LiCl-(2ZnCl2•KCl)-(ZnCl2•2KCl)系中的三个赝二元系

用目测变温、DTA和XRD法研究了LiCl-(2ZnCl2•KCl)-(ZnCl2•2KCl)赝三元系中的三个侧边赝二元系. 结果表明, 在LiCl-(2ZnCl2•KCl)系中有一个组成为3LiCl•2KCl•4ZnCl2或Li3K2Zn4Cl13的三元固液同组成化合物生成, 熔点245 ℃; 在LiCl-(ZnCl2•2KCl)系中有一个组成为12LiCl•2KCl•ZnCl2或Li12K2ZnCl16的三元固液异组成化合物生成, 转熔(包晶)温度432 ℃, 而在另一个赝二元系(2ZnCl2•KCl)-(ZnCl2•2KCl)中有一个固液异组成的二元化合物4ZnCl2•5KCl或K5Zn4Cl13生成, 转熔温度249 ℃.     

ZnCl2熔盐的分子动力学模拟

近年来，若干作者根据几种粒子间函数，对ZnCl2熔盐结构做过分子动力学模拟［1－3］其出的Zn－Cl和Cl－Cl离子间的偏径向分布函数与中子衍射实测值符合较好，但Zn－Zn离子间距以及Zn－Zn间配位数计算值多偏高．鉴于Busing势函数在多价卤化物馆盐的分子动力学计算中应用效果较好[4],我们试用Busing势函数为基础对ZnCl2熔盐结构和能量做分子动力学计算．1研究方法计算所用粒子势为Busing势函数此处，Zi为离子的电行数（ZZn。＋＝2，Zcl－＝1），几；是离子有效半径，人为＊离子的“硬度”参数·据文献问，f二0．005071，尸zn。十二0．…     

Synthesis,Structure and Luminescent Properties of [Zn(btzb)2Cl2]·2H2O[btzb=1,2-Bis(5-tetrazolyl)benzene]

The title compound[Zn(btzb)2Cl2]·2H2O(1·2H2O,btzb=1,2-bis(5-tetrazolyl)benzene)was synthesized in situ by the[2 3] cycloaddition reaction of phthalonitrile with NaN3 in water in the presence of ZnCl2 under refluxing conditions.1·2H2O crystallizes in the monoclinic system,space group P21/c with a=9.0119(18),b=7.5566(15),c=18.076(5)(A),β=114.67(2)°,V=1118.6(4)(A)3,Z=2,Dc=1.784 g/cm3 T=223(2)K,C16H16N16O2Cl2Zn,Mr=600.74,F(000)=608,μ(MoKα)=1.393 mm-1,S=1.081,R=0.0306 and wR=0.0669 for 1896 observed reflections with Ⅰ ＞2σ(Ⅰ).The Zn2 ion of 1 is coordinated by four N atoms from two btzb ligands and two Cl atoms,forming a distorted octahedral coordination geometry.A number of intermolecular hydrogen bonding interactions between molecules 1 and/or the solvated water molecules result in a 3D hydrogen-bonded structure.The luminescent property of 1·2H2O was also investigated.     

A Zinc TTR Complex with a Novel 2-D Structure （TTR = 3-Amino-1H-1,2,4-triazole）

The solvothermal reaction of 3-amino-1H-1,2,4-triazole (ttr) with Zn(ClO4)2·6H2O and NaCl in a 1:1:1 molar ratio gave a new complex [Zn(ttr)Cl]n with a 3-connected (4.82) 2-D struc- ture. The layers stack in the -ABAB- way along the c axis with abundant hydrogen bonding interac- tions to form the crystal structure. The complex [Zn(ttr)Cl]n crystallizes in the orthorhombic space group Pbca with a = 9.369(1), b = 10.049(1), c = 11.905(1) , V = 1120.9(3) 3, Z = 8.00, C2N4H3ZnCl, Mr = 183.90, Dc = 2.180 g/cm3, μ = 4.740 mm-1, F(000) = 720, S = 1.059 and T = 293(2) K. The final R = 0.0662 and wR = 0.2457 for 956 observed reflections with I > 2σ(I), and R = 0.0689 and wR = 0.2504 for all data.     

