含吩噻嗪锌、镉配合物的双光子激发荧光光谱

报道了两种新型配体(10-乙基-3-甲酰吩噻嗪缩肼基二硫代甲酸甲酯(HL¹)及10-乙基-3-甲酰吩噻嗪缩肼基二硫代甲酸苄酯(HL²))及其锌、镉配合物的双光子(激发)荧光性质. 入射激光强度与荧光强度关系的实验测定证明了发射光为双光子激发荧光. 比较了它们在800和400 nm激发波长下的双光子激发光谱和单光子激发光谱特性. 在800 nm的脉冲激光的激发下, 它们均显示出较强的峰值位于550 ~ 595 nm的双光子激发荧光. 用开孔Z-扫描装置测得它们在1064 nm处均具有较大的双光子吸收截面.     

Tb(Ⅲ)金属有机框架材料对Cu^2+和Fe^3+的荧光检测

通过溶剂热法成功合成出一种新型的配位化合物,命名为[Tb(L)(H2O)2]n(1)(H3L=4,4’,4"-((1,3,5-三嗪-2,4,6-三基)三(硫代二基))三苯甲酸)。单晶衍射分析结果显示配合物1属于单斜晶系,C2/c空间群。所有的配体桥连金属离子形成了一个具有一维孔道的三维框架。此外,荧光研究结果表明:Cu^2+和Fe^3+对配合物1具有明显的荧光淬灭响应。     

多价态钼多酸配合物[Mo(Ⅳ)Mo2(Ⅴ)O7(Phen)]的晶体结构及性质

用水热法合成了一种新的多价钼多酸配合物[Mo(Ⅳ)Mo2(Ⅴ)O7(Phen)],并用X射线衍射、元素分析、红外光谱、热重-差热、荧光光谱和磁化率等对其进行了表征.X射线衍射分析表明,配合物晶体属于单斜晶系,P2(1)/c空间群,由十二员环和八员环构成二维网状结构.配合物中强π-π堆积作用构筑成层状三维超分子,稳定了配...     

可光、化学降解聚苯乙烯的合成与性能研究

通过1,3-二碘甲基-2-硝基苯与双(2-甲基丙酸)三硫代碳酸酯的高效聚酯化反应合成了主链中含有邻硝基苄酯和三硫代碳酸酯基团的聚合物,以其作为大分子链转移剂,进行苯乙烯的可逆加成断裂链转移(RAFT)聚合,获得了多嵌段聚苯乙烯.大分子链转移剂和多嵌段聚苯乙烯的结构及分子量通过核磁氢谱(1H-NMR)和凝胶渗透色谱(GPC)进行了表征.考察了多嵌段聚苯乙烯溶液和固态的降解性能及热性能.实验结果表明,多嵌段聚苯乙烯不仅在紫外辐照条件下可发生光降解,而且也可通过胺解和水解反应进行降解.热重分析(TGA)和示差扫描量热(DSC)结果显示,邻硝基苄酯基团和三硫代碳酸酯基团的引入,对于多嵌段聚苯乙烯玻璃化转变温度和热稳定性并没有明显的影响.     

四硫富瓦烯衍生物的银(Ⅰ)配位聚合物的合成与表征

在室温下,以丙酮为溶剂,三氟甲基磺酸银与4,5-二甲硫基-1,3-二硫代环戊烯-2-硫酮(C5H6S5)反应得到一个二维配位聚合物[Ag(C5H6S5)].CF3SO3.(CH3)2CO(1).单晶采用惰性溶剂扩散法培养.X-ray单晶衍射分析表明,1属于正交晶系,P212121空间群,晶胞参数:a=0.825 7(5)nm,b=0.972 1(6)nm,c=2.143(1)nm,V=1.720(1)nm3.在1中一个银离子与不同配体的三个硫原子配位,同时一个配体的两个硫原子参与和银离子配位,形成二维阶梯结构,在二维聚合物分子内存在较强的S…S相互作用,聚合物室温电导率为3.95×10-7S.cm-1,属于半导体.经过碘掺杂后化合物的电导率达到6.80×10-7S.cm-1.     

