类晶加合物(M=Co,Cu, Ni)的晶体结构及分子间相互作用的理论研究

合成了3种化合物 [2-ClPyH]2CoCl4(1), [2-ClPyH]2NiCl4(2)和[2-ClPyH]2CuCl4(3), 单晶X射线衍射法晶体结构测定结果表明, 这3种化合物是同形加合物, 在它们的结构中, [2-ClPyH]+离子呈平面状, 而[MCl4]2-离子为变形的四面体. 晶体结构分析发现晶体中存在N—H…Cl和C—H…Cl氢键, 以及Cl…Cl分子间相互作用和π-π堆积作用. 对自由状态下独立的配位离子进行的几何构型优化, 以及三维周期性条件下几何结构优化的量子化学计算结果表明, 标题化合物中具有方向性和选择性的氢键决定延伸性结构的方向, 而相对较弱的卤素…卤素作用在最终晶体结构的确定中扮演很重要的角色.     

2,2′-二硫代二苯甲酸、2,2′-二羧苯基硫醚及含氮配体构筑的2个配合物的合成、结构与热稳定性研究(英文)

使用2,2′-二硫代二苯甲酸和2,2′-联吡啶(2,2′-bipy)、硝酸铜在水热条件下发生的原位反应合成了一个铜配合物,即[Cu2(C14H8O4S)2(C10H8N2)2](1)(C14H8O4S=2,2′-二羧苯基硫醚,C10H8N2=2,2′-联吡啶);然后又利用2,2′-二硫代二苯甲酸和菲咯啉(phen)、氯化钙在水溶液中合成了一个钙配合物,即{[Ca(C14H8O4S2)(C12H8N2)2]·(H2O)2}n(2)(C14H8O4S=2,2′-二硫代二苯甲酸根,C12H8N2=菲咯啉),并对它们分别进行了元素分析、红外光谱、热稳定性、X射线粉末衍射和X射线单晶衍射的表征。结果表明:配合物1由2,2′-二羧苯基硫醚配体连接形成了一个双核的化合物,通过氢键和氮杂环之间的π…π作用形成三维超分子网络结构。配合物2由二硫代二苯甲酸配体桥联形成了一个一维链状结构,通过氢键和氮杂环之间的π…π作用也形成三维超分子网络结构。并且,对这2个配合物的热稳定性分别进行了研究。     

基于2-氨基对苯二甲酸的镉配位聚合物的合成、晶体结构和性质研究

以2-氨基对苯二甲酸根离子(AT)为配体,合成了3个结构新颖的镉配位聚合物:[Cd(AT)(H2O)]n(1)、[Cd(AT)(Py)]n(2)和[Cd(AT)(BPP)]n(3)(AT=2-氨基对苯二甲酸根离子,Py=吡啶,BPP=1,3-二(4-吡啶基)丙烷)。晶体结构表明,随着辅助配体的改变,AT表现出3种不同的配位模式,分别形成rtl(1)、ths(2)和sql(3)3种不同的拓扑结构。由于分子内/分子间氢键、芳香环之间的π…π堆积与C-H…π相互作用,使得3个化合物展现出较好的热稳定性。     

OCS,CO2,N2O与烯、炔烃之间π…π作用的电子密度拓扑研究

采用MP2/aug-cc-pVDZ方法对氧硫化碳(OCS)、二氧化碳(CO2)、一氧化二氮(N2O)与乙烯(C2H4)、乙炔(C2H2)、2-丁炔(C4H6)之间形成的平行构型复合物中的分子间相互作用进行了理论研究.复合物的相互作用能按照B…C2H4B…C2H2>B…C4H6(B=OCS,CO2,N2O)的顺序依次减小.采用电子密度拓扑分析理论方法,讨论了复合物中π…π作用的成键特性.电子密度拓扑分析表明复合物中形成了弱的分子间相互作用,且以静电作用为主;π电子密度分子图与全电子密度分子图中键径方向是一致的,说明π…π作用在本文所讨论的体系中起着很重要的作用.NBO分析表明净电荷迁移从电子给体C2H4,C2H2,C4H6到电子受体OCS,CO2,N2O,迁移数按照B…C2H4相似文献   

