(000)=298,μ=1.594mm-1,最终偏差因子R1=0.0315,wR2=0.0914,和R1=0.0345,wR2=0.0946,同时采用红外光谱分析、元素分析对其进行表征.     

1-正丁基咪唑合钴(Ⅱ)配合物的合成及其晶体结构分析

由1-正丁基咪唑(C7H12N2)和氯化钴(CoCl2)合成了一种新的配合物1-正丁基咪唑合钴配合物[Co (C7H12N2)6]Cl2.采用元素分析、红外光谱和X射线单晶衍射对配合物结构进行了表征.结果表明,所合成的配合物C42H72Cl2CoN12属于单斜晶系,空间群P2,晶胞参数:a=8.540(3)nm,b=16.851(5)nm,c=17.237(5)nm;α=90.00°,β=104.037(5)°,γ=90.00°;V=2406.5 (13)nm3,Z=2,Dc=1.207g· cm-3,F(000)=938,μ=0.509mm-1,R1 =0.0526,wR,=0.1664.     

二(3,5-二硝基苯甲酸)双(1,10-二氮杂菲)锌(Ⅱ)配合物的合成及晶体结构

用3,5-二硝基苯甲酸、1,10-二氮杂菲、Zn(Ac)2.2H2O合成了二(3,5-二硝基苯甲酸)双(1,10-二氮杂菲)锌(Ⅱ)配合物,通过元素分析和红外光谱对其结构进行了表征。用X-射线单晶衍射测定了它的晶体结构。结果表明,配合物的晶体属单斜晶系,空间群P2(1)/c,a=1.9141(7)nm,b=1.9681(8)nm,c=1.0052nm,β=95.668(7)°,V=3.768nm3,Dc=1.576kg.m-3,Z=4,μ=0.734mm-1,F(000)=1832,R1=0.0482,Rw2=0.0940。配合物通过1,10-二氮杂菲中的两个氮原子和3,5-二硝基苯甲酸根离子中的羧基氧原子配位,形成六配位不规则八面体结构。     

三维超分子配合物[Zn（C_（12）H_8N_3）_2·H_2O]的水热合成、晶体结构及光致发光1

通过水热法合成了一种三维超分子配合物Zn（C12H8N3）2.H2O,经元素分析、紫外和红外光谱对其进行表征。用X射线单晶衍射测定了其晶体结构,该配合物晶体属单斜晶系,P21/c空间群,晶胞参数为：a=1.25239（10）nm,b=1.30233（11）nm,c=1.33167（11）nm,β=102.6950（10）°,Z=4,[Zn（C12H8N3）2.H2O],Mr=471.81,V=2.1189（3）nm^3,Dc=1.479g·cm^-3,μ=1.189mm^-1,F（000）=968,R1=0.0300,WR2=0.1017,GOF=1.005。该化合物由1个Zn（Ⅱ）离子、2个2-（2-吡啶基）苯并咪唑阴离子和1分子配位水组成。其中2-（2-吡啶基）苯并咪唑的1位氮原子、吡啶环上氮原子及水分子中氧原子与锌（Ⅱ）离子配位,形成五配位的畸变三角双锥结构,单胞分子之间通过氢键O（w）-H…N和π-π堆积作用相互构成三维网状超分子体系。固态荧光测试显示,该配合物具有强的蓝色荧光发射（λmax=456nm）。     

Infrared Spectra of Morfolonium (mpH)2Mo2Cl6(H20)2(I),(mpH)2Mo2ClxBr6-x(H2O)2(II)/ (mpH)2Mo2Br6(H2O)2(III) and the Pyridinium (PyH)2Mo2I6(H2O)2(IV)Hexahalo-di(aquo): dimolybdate(II) Complexes,Containing Quadruple Metal-Metal Bounds

Abstract

The electronic (800–400 nm), infrared (4000–200,400–20 cm^?1), ordinary Raman (400–200 cm^?1) spectra of morpholinium and the pyridium hexahalo-di(aquo) dimolybdate(II) complexes, containing quadruple metal-metal bonds were investigated. The electronic spectra of the solid compounds at various temperatures (25,100 and 300K) demonstrate intense and structured bands in the visible region (510–582 nm) attributed to the expected δ→δ? transitions.

From the infrared and Raman spectra, the skeletal stretching modes in these complexes have been localized, and the charectenstic bands of these ions were observed in the expected regions.

Finally, the ionic interections were relatively weak, but the existance of phenomena was perceptible and the result was obtained in agreement with X-ray data.     

