二维网状结构双核配合物[Ca_2(C_(10)H_8N_2O_4)_2(DMSO)_2(H_2O)_4]·2DMSO的合成、热分解及晶体结构

以2-羰基丙酸水杨酰腙(C_(10)H_(10)N_2O_4)作为配体与碳酸钙在水中反应， 在DMF(N,N'-二甲基甲酰胺)和DMSO（二甲基亚砚）的混合溶剂中培养了单晶，其组 成为 [Ca_2(C_(10)H_8N_2O_4)_2(DMSO)_2(H_2O)_4]·2DMSO [C_(10)H_8N_2O~2- _4为2-羰基丙酸水杨酰腙负离子]。测字了单晶的结构，该单晶为黄色，属单斜晶 系，空间群为P2(1)/C，晶胞参数a=1.0634(3)nm, b=1.7035(5)nm, c=1.2183(3) nm, β=106.180(5)°, V=2.1192(10)nm!, Dc=1.412Mg·m~(-3), Z=2, F(000) =944, μ=0.534m~(-1)，GOF=0.867。所测单晶是以2-卷曲在丙酸水杨酰腙羧基上 的一个氧原子作为桥联的双核钙（II）配合物，两个Ca~(2+)均处于五角双锥的七 配位环境中，锥底为配体2-羰基丙酸水杨酰腙中的三个配位原子，以及另一2-羰基 丙酸水杨酰腙羧基上的桥联氧原子和一个水分子的配位氧原子，锥顶为一配位水和 一想位的DMSO分子，即溶剂DMSO也参也了配位，从晶胞结构看，晶体中除配位的 DMSO分子外，还有自由的DMSO溶剂分子，它们与配位水以氢键连接存在于晶格之中 ，在空间形成的二维网状结构。通过TG-DTG还测定了配合物的热稳定性。     

Synthesis and characterization of 2CuCN·DMSO and [CuII(DMSO)6][CuI 6(CN)8] 3-D framework compounds

Two novel complexes of CuCN were characterized by using a single-crystal X-ray diffraction technique and Raman spectroscopy. In the structure of 2CuCN·DMSO ligand molecule demonstrates unique bridging mode, being bound to two Cu^I centers via oxygen and sulfur atoms. The bridging role of both CN groups and DMSO molecules results in the formation of (CuCN·DMSO)_n framework. Along the channels of the network are running infinite zig-zag (CuCN)_n chains, which are bound to the framework by elongated Cu…(CN) bonds. A mixed-valence [Cu^II(DMSO)₆][Cu^I ₆(CN)₈] compound is composed of 3-D [Cu^I ₆(CN)₈]_n anionic framework and located in the channels of partially disordered [Cu^II(DMSO)₆]²⁺ cations.     

Dawson结构聚金属氧酸盐有机-无机复合物[{Y(DMSO)5(H2O)3}{Y(DMSO)8}][P2W18O62]·2DMSO·2H2O的合成、性质及晶体结构

以α-H6P2W18O62·nH2O,Y2O3,DMSO(二甲亚砜)为原料合成了Dawson结构聚金属氧酸盐有机-无机复合物犤狖Y(DMSO)5(H2O)3狚狖Y(DMSO)8狚犦犤P2W18O62犦·2DMSO·2H2O(1),化合物晶体属于单斜晶系,P21/c空间群,Mr=5803.06,a=1.7614(4)nm,b=3.1527(6)nm,c=2.1523(4)nm,β=90.40(3)°,V=11.963(4)nm3,Dc=3.222g·cm-3,μ=18.566mm-1,Z=4,F(000)=10464。由17342个可观测衍射点犤I≥2σ(I)犦用于精修所有的结构参数,得一致性因子R=0.0745,wR=0.1438。结构解析表明,化合物中两个Y3+离子的配位环境均为八配位的畸变双冠三棱柱构型。CV行为研究表明,标题化合物中阴离子(pH=5.5)存在五步还原过程,得电子数依次为1,1,1,1,2。化合物的IR光谱和X-射线衍射结果表明,固态条件下配阳离子与杂多阴离子之间存在较强的相互作用。     