一种新型单体引发转移终止剂合成精细结构功能化的聚苯乙烯

自从1982年Ｏｔｓｕ[1]等提出引发转移终止剂(Ｉｎｉｆｅｒｔｅｒ)以来,这类化合物得到了广泛的研究和发展.使用引发转移终止剂的聚合反应是实现“活性”聚合的一个重要方法.引发转移终止剂又分为热引发转移终止剂和光引发转移终止剂两种.热引发转移终止剂除了三苯甲基偶氮苯外[2],均是六取代乙烷类化合物[3～7];而光引发转移终止剂则一般是一些含二硫代氨基甲酰氧基基团的化合物,如Ｎ,Ｎ二乙基二硫代氨基甲酸苄酯(ＢＤＣ)、双(Ｎ,Ｎ二乙基二硫代氨基甲酸)对苯二甲酯(ＸＤＣ)、Ｎ乙基二硫代氨基甲酸苄酯(ＢＥＤＣ)、双(Ｎ乙基二硫代氨基甲酸…     

离子液热条件下金属有机骨架化合物的合成

以1-丁基-3-甲基咪唑氟硼酸盐为溶剂, 在离子液热条件下得到两个化合物Zn3(BDC)3(MIA)2(1) 和Zn(HBTZ)(MIA)(BPY)(2). X射线衍射分析表明, 两种化合物的晶体分别属于单斜晶系, C2/c空间群和正交晶系, Fdd2空间群. 化合物1为三维结构, 在除去端基的N-甲基咪唑后, 形成了大约0.9 nm×0.9 nm的一维菱形孔道. 化合物2中的链状次级结构单元则通过π键和氢键作用形成了超分子结构.     

3-羟基邻苯二甲酰亚胺全水溶性次氯酸荧光探针及其应用

利用二甲基硫代氨基甲酸酯对次氯酸(HOCl)的特异性和吡啶盐的水溶性,以4-羟基异苯并呋喃-1,3-二酮作为原料,设计合成了一种检测HOCl的全水溶性激发态分子内质子转移(ESIPT)荧光探针.由于二甲氨基硫代甲酸酯对羟基的保护,探针分子内的ESIPT作用被阻碍,自身无荧光;当加入HOCl时,HOCl氧化二甲氨基硫代甲...     

3,5-二氨基苯甲酸构筑的Zn(Ⅱ)、Cd(Ⅱ)两种配合物的合成及晶体结构(英文)

利用3,5-二氨基苯甲酸配体合成了2种新的配合物[Cd(diaba)(phen)2]NO3·H2O(1)和[Zn(diaba)(2,2′-bipy)2](2)(H2diaba=3,5-diaminobenzoic acid;phen=1,10-phenanthroline,2,2′-bipy=2,2′-bipyridine),并对其进行了元素分析、红外光谱和X射线单晶衍射测定。配合物1属于正交晶系,空间群为Fddd,a=1.425 81(7)nm,b=2.564 62(13)nm,c=3.092 47(17)nm。配合物2属于单斜晶系,空间群为C2/c,a=1.273 62 nm,b=1.592 78 nm,c=1.519 35 nm,β=107.334°。配合物1和2都为单核晶体。配合物1的结构单元由1个CdII、1个3,5-二氨基苯甲酸和2个phen构成。配合物2的结构单元由1个ZnII、1个3,5-二氨基苯甲酸和2个2,2′-bipy构成。两种配合物再通过氢键或π-π堆积形成三维超分子网络。研究了配合物的热稳定性和荧光性质。     

含S,N的配体及其铜(Ⅱ)配合物的合成与晶体结构

肼基二硫代甲酸苄酯与丙酮在冰醋酸的催化下合成了丙酮-肼基二硫代甲酸苄酯配体(HL);HL与氯化铜反应合成了配合物CuL2,其结构经IR,元素分析及X-射线单晶衍射表征.HL属单斜晶系,P21/c空间群,晶胞参数:a=11.952 6(8)(A), b=6.155 8(4)(A), c=16.959 3(12)(A), V=1 243.68(15)(A)3, Z=4, Dc=1.273 g·cm-3, R1=0.032 2, wR2=0.084 1;CuL2属单斜晶系,P21/c空间群,晶胞参数:a=7.440(13)(A), b=18.286(3)(A), c=19.294(3)(A), V=2 607.1(8)(A)3, Z=4, Dc=1.376 g·cm-3, R1=0.044 5, wR2=0.081 7. CuL2的晶体是由孤立的分子所组成,四配位的铜离子呈畸变的四面体构型.CuL2通过分子间弱的C-H┈S氢键形成一维链状结构.     