Isomeric Cl(2)O(2)(+) and Cl(2)O(2)(-) ions

Charged species structurally related to several isomers of Cl(2)O(2), of considerable importance in atmospheric chemistry, were obtained by chemical ionization (CI) and characterized by collisionally activated dissociation (CAD) mass spectrometry. The ClOClO(+) and [Cl(2)-O(2)](+) species were prepared by positive ion Cl(2)/CI of ClO(2) and O(2), respectively, whereas the ClClO(2)(+) isomer proved an elusive species of considerably lower stability. The ClClO(2)(-) anion was obtained from the negative ion Cl(2)/CI of ClO(2). The formation process, structure and stability of the ions are discussed in connection with available theoretical results and related to the recent preparation of (Cl(2)O(2))(+)SbF(6)(-) and (Cl(2)O(2))(+)Sb(2)F(11)(-) salts in the solid phase. Copyright 1999 John Wiley & Sons, Ltd.     

The 2(3)Delta(g) State of (7)Li(2)

Using pulsed perturbation-facilitated optical-optical double resonance (PFOODR) spectroscopy, the 2(3)Delta(g) state of (7)Li(2) (electronic configuration (varsigma(g)2s) (4ddelta(g)), effective principal quantum number n* = 4.101) has been observed and assigned. Molecular constants and a RKR potential energy curve were obtained. The major molecular constants are Copyright 2000 Academic Press.     

Isotope fractionation in aqua-gas systems: Cl(2)-HCl-Cl(-), Br(2)-HBr-Br(-) and H(2)S-S(2-)

We report calculated values of isotope fractionation factors between chlorine, bromine and sulphide hydrated anions and respective gaseous compounds: hydrogen chloride, hydrogen bromide, molecular chlorine and bromine and hydrogen sulphide. For the calculation of the reduced partition function ratios (β-factors) of hydrated Cl(-), Br(-) and S(2-) anions, we used a model of a cluster composed of the considered ion surrounded by two shells of H(2)O molecules. Only the electrostatic interaction between ion and water molecules treated as electric dipoles was taken into account. The β-factors for the gaseous compounds (HCl, Cl(2), HBr, Br(2) and H(2)S) were calculated from vibrational frequencies reported by Urey and Greiff [Isotopic Exchange Equilibria, J. Am. Chem. Soc. 57, 321 (1935)] and Schauble et al. [Theoretical Estimates Equilibrium Chlorine-Isotope Fractionation, Geochim. Cosmochim. Acta 67, 3267 (2003)]. Low-temperature isotope fractionation between chlorine-hydrated anion and hydrogen chloride attains 1.55-1.68‰ (this work), which is in good agreement with experimental data (1.4-1.8‰) [Z.D. Sharp, J.D. Barnes, T.P. Fischer and M. Halick, An Experimental Determination of Chlorine Isotope Fractionation in Acid Systems and Applications to Volcanic Fumaroles, Geochim. Cosmochim. Acta 74, 264 (2010)]. The predicted isotope fractionations for hydrated bromine and HBr, Br(2) gases are very small, 1000?ln α, do not exceed 0.8‰; thus, the expected variations of bromine isotope composition in aqua-gas systems will require enhanced precision for their detection. In contrast, the sulphur isotope fractionation between H(2)S( gas ) and S(2-) attains 6.0‰ at room temperature and drops nearly linearly to 3.1‰ at 350°C.     

Infinite period and Hopf bifurcations for the pH-regulated oscillations in a semibatch reactor (H(2)O(2)-Cu(2+)-S(2)O(2-) (3)-NaOH system)

Dynamic behavior of the pH-regulated oscillations has been studied for the hydrogen peroxide oxidation of thiosulfate ions in the presence of trace amounts of copper(II) ions in a semibatch reactor. A solution of 0.08 M Na(2)S(2)O(3) and 0.112 M NaOH was flowed at 0.160 mL/min into 300 mL of solution containing the H(2)O(2) and Cu(2+) in a vessel. There exists a critical value of the H(2)O(2) or Cu(2+) concentrations below which the system does not oscillate. The oscillations appear due to an infinite period bifurcation at low initial concentrations of the H(2)O(2). The initial concentration of Cu(2+) may be considered as a bifurcation parameter in this case. Increase of the initial hydrogen peroxide concentration causes the pH-regulated oscillations through a nondegenerate supercritical Hopf bifurcation. The classification of bifurcations is based on the analysis of the behavior of oscillation amplitude and period at different initial concentrations of the H(2)O(2) and Cu(2+). Our results show a possibility to distinguish different scenarios for the appearance of transient oscillations in semibatch experiments. (c) 1996 American Institute of Physics.     