三维混配型三核镉(Ⅱ)配合物的合成及荧光性质

水热合成法合成了新颖的三核超分子配合物[Cd3(PDA)3(2,2′-bipy)3(H2O)2].2H2O(1)(H2PDA=pyridine-2,6-dicarboxylic acid),并进行了元素分析、红外、热重、荧光及单晶衍射测试。该化合物属单斜晶系,P21/n空间群,晶胞参数分别为:a=2.12281(14)nm,b=1.006 09(7)nm,c=2.830 64(19)nm,β=108.937 0(10)°。中心原子配位数为7,羧基以双齿形式将Cd1、Cd2、Cd3桥联组成三核配合物。分子间氢键与π-π堆积构筑成三维超分子结构。荧光分析表明该配合物在室温下发出强烈的蓝色荧光,具有潜在的应用价值。     

Topological Studies on the П…П Interactions between OCS, CO2, N2O and Hydrocarbon

采用MP2/aug-cc-pVDZ方法对氧硫化碳（OCS）、二氧化碳（CO2）、一氧化二氮（N2O）与乙烯（C2H4）、乙炔（C2H2）、2-丁炔（C4H6）之间形成的平行构型复合物中的分子间相互作用进行了理论研究.复合物的相互作用能按照B…C2H4〈B…C2H2〈B…C4H6（B=OCS,CO2,N2O）的顺序依次增大,相互作用距离按照B…C2H4〉B…C2H2〉B…C4H6（B=OCS,CO2,N2O）的顺序依次减小.采用电子密度拓扑分析理论方法,讨论了复合物中π…π作用的成键特性.电子密度拓扑分析表明复合物中形成了弱的分子间相互作用,且以静电作用为主;π电子密度分子图与全电子密度分子图中键径方向是一致的,说明π…π作用在本文所讨论的体系中起着很重要的作用.NBO分析表明净电荷迁移从电子给体C2H4,C2H2,C4H6到电子受体OCS,CO2,N2O,迁移数按照B…C2H4〈B…C2H2〈B…C4H6（B=OCS,CO2,N2O）的顺序依次增大,与相互作用能的顺序一致.     

柔性二元羧酸桥联双核镉(II)配合物的合成及晶体结构研究

晶体工程是根据分子堆积和分子间的相互作用,将超分子化学的原理、方法以及控制分子间作用的策略用于晶体,以设计出结构新颖、具有独特的物理性质和化学性质的新晶体[1].超分子间的非共价作用主要包括氢键 [2]、π-π堆积作用 [3]、阳离子-π作用和疏水缔合等,通过选择不同结构的配体,使其在配合物中产生多种非共价作用,是实现从分子到材料的一条重要途径.在配位超分子化合物的设计中,柔性配体相对于刚性配体使用较少[4].α,ω-二元脂肪羧酸根[-OOC-(CH)2n -COO-]具有C-C单键骨架和4个终端羧酸氧原子,单键展现出优良的挠性,而羧基有多种配位方式[5,6].如果再引入端基配体邻菲啰啉,邻菲啰啉的的刚性与二元脂肪羧酸根的柔性进行有机结合,可能形成结构新颖的超分子体系[7,8].本文以镉(II)为中心离子,分别以丁二酸和戊二酸作为第一配体,以邻菲啰啉作为端基配体,在常温下合成了配合物 [Cd2(phen)2(succ)(H2O)2](NO3-)2 ·3H2O (1)和[Cd2(phen)2(glut)2][Cd2(phen)2(Cl-)2]·2NO3-·14H2O(2)(succ =丁二酸,glut=戊二酸,phen=邻菲啰啉).X-射线单晶衍射测试表明,配合物1由丁二酸根单齿桥联两个Cd2+形成双核单元,进一步由氢键桥联成一维链状结构.配合物2含有两个独立结构,分别由戊二酸根和CI-桥联为双核单元,相邻的双核独立单元之间依靠氢键和π-π堆积作用构筑成二维网状结构.     