2(S),3(R)-二羟基甲基-N-环己基氮杂环丙烷的合成及其晶体结构

合成了5-(R)-(1R,2S,5R)-孟氧基丁内酯并[3,4-b]-2(S)-6(R)-1-N-环己基氮杂环丙烷(3)和2(S),3(R)-二羟基甲基-N-环己基氮杂环丙烷(4),其晶体结构经四圆单晶X-射线衍射仪测定。3属三斜晶系,p1空间群,a=5.438(11),b=8.117(2),c=11.572(2),Mr=335.47,α=96.84(3)°,β=94.48(3)°,γ=101.86(3)°,V=493.5(2)3,Z=1,Dc=1.129g·cm-3,μ=0.074mm-1,F(000)=184,R=0.086,wR=0.2344,1527个独立衍射点。4属单斜晶系,P2(1)/n空间群,a=8.0915(15),b=7.2055(13),c=18.6120(3),Mr=185.26,β=102.086(2)°,V=1061.1(3)3,Z=4,Dc=1.160g·cm-3,μ=0.080mm-1,F(000)=408,R=0.0466,wR=0.1224,1485个独立衍射点。4分子中存在两种分子间氢键。     

Synthesis and Crystal Structure of 3,6-Bis(4,4,4-trifluorobutane-1,3-dione)-9-n-butylcarbazole

A novel bis(β-diketonate) derivate, 3,6-bis(4,4,4-trifluorobutane-1,3-dione)-9-n- butylcarbazole 1, was synthesized and structurally characterized by single-crystal X-ray diffrac- tion. The crystal belongs to the monoclinic system, space group P21/c with a = 10.961(6), b = 22.942(13), c = 9.408(6) , α = 90, β = 109.663(9), γ = 90o, V = 2228(2) 3, Z = 4, Dc = 1.489 g/cm3, C24H19F6NO4, Mr = 499.40, F(000) = 1024 and μ = 0.134 mm–1. The structure was refined to the final R = 0.0699 and wR = 0.1627 for 3744 independent reflections (Rint = 0.1288) and 1349 observed reflections (I > 2σ(I)). Compound 1 consists of carbazole unit and two terminal diketonate groups, in which carbazole and its two adjacent diketonate rings are almost coplanar. Moreover, compound 1 was characterized with IR, elemental analysis, 1H NMR, MS, electronic absorption, and single-photon fluorescence.     

Syntheses, Crystal Structures and Fluorescent Properties of Two New Imidazolidino Schiff Base Compounds

Two new imidazolidino Schiff base compounds, （E）-N-（（quinoxalin-2-yl）methylene）- 2-（2-（quinoxalin-3-yl）imidazolidin-1-yl）ethanamine 1 and 2-（1-（2-（2-（quinoxalin-3-yl）imidazolidin- 1-yl）ethyl）imidazolidin-2-yl）quinoxaline 2, have been synthesized and characterized by elemental analysis, ^1H NMR, IR, MS and single-crystal X-ray diffraction. Crystallographic data for 1： C22H21N7, Mr = 383.46, monoclinic, space group P21, a = 7.0036（14）, b = 6.9151（14）, c = 19.701（4）A, β = 96.57（3）°, Z = 2, V = 947.9（3）A^3, Dc = 1.344 g/cm^3, F（000） = 404, μ = 0.085 mm^-1, Flack parameter = 0（2）, R = 0.0464 and wR = 0.1055; and those for 2： C24H26N8, Mr = 426.53, triclinic, space group PI, a = 9.6680（19）, b = 10.334（2）, c = 11.389（2）A, α= 104.12（3）, β = 102.95（3）, γ= 100.48（3）°, Z= 2, V = 1041.2（4）A3, Dc= 1.361 g/cm^3, F（000） = 452, μ = 0.086 mm^-1, R = 0.0373 and wR = 0.1155. For the two compounds, the five-membered imidazolidine rings all adopt envelope conformation. Moreover, the title compounds show one-dimensional layered and three-dimensional supramolecular chainlike structures, respectively. Fluorescent properties of the two compounds have been investigated in the solid state at room temperature. Compound 1 exhibits strong fluorescence and thus may serve as excellent candidates of green fluorescent materials.     