Vortex fluctuations in underdoped Bi(2)Sr(2)CaCu(2)O(8+delta) crystals

Vortex thermal fluctuations in heavily underdoped Bi(2)Sr(2)CaCu(2)O(8+delta) (T(c)=69.4 K) are studied using Josephson plasma resonance. From the zero-field data, we obtain the c-axis penetration depth lambda(L,c)(0)=230+/-10 micrometer and the anisotropy ratio gamma(T). The low plasma frequency allows us to study phase correlations over the whole vortex solid state and to extract a wandering length r(w) of vortex pancakes. The temperature dependence of r(w) as well as its increase with dc magnetic field is explained by the renormalization of the vortex line tension by the fluctuations, suggesting that this softening is responsible for the dissociation of the vortices at the first order transition.     

The nu(2) Band of Formaldehyde-d(2)

High-resolution Fourier transform infrared spectrum of the nu(2) band (1590-1780 cm(-1)) of deuterated formaldehyde D(2)CO has been recorded. More than 2500 rovibrational transitions have been assigned up to J(max) = 52 and K(max)(a) = 17. The upper state v(2) = 1 (A(1)) was found to be perturbed by a DeltaK(a) = 2 interaction with the v(4) = 2 (A(1)) state. To explain the resonance perturbation in the v(2) = 1 state, some lines of the 2nu(4) band (the band center at about 1868 cm(-1)) have also been assigned. Both bands were fitted simultaneously to the Watson-type rotational Hamiltonian using I(r) representation in A reduction, and the mutual interaction was taken into account. As a result, the rotational parameters of the v(2) = 1 state up to eighth order and the interaction parameter have been obtained. Copyright 2001 Academic Press.     

The Dynamics of N(2)-O(3) and N(2)-SO(2) Probed by Microwave Spectroscopy

The microwave spectra of N(2)-O(3) and N(2)-SO(2) have been recorded in the 6-18 GHz range using a pulsed-nozzle, Fourier transform microwave spectrometer. C-type transitions have been observed for both complexes which are slightly shifted by internal tunneling motions of the O(3) or SO(2) moieties. In addition, unshifted a-type transitions have been observed for N(2)-O(3). The nuclear hyperfine pattern is typical of equivalent nitrogen nuclei. Two sets of rotational and hyperfine constants are required to fit the symmetric and antisymmetric nuclear spin states, indicating that the equivalence arises from tunneling rotation of the nitrogen molecule. Internal tunneling motions along three tunneling pathways have been identified, although no information on the N(2) tunneling frequency is available from the spectra. From the N(2)-O(3) data the tunneling frequencies cannot be decorrelated from the rotational parameters; however, the O(3) tunneling frequency upper limit is estimated to be 2.0 MHz and the frequency of the concerted tunneling motion of both moieties is estimated to be about 8.9 MHz. For N(2)-SO(2), the SO(2) tunneling frequency is 11.5 kHz and the concerted frequency 173.9 kHz. Both complexes are roughly T shaped with the N(2) axis approximately perpendicular to the O(3) or SO(2) plane. In the equilibrium structures of both complexes, the a-c inertial plane is a plane of symmetry. The centers of mass separations are estimated from the rotational parameters to be 3.582 ? for N(2)-O(3) and 3.875 ? for N(2)-SO(2). The angle between the symmetry axes of the O(3) or SO(2) and the line joining their centers of mass have been calculated as 130.84 degrees (or 49.16 degrees ) and 119.71 degrees (or 60.29 degrees ), respectively. From the quadrupole analysis, the average angle between the N(2) axis and the a-inertial axis is 32.12 degrees for N(2)-O(3) and 27.81 degrees for N(2)-SO(2). Model electrostatic and ab initio calculations confirm these structures. Differences between the experimental and calculated structural parameters highlight the role of tunneling dynamics in these complexes. Copyright 2000 Academic Press.     

New vortex-matter size effect observed in Bi(2)Sr(2)CaCu(2)O(8 + delta)

The vortex-matter 3D to 2D phase transition is studied in micron-sized Bi(2)Sr(2)CaCu(2)O(8 + delta) single crystals using local Hall magnetization measurements. At a given temperature, the second magnetization peak, the signature of a possible 3D--2D vortex phase transition, disappears for samples smaller than a critical length. We suggest that this critical length should be equated with the 2D vortex lattice ab-plane correlation length R(2D)(c). The magnitude and temperature dependence of R(2D)(c) agree well with Larkin-Ovchinnikov collective pinning theory.