[Et_4N]_2[Zn_2(OPh)_2Cl_4]的合成和晶体结构

ZnCl2, PhONa和Et4NCl稨2O在乙腈溶剂中反应合成了一种二核锌配合物[Et4N]2[Zn2(OPh)2Cl4]。X射线衍射结果表明,晶体属单斜晶系,C2/m空间群,晶胞参数 a = 14.1366(2), b=13.6985(5), c=9.3308(3)牛?107.851(2)o, V=1719.92(9)?,C28H50O2N2Zn2Cl4,Mr=721.24,Z=2,Dx=1.393g/cm3,μ(MoKα)=1.732mm—1,F(000)=756, R=0.0552, wR=0.1534, S=1.027。 配合物是由2个阳离子Et4N+和1个阴离子[Zn2(OPh)2Cl4]2—组成。阴离子[Zn2(OPh)2Cl4]2—包含着1个中心Zn2O2菱形平面。配合物中的2个锌原子通过2个苯酚中的氧原子桥连,每个锌原子还与2个氯原子配位形成变形四面体结构。     

Synthesis,Structure and Luminescent Properties of [Zn（btzb）2Cl2]·2H2O [btzb = 1,2-Bis（5-tetrazolyl）benzene]

The title compound [Zn（btzb）2Cl2]·2H2O （1·2H2O, btzb = 1,2-bis（5-tetrazolyl）ben- zene） was synthesized in situ by the [2＋3] cycloaddition reaction of phthalonitrile with NaN3 in water in the presence of ZnCl2 under refluxing conditions. 1·2H2O crystallizes in the monoclinic system, space group P2 1/c with a = 9.0119（18）, b = 7.5566（15）, c = 18.076（5）A, β= 114.67（2）°, V= 1118.6（4）A^3, Z = 2, Dc = 1.784 g/cm^3, T= 223（2） K, C16H16N16O2Cl2Zn, Mr = 600.74, F（000） = 608, μ（MoKα） = 1.393 mm^-1, S = 1.081, R = 0.0306 and wR = 0.0669 for 1896 observed reflections with I 〉 2σ（I）. The Zn^2＋ ion of 1 is coordinated by four N atoms from two btzb ligands and two Cl atoms, forming a distorted octahedral coordination geometry. A number of intermolecular hydrogen bon- ding interactions between molecules 1 and/or the solvated water molecules result in a 3D hydrogen-bonded structure. The luminescent property of 1·2H2O was also investigated.     

ZnCl2/粘土-SA01催化合成二苯甲烷反应动力学研究

在ZnCl2/粘土-SA01催化剂上合成了二苯甲烷,考察了负载量、苯/苄基氯摩尔比、催化剂用量、反应温度和时间对该反应的影响,研究了以ZnCl2/粘土-SA01为催化剂合成二苯甲烷的反应动力学,为探讨其反应机理和研究烷基化反应动力学提供了依据.结果表明,温度在303-318K时,本征动力学方程为r=k[ZnCl2/粘土-SA01]0.8[C6H6][C6H5CH2Cl],属二级反应,表观反应活化能为88.6kJ/mol;在328-353K时,其本征动力学方程为r=k[ZnCl2/粘土-SA01]0.1,反应属零级反应,表观活化能为52.8kJ/mol.     

[Co(2,3-tri)(amp)Cl][ZnCl4]体系中部分几何经式异构体的结构测定

利用单晶X-射线衍射分析了[Co(2,3-tri)(amp)Cl][ZnCl4](2,3-tri=N-(2-Aminoethvl)-1,3-propanediamine;amp=2-(Aminomethyl)pyridine)体系中的一异构体(m3-[Co(2,3-tri)(amp)Cl][ZnCl4]@2.5H2O)结构,用二维核磁共振DQCOSY和NOESY技术联合解析了另两个异构体(m2-[Co(2,3-tri)(amp)C1][ZnCl4]及m4-[Co(2,3-tri)(amp)Cl]][ZnCl4])在溶液中的结构.结构解析显示它们为该体系的三个几何经式异构体.解析的晶体结构属中心对称的空间群,表明它是外消旋的对映体.     