杯［4］芳烃衍生物一维超分子的晶体结构研究

杯芳烃是继冠醚、环糊精之后的第三代主体分子 ,在主客体化学、超分子化学中占有重要地位 [1～ 3] .据文献报道 ,在杯 [4]芳烃衍生物中存在各种各样的作用力 [4 ] ,如分子内氢键 [3,4 ]、分子间氢键 [5]、阳离子 -π作用 [6 ]、CH3-π作用 [7]和 π-π相互作用 [8,9]等 .本文报道了杯 [4]芳烃衍生物 5 ,1 1 ,1 7,2 3 -四叔丁基 -2 6,2 8-二 [2 -(甲氧基羰基 )苄氧基 ]-2 5 ,2 7-二羟基杯 [4]芳烃 (简称 L,结构式见 Scheme1 )的晶体结构 .研究中发现 ,分子中存在分子内氢键和分子间π-π相互作用 ,后者使化合物 L形成了一维锯齿形的超分子…     

1，2-环己二羧酸及芳香含氮配体的双核镉、锰配合物的合成和晶体结构

用水热法合成了两种新的配合物[Cd2(e,e-trans-chdc)2(bipy)2(H2O)2].H2O(1)和[Mn2(e,a-cis-chdc)2(phen)2(H2O)2].2H2O(2)(chdc=1,2-环己二羧酸,bipy=2,2′-联吡啶和phen=1,10-邻菲咯啉),用X-射线单晶衍射分析确定了配合物的晶体结构。配合物1和2均为双核分子。配合物1中,2个镉髤离子由2个1,2-环己二羧酸根以e,e-trans配位方式桥联,每个镉髤离子与1个2,2′-联吡啶的2个氮原子、2个1,2-环己二羧酸根的4个氧原子及1个水分子中的氧原子配位,形成了单帽变形三棱柱构型。配合物2中,2个锰髤离子由2个1,2-环己二羧酸根以e,a-cis配位方式桥联,每个锰髤离子与1个1,10-邻菲咯啉的2个氮原子、2个1,2-环己二羧酸根的3个氧原子及1个水分子中的氧原子配位,形成了畸变的八面体构型。配合物1和2分子之间都存在π-π堆积和O-H…O、C-H…O弱作用,进而将双核分子连接成三维超分子网络结构。配合物的荧光均来自于配体的荧光。     

pH控制下3，5-二羧基苯氧乙酸-Cd(Ⅱ)配合物的合成及晶体结构

以3,5-二羧基苯氧乙酸(H3L)为配体与醋酸镉在不同pH条件下获得了2个Cd(Ⅱ)配合物[Cd(H2L)2(H2O)4](1)、[Cd(HL)]n(2),通过红外、X-射线单晶衍射等检测手段对所合成的化合物进行了结构表征。测定结果表明,这2个配合物分别为配位分子和三维配位聚合物,其结构的形成与水热条件的pH值密切相关。该结果对以pH值控制配合物结构提供了研究基础。     

Synthesis,Spectroscopic Properties and Crystal Structure of 3,3＇-（Anthracene-9,10-diyl）bis（1-phenylpropan-1-one）

The compound 3,3'-(anthracene-9,10-diyl)bis(1-phenylpropan-1-one)(C32H26O2,Mr=442.55) has been synthesized by the reaction of 2,2'-(anthracene-9,10-diylbis(methy-lene))bis(1,3-diphenylpropane-1,3-dione) with CsCO3,and its structure was characterized by 1H NMR and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group P21/c with a=9.154(3),b=5.2777(16),c=24.897(7) nm,β=107.337(10)°,Z=2 and V=1.1482 nm3.X-ray analysis indicates that an intermolecular hydrogen bond C(8)-H(8A)…O(1),weak C-H···π between H(9A) and the centre of anthracene rings and weak π-π interactions between two anthracene ring planes are observed.     