Synthesis, crystal structure and photoluminescence of a novel tetra-nuclear calcium complex [{Ca(C_(15)H_8O_7S)-(H_2O)(DMSO)}_3{Ca(C_(15)H_8O_7S) (DMSO)_2}]·4DMSO

Calcium ions play a key role in many biochemi-cal and biological processes. They have various m- iportant structure and catalysis during metabolism ofcell and make cell membrane intensified by linkingadjacent carboxyl in lipoprotein. Furthermore, calciumcan play an adjustive and controlled role in the activa-tion of enzymes, nerve impulse transmission, musclecontraction, hormone release and blood congealmentduring the complex life[1— . Chrysin is one of flavones …     

二重穿插锰配合物Mn2(ADB)2(DMSO)4DMSO的溶剂热合成和结构研究

多孔配位聚合物的研究兴趣在于它们多样的结构特征和潜在的应用价值.配合物的性质和结构密切相关,特别是对于多孔配位聚合物,孔径越大,越有利于性质的发挥[1-6].     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O and [La(DMSO)4(H2O)3Co(CN)6]·H2O (DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O 1 and [La(DMSO)4(H2O)3Co(CN)6]·H2O 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1:C14H32CeFeN6O8S4, Mr = 736.67, monoclinic, space group P21/n, a = 14.952(1), b =13.7276(9), c = 15.392(1) (A), β = 108.288(1)°, V = 2999.6(4) (A)3, Z = 4, Dc= 1.631 g/cm3,μ =2.304 mm-1, F(000) = 1480, R = 0.0593 and wR = 0.1611; and those for 2: C14H32CoLaN6O8S4,Mr=738.54, monoclinic, space group P21/n, a = 14.945(3), b = 13.731(3), c = 15.300(3) (A), β=107.806(1)°, V= 2989.3(11) (A)3, Z = 4, Dc = 1.641 g/cm3,μ = 2.288 mm-1, F(000) = 1480, R =0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe(Ⅲ) or Co(Ⅲ) ion in a nearly regular octahedral environment.The [LnM(CN)6(DMSO)4(H2O)3]·H2O (Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2)species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.     

Crystallization of Two Cyanide-bridged Bimetallic Complexes [LN(DMSO)2(H2O)3Co(CN)6]·H2O (LN = Pr or Nd, DMSO = Dimethylsulfoxide)

1INTRODUCTIONRecently,therehasbeenconsiderableinterestinthelanthanide(III)hexacyanoferrates,theanalogoushexacyanocobaltateandhexacyanochromiumatecom-plexesbecauseoftheirpotentialapplicationsascata-lyticandsemi-conductivematerials.InitialstudiesofmetalhexacyanocobaltateswerecarriedoutbyJa-mesandWilland[1]whoreportedtheamountofhy-drationassociatedwithmicroscopiccrystalsofsever-allanthanidecomplexes.FurtherBonnetandParis[2]studiedtheLNCo(CN)6?nH2Oseries(n=4)byusinginfraredandX-raymethod…     

四核钙配位化合物[{Ca(C15H8O7S)(H2O)(DMSO)}3{Ca(C15H8O7S)(DMSO)2}]·4DMSO的合成和晶体结构及光致发光性能

采用浓硫酸对白杨素进行磺化,磺化产物与Ca(Ⅱ)络合,合成了结构新颖的四核钙配位标题化合物[{Ca(C15H8O7S)(H2O)(DMSO)}3{Ca(C15H8O7S)(DMSO)2}]·4DMSO.采用IR,1HNMR和X射线单晶衍射法对其进行了表征和晶体结构测定.标题化合物属于三斜晶系,空间群P,晶胞参数a=1.4725(6),b=1.6480(7),c=2.1006(8)nm,a=83.928(7)?b=85.938(7)?g=85.212(7)?V=5.041(3)nm3,Dc=1.476g/cm3,Z=2,m=0.568nm-1,F(000)=2324,R=0.0778,wR=0.1821.标题化合物为四核钙配位化合物,4个Ca(Ⅱ)被4个配体5-羟基氧负离子-7-羟基黄酮-6-磺酸根的羰基和羟基氧负离子桥联,形成近似正方形.Ca(Ⅱ)的配位数都是7,配位原子分别来自5-羟基氧负离子-7-羟基黄酮-6-磺酸根的羟基、羰基、磺酸根的氧原子,以及水和DMSO的氧原子.4个配体位于4个配位Ca(Ⅱ)组成的正方形平面两侧,同侧配体两两平行且它们之间存在p-p堆积作用,异侧配体之间近似垂直.同时,发现了标题化合物固体具有光致发光现象,在lex=410nm条件下可发出lem=520nm的绿色荧光,并对其发光机制进行了探讨.     