一种新颖的二维4f-3d-5d多金属-异烟酸配合物的合成、晶体结构和磁性研究

通过水热方法合成了一种新颖的异金属金属-异烟酸无机-有机杂化体[Zn0.5(H2O)]{(Hg2Cl5)[Er(C6NO2H4)3(H2O)2]}(HgCl2)·0.5CH3OH·0.5H2O (1)并对其进行了单晶X-射线衍射结构表征。该化合物是首例4f-3d-5d多金属-异烟酸配合物。化合物1属于单斜晶系C2/c空间群,每个单胞中有8个分子,晶体学参数为：a = 34.165(4) Å,b = 9.4692(8) Å,c = 24.575(3) Å,β = 115.090(5)°,V = 7200(1) Å3,C18.50H21Cl7ErHg3N3O10Zn0.50,Mr = 1495.25,Dc = 2.759 g/cm3,T = 293(2) K,μ(MoKα) = 15.954 mm-1,F(000) = 5400, R1/wR2 = 0.0561/0.0909,共有6468个独立衍射点,其中[I > 2σ(I)]的有3157个。该化合物具有新颖的二维{(Hg2Cl5)[Er(C6NO2H4)3(H2O)2]}层状结构,由Hg2Cl5–连接[Er(C6NO2H4)3(H2O)2]链形成。该二维层和氯化汞及结晶水之间通过氢键形成三维结构,甲醇分子和水合锌离子位于该三维结构的空隙中。对化合物1的磁性测试显示该化合物具有反铁磁作用。     

Pd~n-CO(n=1～7)簇模型的从头算研究

本文采用带相对论校正赝势的金属态原子基组, 对Pd~n-CO(n=1～7)簇模型进行了从头算研究。通过比较依据最低自旋态原则和金属态原则的计算结果,指出了两种原则的优缺点。总的计算结果表明, 依据金属态原则, 其结果可以更好地符合CO/Pd吸附体系的实验数据, 并认为CO/Pd吸附过程的成键作用主要是CO(5σ)→Pd(5sp)与Pd(5sp)→CO(2π^*)的σ/π授受作用。     

Synthesis and structure of new compounds with Zn-Ga bonds: insertion of the gallium(I) bisimidinate Ga(DDP) into Zn-X (X = CH3, Cl) and the homoleptic complex cation [Zn(GaCp*)4]2+

Insertion reactions of the low-valent group 13 bisimidinate ligand Ga(DDP) {DDP = 2-[(2,6-diisopropylphenyl)amino]-4-[(2,6-diisopropylphenyl)imino]-2-pentene} into Zn-Me and Zn-Cl bonds are reported. The reaction of ZnMe2 with 2 equiv of Ga(DDP) yields the double-insertion product [{(DDP)GaMe}2Zn] (1), whereas the insertion of Ga(DDP) into the Zn-Cl bond of ZnCl2 in tetrahydrofuran (THF) leads to the monoinsertion product [{(DDP)GaCl}ZnCl(THF)2] (2). Treatment of 2 with Na[BArF] results in the salt [{THF.Ga(DDP)}Zn(THF)(mu-Cl)]2[BArF]2 (3), with two Cl atoms bridging the Zn centers. The structural features of the Zn-Ga-bonded compounds 1-3 were compared with related complexes and in particular with the compound [Zn(GaCp*)4][BArF]2 (4), which was synthesized by the reaction of ZnMe2, [H(OEt2)2][BArF], and GaCp* in fluorobenzene. The complex cation [Zn(GaCp*)4]2+ of 4 relates to previously reported d10 analogues [M(GaCp*)4] (M = Ni, Pd, Pt). All new compounds were fully characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction analysis.     

CRYSTAL AND MOLECULAR STRUCTURE OF DICHLOROBIS-(PYRIDINIOPROPIONATO)ZINC(Ⅱ) ,Zn(C_5H_5NCH_2CH_2CO_2)_2Cl_2

<正> A 1:2 adduct of ZnCl2 with pyridiniopropionate (C5H5N + CH2CH2CO2-,ppBET ) has been prepared and characterized by single-crystal X-ray analysis. The complex crystallizes in the monoclinic space group P21/c(No. 14) with a = 13. 524(2), 6 = 9.322(3), 15. 474(2) A, β=106. 34(2)°, V = 1871. 9(5) A3, Z = 4, Dm = 1. 554gcm-3, Dc=1. 557gcm-3, and μ = 16. 5cm-1. The crystal structure comprises discrete [Zn(ppBET)2Cl2] molecules in which the Zn atom is tetrahe-drally coordinated by two unidentate;carboxylato groups [Zn - O = 1. 965(4) , 1. 969 (4)A] and two chloro ligands [Zn-Cl=2. 269(2),2. 266(1)A].     