Three New Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Constructed with 2-Mercaptonicotinic Acid and 1,2-Di(4-pyridyl)ethylene: Syntheses and Structure Analysis

Three new Zn(Ⅱ)/Cd(Ⅱ) coordination polymers based on 2-mercaptonicotinic acid (H2mna) with 1,2-di(4-pyridyl)ethylene (dpe) introduced as a bridging ligand have been synthesized via hydrothermal method and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. As reported in this paper, [Zn2(dpe)0.5(mna)2] (1) can be classified as a two-dimensional layer structure in which the 1D chain composed of Zn(Ⅱ) and mna ligands is bridged by dpe ligands, while the complex named [Zn4(dpe)4(mna)4] (2) is a tetra-nuclear cluster compound. These two compounds are further extended to three-dimensional structures by hydrogen bonds along with C-H…π and π…π interactions. Compound 3 with general formular [Cd2(dpe)0.5(mna)2]·H2O belongs to a three-dimensional porous structure in which the 2D metal layers formed by the coordination of Cd(Ⅱ) and mna ligands are connected with the bridging of dpe ligands.     

Synthesis, Crystal Structure and Property of a Series of Supramolecular Polymers Based on Novel 3,5-Dimethyl- 2,6-bis（3-（pyrid-2-yl）-1,2,4-triazolyl）pyridine Ligand

Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of MII (M = Mn, Co, Cd) in the presence of oxalic acid (H2ox) afford three novel supramolecular polymers (CPs), namely, {[M2(ox)(L)2][bdc][M2(Hox)2(OH)2(H2O)4].3H2O}n (M=Mn for 1, Co for 2, Cd for 3). Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2(ox)(L)2]2+ building block. The bdc2- ligand linked with the unprecedented [M2(Hox)2(OH)2(H2O)4] units through strong O-H…O hydrogen bonds forming a zigzag chain, which are further connected through π…π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.     

基于八配位铁的化合物(H2prz)[Fe(bpdc)2]·3H2O的合成、晶体结构及磁性质

通过水热方法,采用H2bpdc(H2bpdc=2,2′-bipyridine-6,6′-dicarboxylic acid)和prz(prz=piperazine)与FeSO4.7H2O反应,合成了一个质子传递化合物(H2prz)[Fe(bpdc)2].3H2O(1),并对其结构、热稳定性和磁性质进行了研究。结构分析结果表明该化合物的晶体属于单斜晶系,P21/n空间群。该化合物的分子由1个[Fe(bpdc)2]2-阴离子,1个H2prz2+阳离子和3个水分子组成。其中,Fe原子采取了少见的八配位畸变的十二面体构型。这些化合物分子通过分子间的氢键和π-π堆积作用形成了1个三维的超分子框架。     

A Tetranuclear Complex Assembled from N,N'-Bis(4-(3'-formyl-5'-methylsalicyclidene)-iminoethyl)-4-methyl-2,6-bimethyliminophenol