Synthesis and Crystal Structure of an Organic-inorganic Complex [Hg(DMSO)_2(H_2O)]_2 [GeW_(12)O_(40)]·DMSO·H_2O

Hybrid organic-inorganic compounds have attracted increasing interest in recent years due to the possibility of combination of different characteristics of the compounds to get unusual structures, properties, or applications1. Polyoxometalates (POMs) whic…     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)_4(H_2O)_3Fe(CN)_6]·H_2O and [La(DMSO)_4(H_2O)_3Co(CN)_6]·H_2O(DMSO = Dimethylsulfoxide)

1INTRODUCTION Recently,cyano-bridged lanthanide-transition me-tal complexes have been extensively investigateddue to their potential applications as precursors in the preparation of rare earth orthoferrites,fluores-cent and magnetic materials[1].Various complexes of this system have been obtained in order to ex-plore the relations between structures and pro-perties by using different ligands,such as DMF,4,4?-bipy,and so on,to fill the coordination sites of lanthanide ions[2～9].But up to…     

Ce(C_8H_8)_2和Ce(C_8H_8)_2~-的化学键性质

结合改进的重叠模型Xa-SW法和Ziegler过渡态法,通过将中心原子与配体的作用选成离子聚集、中心原子只有s和p轨道参与成键、中心原子只有d轨道参与成键、中心原子只有f轨道参与成键、中心原子的s、p、d和f轨道同时参与成键5种类型,从能量角度分析了Ce(C_8H_8)_2和Ce(C_8H_8)~-_2的化学键性质。     

溶剂工程调控钙钛矿薄膜中PbI2和PbI2(DMSO)的形成

钙钛矿太阳能电池以其高效、低成本的特点备受关注。到目前为止,钙钛矿太阳能电池的最高光电转换效率已经超过25%,显示出良好的应用前景。钙钛矿薄膜的结晶性能是决定器件性能的关键,因此,调控钙钛矿薄膜的生长过程至关重要。本工作中,我们发现通过简单调节前驱体溶剂,即调节二甲基亚砜：1, 4-丁内酯: N, N-二甲基甲酰胺(DMSO : GBL : DMF)的三种混合溶剂的比例,可实现钙钛矿薄膜中PbI₂和PbI₂(DMSO)含量的调节,从而调节电池的器件性能。此外,本工作系统研究了PbI₂和PbI₂(DMSO)的含量对器件性能的影响。结果表明,PbI₂(DMSO)的形成会导致300–425 nm波长范围内电池的外量子效率(EQE)降低,从而导致器件性能下降。相反,通过在前驱体溶液中添加额外的碘化亚甲基铵(MAI),可以抑制PbI₂和PbI₂(DMSO)的形成。     

Synthesis and structure of [Zn8(HPO4)8(H2PO4)8]•[(C2H8N)8]•4H2O

A chain-like zincophosphate [Zn₈(HPO₄)₈(H₂PO₄)₈]•[(C₂H₈N)₈]•4H₂O was obtained at room temperature from a ZnO/P₂O₅/dimethylamine/H₂O mixture. The crystal structure was determined by single crystal X-ray diffraction. The symmetry is monoclinic a=1.26450(7)nm, b=1.08477(5)nm, c=1.46311(4)nm, β=98.793(5)°, space group Cc. The structure consists of chains of zinc-corner-sharing Zn₂P₂O₄ four rings. The negative charge of the chains is compensated by the protonated dimethylamine. The characterization by ³¹P solid state nmr spectroscopy is also reported.     