LZnX complexes of tripodal ligands with intramolecular RN-H hydrogen bonding groups: structural implications of a hydrogen bonding cavity, and of X/R in the hydrogen bonding geometry/strength

Tripodal ligands N(CH2Py)3-n(CH2Py-6-NHR)n(R=H, n=1-3 L1-3, n=0 tpa; R=CH2tBu, n=1-3 L'1-3) are used to investigate the effect of different hydrogen bonding microenvironments on structural features of their LZnX complexes (X=Cl-, NO3-, OH-). The X-ray structures of [(L2)Zn(Cl)](BPh4)2.0.5(H2O.CH3CN), [(L3)Zn(Cl)](BPh4)3.CH3CN, [(L'1)Zn(Cl)](BPh4) 1', [(L'2)Zn(Cl)](BPh4)2'.CH3OH, and [(L'3)Zn(Cl)](BPh4)3' have been determined and exhibit trigonal bipyramidal geometries with intramolecular (internal) N-HCl-Zn hydrogen bonds. The structure of [(L'2)Zn(ONO2)]NO3 4'.H2O with two internal N-HO-Zn hydrogen bonds has also been determined. The axial Zn-Cl distance lengthens from 2.275 A in [(tpa)Zn(Cl)](BPh4) to 2.280-2.347 A in 1-3, 1'-3'. Notably, the average Zn-N(py) distance is also progressively lengthened from 2.069 A in [(tpa)Zn(Cl)](BPh4) to 2.159 and 2.182 A in the triply hydrogen bonding cavity of 3 and 3', respectively. Lengthening of the Zn-Cl and Zn-N(py) bonds is accompanied by a progressive shortening of the trans Zn-N bond from 2.271 A in [(tpa)Zn(Cl)](BPh4) to 2.115 A in 3 (2.113 A in 3'). As a result of the triply hydrogen bonding microenvironment the Zn-Cl and Zn-N(py) distances of 3 are at the upper end of the range observed for axial Zn-Cl bonds, whereas the axial Zn-N distance is one of shortest among N4 ligands that induce a trigonal bipyramidal geometry. Despite the rigidity of these tripodal ligands, the geometry of the intramolecular RN-HX-Zn hydrogen bonds (X=Cl-, OH-, NO3-) is strongly dependent on the nature of X, however, on average, similar for R=H, CH2tBu.     

ZnCl＿2－尿素熔体的电化学研究

研究了温度、浓度对ＺｎＣｌ２－尿素熔体电导的影响,ＺｎＣｌ２－ＮａＣｌ－尿素熔体的电导率（１２５℃）可达３０ｍｓ·ｃｍ－１以上．用循环伏安曲线、恒电位电解及断电后的电位－时间曲线,研究尿素熔体中Ｚｎ２＋的电还原和锌在钛、铜电极上的电沉积．Ｚｎ２＋的电还原为一步可逆过程,锌沉积在铜电极上会形成ＣｕＺｎ５合金．Ｚｎ２＋在熔体中扩散系数为１．３×１０－６ｃｍ２·ｓ－１（１２５℃）     

Molecular dynamics studies of the kinetics of phase changes in clusters III: structures, properties, and crystal nucleation of iron nanoparticle Fe331

Molecular dynamics (MD) computer simulations have been carried out to study the structures, properties, and crystal nucleation of iron nanoparticles with 331 Fe atoms or with diameter around 2 nm. Structure information for the nanoparticles was analyzed from the MD simulations. Three crystalline phases and one amorphous phase were obtained by cooling the nanoparticles from their molten droplets at different cooling rates or with different lengths of cooling time periods. Molten droplets froze into three different solid phases and a solid-solid transition from a disordered body-centered cubic (BCC) phase to an ordered BCC phase were observed during the slow cooling and the quenching processes. Properties of nanoparticle Fe₃₃₁, such as melting point, freezing temperature, heat capacity, heat of fusion, heat of crystallization, molar volume, thermal expansion coefficient, and diffusion coefficient, have been estimated. Nucleation rates of crystallization to two solid phases for Fe₃₃₁ at temperatures of 750, 800, and 850 K are presented. Both classical nucleation theory and diffuse interface theory are used to interpret our observed nucleation results. The interfacial free energy and the diffuse interface thickness between the liquid phase and two different solid phases are estimated from these nucleation theories.     