The reaction of 2,6-diformyl-4-methylphenol, ethylenediamine and Cu(Ⅱ) in the proportion of 3:2:2 yields a new tetranuclear copper(Ⅱ) complex, [Cu2L]2(ClO4)2·2H2O (H3L = N,N'-bis(4-(3'-formyl-5'-methylsalicyclidene)iminoethyl)-4-methyl-2,6-bimethyliminophenol). The complex has been characterized by ES-MS, IR and X-ray diffraction analysis, and its crystal crystallizes in the triclinic system, space group P1 with a = 10.8673(11), b = 12.0829(12), c = 14.4834(15) A, α = 111.946(2), β = 105.828(2), γ = 99.583(2)°, V = 1618.5(3) A3, Dc = 1.605 g/cm3, Z = 2, Mr = 1564.26, F(000) = 800.0,μ(MoKa) = 1.460/mm, S = 1.063, R = 0.0612 and wR = 0.1163 for 6245 observed reflections (I > 2σ(Ⅰ)). The complex is a dimer of dinuclear copper(Ⅱ) acylic enantiomorph subunit [Cu2L]CIO4·H2O, held together by π…π, weak coordination and hydrogen bonding interactions. In addition, the π…π interactions related to phenyl moieties as well as CH=N…π interactions were also found to stabilize the supramolecular architectures in the solid state.     

Syntheses, Crystal Structures and Properties of Two Supramolecules Assembled from Weak Interactions

Two complexes, [Cu2(Htdb)4(H2O)2] (1) and [Cd(bipy)2(Hmcmbc)2] (2) (H2tdb = 2,2-thiodibenzoic acid, H2mcmbc = m-(carboxyl-methyloxy)-benzenecarboxylic acid, bipy = 4,4'-bipyridine), have been prepared, and were characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. Structures indicate that complex 1 is a single molecule, and 2 is a one-dimensional chain. Their two-and three-dimensional frameworks are constructed through hydrogen bonding, π…π or C–H…π stacking, and such other weak interactions. The cyclic voltametric behavior of complex 1 and luminescence property of complex 2 were investigated. 1 belongs to the triclinic system, space group P with a = 7.8607(6), b = 11.7619(9), c = 15.3481(12) , α = 109.3670(10), β = 92.4420(10), γ = 92.0450(10)°, V = 1335.65(18) 3, Mr = 1256.26, Dc = 1.5619(2) g/cm3, F(000) = 642, μ = 1.029 mm–1, Z = 1, the final R = 0.0289 and wR = 0.0763 for 5199 observed reflections with I > 2σ(I). Complex 2 crystallizes in triclinic, space group P with a = 9.6378(10), b = 9.7508(10), c = 19.055(2) , α = 88.7020(10), β = 80.5260(10), γ = 69.2000(10)o, V = 1649.9(3) 3, Mr = 815.07, Dc = 1.641 g/cm3, μ = 0.732 mm-1, F(000) = 828, Z = 2, the final R = 0.0511 and wR = 0.1149 for 4729 observed reflections (I > 2σ(I)).     

Synthesis, Characterization and Crystal Structure Determination of a Thiocyanato Bridged One-dimensional Polymeric Complex of Cadmium(Ⅱ)

A new one-dimensional polymeric complex [Cd(SCN)2(H2O)]L (L = N,N?-bis(furan- 2-ylmethylene)hydrazine) has been synthesized and characterized by IR, UV spectra, TG-DTA technique and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, pace group P1 with a = 5.9268(8), b = 10.8678(15), c = 13.3671(19) , α = 109.295(2), β = 95.092(2), γ = 97.8580(10)°, V = 796.70(19) 3, Z = 2, C12H10CdN4O3S2, Mr = 434.76, μ = 1.648 mm–1, Dc = 1.812 g/cm3, F(000) = 428, R = 0.0308 and wR = 0.0769. The crystal structure reveals that the structure of [Cd(SCN)2(H2O)]n features di-μ-1,3-thiocyante bridges and 1D chains. The octahedrally coordinated Cd atom is surrounded by one oxygen atom from water molecule, three S atoms and two Natoms from five di-μ-1,3 thiocyanato bridges. The Cd atoms are connected by two di-μ-1,3 thiocyanato bridges with the Cd(1)…Cd(1A) separation of 4.239(1)  and Cd(1)…Cd(1B) of 5.852(1). In addition, the one-dimensional straight chain structure is further connected by multiform intermolecular N-H…O hydrogen bonds and π…π interactions to form a three-dimensional supramolecular structure.