双核有机锡配合物CH_2(SnPhBr_2)_2·2DMSO的合成及晶体结构

通过双 (苯基二溴化锡基 )甲烷CH2 (SnPhBr2 ) 2 与DMSO的配位反应或者双 (苯基二溴化锡基 )甲烷的双 (三唑 )甲烷配合物CH2 (SnPhBr2 ) 2 ·CH2 Tz2 与DMSO的配体取代反应 ,可以制得标题化合物。用X 射线衍射测定了该化合物的晶体结构。结果表明 ,该晶体属于单斜晶系 ,C2 /c空间群。分子式为C1 3H1 2 Br4Sn2 ·2 (C2 H6SO) ,Mr=881 .52 ,a =1 0 .0 4 0 (2 ) ,b =1 5.345(3) ,c =1 7.992 (4) ,β =1 0 5.99(3)°,V =2 665(1 ) 3,Z =4,Dc=2 .1 92Mg·m- 3,μ =7.9674mm- 1 ,1 31 4个可观测衍射点 (I≥ 3σ(I) ) ,最终结构偏离因子R =0 .0 4 2 ,Rw =0 .0 4 6。分子中 2个锡原子均为六配位的变形八面体构型 ,通过DMSO中的氧原子桥联 2个锡原子。     

A New Preparation of Mo2(CO)8(μ-PPh2)2 and W2(CO)8(μ-PPh2)2 by a Phosphorus-Carbon Bond Cleavage Reaction. Crystal Structure of a New Polymorph of Mo2(CO)8(μ-PPh2)2

A new synthesis of Mo₂(CO)₈(-PPh₂)₂ and W₂(CO)₈(-PPh₂)₂ by the reaction of molybdenum and tungsten hexacarbonyls with a tetraazamacrocyclic ligand containing —CH₂PPh₂ side chains, comprising cleavage of the phosphorus-methylene bond has been performed. The complexes have been investigated by magnetic and spectroscopic measurements and by single-crystal structure analyses. The structural characterization of a new polymorph of Mo₂(CO)₈(-PPh₂)₂ has been described.     

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex[La(DMSO)3(H2O)3Cr(CN)6]·H2O (DMSO = Dimethylsulfoxide) with One-dimensional Chain Molecular Structure

The title complex [La(DMSO)3(H2O)3Cr(CN)6](H2O was obtained by the reaction of LaCl3(7H2O, DMSO and K3[Cr(CN)6] in aqueous solution on a hot water bath. The crystal crystallizes in orthorhombic, space group P212121 with a = 9.827(3), b = 15.037(4), c = 17.633(5)A, C12H26CrLaN6O7S3, Mr = 653.48, Z = 4, V = 2605.7(13) A3, Dc = 1.666 g/m3, μ (MoKα) = 2.314 mm-1, F(000) = 1300, R = 0.0205 and wR = 0.0481 for 5038 observed reflections (I > 2σ(I)). La3+ ion is eight-coordinated by three DMSO molecules, three H2O molecules and two [Cr(CN)6]3- units. The structure of the title complex possesses a cyano-bridged onedimensional zigzag chain structure with alternating La(DMSO)3(H2O)3 and Cr(CN)6 moieties, which are linked by some hydrogen bonds to form a 3D network structure.     

Synthesis and Crystal Structure of Complex [Pb(qina)2(DMSO)]·H2O

A novel complex [Pb(qina)2(DMSO)]·H2O was synthesized, of which qina- is the quinaldic acid radical and DMSO the dimethyl sulfoxide. Elemental analysis, IR spectra, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. This complex belongs to monoclinic system, space group P121/n1, with a = 7.1553(17), b = 17.543(2), c = 17.306(2)(A),β = 91.671(4)°, C22H20N2O6PbS, Mr = 647.65, Z = 4, V= 2171.5(6)(A)3, Dc= 1.981g/cm3,μ = 7.908 mm-1, F(000) = 1248, -9≤h≤6, -23≤k≤ 19, -22≤l≤22, R= 0.0221 and wR =0.0488. Weak coordinate bond is formed between oxygen atom in DMSO and Pb(Ⅱ ). There are also weak interactions, such as π-π interaction, hydrogen bonds and so on, among the complex molecules.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ln(DMSO)2(H2O)(μ-CN)4Fe(CN)2](Ln= Ce and Eu, DMSO= Dimethylsulfoxide) with Layered Structure