Comparison of bulk and thin film structures of the liquid crystal 28OBC: measurements and simulations

Freely-suspended liquid crystalline films of ethyl 4'-n-octyloxybiphenyl-4-carboxylate (28OBC) were prepared and transferred onto different substrates which enable detailed structural characterization. The structures of these thin film assemblies, which are only accessible in this way, were determined and compared with the crystal and molecular structure of 28OBC as formed by crystallization from toluene solution. The compound crystallizes in the monoclinic space group P21/c, a = 11.168(1) A, b = 7.595(2) A, c = 49.106(1) A, beta = 94.01(1) degree, Z = 8. The two symmetrically independent molecules of the asymmetric unit have been used as starting geometries for semi-empirical MO calculations. The difference between the experimentally observed and the optimized molecular structures is interpreted as the influence of the crystal field. The structures of the crystalline and E film phases have been investigated by SAXR and TED and the former has been found to be different from the bulk structure. The structural relationships between the different phases are discussed and a suggestion for the crystalline film structure is given as deduced from simulations of electron diffraction patterns.     

熔融CaF2的径向分布函数

熔融CaF_2是一种典型的离子液体,又是一种重要的冶金熔体.径向分布函数不仅是描述熔体结构的重要物理量,而且是计算熔体热力学性质的基础.实验上可以通过X 射线、中子衍射测得结构因子经Fourier 变换得到径向分布函数.已有使用X 射线衍射方法实验测定熔融CaF_2结构因子的报导.但由于实验上分解三种离子对Ca~(2+)-Ca~(2+),Ca~(2+)-F~-、F~--F~-偏结构因子的困难,未能给出相应的三种径向分布函数g++(r)、g+-(r)、g--(r),仅估计出三种径     

加热覆盖有ZnCl2溶液的锌片制备ZnO亚微米棒阵列

将表面覆盖有ZnCl2溶液的锌片加热到400 ℃反应1 h, 在锌片上生长出了ZnO亚微米棒阵列. 采用扫描电镜、透射电子显微镜和X射线衍射仪对所制备的产物进行了表征和分析. 结果表明产物为六方相纤锌矿单晶结构的ZnO亚微米棒, 其直径和长度分别为300～650 nm和6 μm, 提出了ZnO亚微米棒可能的生长机理. 在波长为300 nm光的激发下, 发现了ZnO亚微米棒阵列具有发光峰位于395 nm强的紫外光发光和位于490 nm弱的蓝绿光发光, 这两种发光分别起源于ZnO宽带隙带边发射和ZnO中相应的缺陷结构.     

Dramatic structural rearrangements in porous coordination networks

With the use of ab initio X-ray powder diffraction, a family of isostructural crystalline porous coordination networks, [(ZnX(2))(3)(TPT)(2)](n)· (solvent) (X = I, Br, Cl), has been studied at elevated temperatures of 573-723 K. Upon heating, all three networks exhibited crystalline-to-amorphous-to-crystalline (CAC) phase transformations to three new networks, [(ZnI(2))(3)(TPT)(2)](n), [(ZnBr(2))(3)(TPT)(2)](n)·(H(2)O) and [(ZnBr(2))(μ-Br)(ZnBr)(TPT)](n), and [(ZnCl(2))(μ-Cl)(ZnCl)(TPT)](n), respectively. A set of control experiments was used to obtain detailed mechanistic aspects of the CAC transformations. We demonstrate how bonds are broken and formed in these significant molecular rearrangements and how the initial arrangement plays a crucial role in the formation of the new networks after the CAC transformations. The structural information in the amorphous phase is retained and passed from a metastable to a more stable crystal, thus, reinforcing the notion that coordination networks are flexible and chemically active.