Two new bimetallic cyano-bridged complexes [Ln(DMSO)2(H2O)(μ-CN)4Fe(CN)2] (Ln = Ce 1, Eu 2) have been prepared by the grinding reaction method and structurally characterized by X-ray single-crystal structure analysis. Crystallographic data for 1: C10H14CeFeN6O3S2, Mr = 526.36, monoclinic, P2/n, a = 7.852(4), b = 10.729(5), c = 11.181(5) (A), β = 96.992(8)°, V = 935.0(7) A3, Z = 2, Dc = 1.870 g/cm3, μ = 3.421 mm-1, F(000) = 512, R = 0.0363 and wR = 0.0971; and those for 2: C10H14EuFeN6O3S2, Mr = 538.20, monoclinic, P2/n, a = 7.739(5), b = 10.668(7), c = 11.008(7) A, β = 96.943(3)°, V = 902.1(11) A3, Z = 2, Dc = 1.981 g/cm3, μ= 4.499 mm-1, F(000) = 522, R = 0.0345 and wR = 0.0855. In each complex the lanthanide ion is seven-coordinated in a pentagonal bipyramidal arrangement, and the Fe(Ⅲ) ion is in a nearly regular octahedral environment. The title complexes can be described as two-dimensional (2-D) stair-like structures, which are further connected by hydrogen bonds to form three-dimensional (3-D) frameworks.     

Synthesis and structure of palladium complexes [Ph3PhCH2P]+[PdCl3(DMSO)]− · DMSO, [Ph4P]+[PdCl3(DMSO)]−, and [Ph4Sb(DMSO)]+[PdCl3(DMSO)]−

[Ph₃PhCH₂P]⁺[PdCl₃(DMSO)]^? · DMSO (I), [Ph₄P]⁺[PdCl₃(DMSO)]^? (II), and [Ph₄Sb(DMSO)]⁺[PdCl₃(DMSO)]^? (III) complexes have been synthesized via the reaction of palladium chloride with equimolar amounts of triphenylbenzylphosphonium chloride, tetraphenylphosphonium chloride, and tetraphenylstibonium chloride, respectively. According to X-ray diffraction data, the cations of complexes I (CPC = 104.90(8)°–111.61(9)°) and II (CPC = 105.12(10)°–111.46(10)°) have slightly distorted tetrahedral structures with P-C bond lengths of 1.786(2)–1.809(2) and 1.791(2)–1.799(2) Å, respectively. The antimony atom in the [Ph₄Sb(DMSO)]⁺ cation has a trigonal bipyramidal surrounding with the dimethyl sulfoxide (DMSO) oxygen atom in an axial position (Sb...O 2.567(2) Å). The palladium atoms in the square mononuclear anions of complexes I, II, and III are tetracoordinate, and Pd-Cl distances are 2.3101(5)–2.3104(5) Å, 2.2950(7)–2.2038(7) Å, and 2.2986(9)–2.3073(9) Å, respectively. The DMSO ligands are coordinated to the palladium atom through the sulfur atom (Pd-S, 2.2318(5) (I), 2.2383(6) (II), and 2.2410(9) Å (III)).     

Synthesis and Crystal Structure of Complex [Pb(qina)_2(DMSO)]·H_2O

A novel complex [Pb(qina)2(DMSO)]·H2O was synthesized,of which qina-is the quinaldic acid radical and DMSO the dimethyl sulfoxide. Elemental analysis,IR spectra,and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. This complex belongs to monoclinic system,space group P121/n1,with a=7.1553(17),b=17.543(2),c=17.306(2) ,β=91.671(4)°,C22H20N2O6PbS,Mr=647.65,Z=4,V=2171.5(6) 3,Dc=1.981 g/cm3,μ=7.908 mm-1,F(000)=1248,–9≤h≤6,–23≤k≤19,–22≤l≤22,R=0.0221 and wR= 0.0488. Weak coordinate bond is formed between oxygen atom in DMSO and Pb(Ⅱ ) . There are also weak interactions,such as π-π interaction,hydrogen bonds and so on,among the complex molecules.