Syntheses, Structures, and Some Properties of Three Vanadium Selenites

Three novel vanadium selenites with the formulae [（VO2）（1,10-phenanthtoline）（SeO3H）]2 1, [（VO2）（2,2′-bipyridine）]2（SeO3） 2 and [（VO）（H2O）（SeO3）2]2（HaEDD） 3 （EDD = N1,N1′-（ethane-1,2-diyl）diethane-1,2-diamine） were hydrothermally synthesized, and characterized with elemental analysis, FT-IR spectrum, Raman spectrum, TG-DTA analysis, EPR spectra, and single-crystal X-ray diffraction analysis. Compound I belongs to the triclinic system, space group P1^- with a = 7.7527（5）, b = 9.5345（10）, c = 9.8192（8） A^°, α = 92.712（3）, β = 105.540（3）, γ = 108.154（4）°, V = 657.66（1） A^°^3, Mr = 782.22, Z = 1, F（000） = 384,μ（MoKa） = 3.544 mm^-1, R = 0.0432 and wR = 0.1142; Compound 2 is of orthorhombic system, space group F212121 with a = 7.6574（15）, b = 14.916（3）, c = 19.085（4） A, V = 2179.8（8） Aa, Mr = 605.21, Z = 4, F（000） = 1200, μ（MoKa） = 2.579 mm^-1, R = 0.0338 and wR = 0.0658; Compound 3 belongs to the triclinic system, space group P1^- with a = 9.247（2）, b = 9.659（2）, c = 7.2651（19） A^°, α = 98.171（7）, β = 103.709（5）, γ = 114.712（13）°, V = 550.9（2） A^°^3, Mr = 828.03, Z = 1, F（000） = 400, μ（MoKa） = 7.537 mm^-1, R = 0.0641 and wR = 0.2118. Compound 1 is constructed from alternating corner-shared [VO4N2] octahedra and SeO3H units, forming a dimeric vanadium unit. These assemblies are further linked into an infinite chain via hydrogen bonds along the a axis. In the structure of 2, two distinct V centers form centrosymmetric [V2O6N4] clusters through edge-sharing, and the SeO3 unit serves as a capping unit to fix the oxovanadate cluster. In the structure of 3, each [VO6] octahedron shares four oxygen atoms with adjacent Se atoms, while every SeO3 unit shares two oxygen atoms with neighboring V atoms. This connectivity of alternating VO6 and SeO3 units results in a joint-like chain. Based on the TGA analysis, these three compounds are thermally stable under 200℃ .     

Synthesis and Crystal Structure of a Heterometallic Chain Coordination Polymer:{[Ni_2Mn_2L_2(CH_3CH_2OH)(H_2O)]·CH_3OH·2H_2O}_n

A chain-like coordination polymer with the chemical formula of {[Ni2Mn2L2(CH3CH2OH)-(H2O)]·CH3OH·2H2O}n has been synthesized by the assembly reaction of K2NiL·H2O and Mn(OAC)2·4H2O with a 1:1 mole ratio in methanol,where OAC-=CH3COO-and H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl}imino)methyl]benzoic acid.The crystal structure was determined by single-crystal X-ray diffraction analysis.It belongs to the triclinic system,space group P1,with a=9.9464(8),b=13.4718(11),c=14.3877(12),α=87.1930(10),β=85.4280(10),γ=74.6470(10)°,V=1852.4(3)3,Z=2,Dc=1.807g/cm3,Mr=1008.03,λ(MoKα)=0.71073,μ(MoKα)=1.794 mm-1,F(000)=1032,R=0.0527 and wR=0.1284(Ⅰ2σ(Ⅰ)).The compound exhibits a chain-like structure formed by dissymmetrical tetranuclear units.     

N-(1-甲基-4,5-二溴-2-三氯乙酰基)甘氨酸甲酯的合成与晶体结构

合成了N-(1-甲基-4,5-二溴-2-三氯乙酰基)甘氨酸甲酯(C9H10Br2N2O3, Mr=354.01),X-射线单晶衍射确定其属于正交晶系,P2(1)2(1)2(1) 空间群, a=6.4237(18)(A), b=13.445(4)(A), c=14.054(4)(A), α=β=γ= 90°, V=1213.8(6)(A)3, Z=4, Dc=1.937 Mg·m3, μ=6.672 mm-1, F(000)=688.有2257个可观察点[I>2σ(I)],最终R1=0.0275, wR2=0.0682.X-射线晶体结构的分析表明该化合物含羰基、酰胺基、酯基与溴原子,并且通过N(2)H与O(2)分子间氢键连成一维链状结构.     

由吡嗪二甲酸及双咪唑基配体构筑的锌配位聚合物的合成、晶体结构及荧光性质

通过水热法合成了一个新的金属-有机配位聚合物[Zn(pzdc)(bix)0.5(H2O)]n(1)(H2pzdc=吡嗪-2,3-二甲酸,bix=1,4-双(咪唑基1-甲基)-苯)。并对其进行了元素分析、红外光谱、紫外光谱和X-射线单晶衍射测定。该配合物属于三斜晶系,P1空间群。晶体学数据:a=0.737 27(8),b=1.004 45(12),c=1.079 10(13)nm,α=113.771(2),β=102.005(2),γ=93.586(2)°,V=0.705 71(14)nm3,C13H11N4O5Zn,Mr=368.63,Dc=1.735 g.cm-3,μ(Mo Kα)=1.773 mm-1,F(000)=374,Z=2,最终R=0.027 6,wR=0.067 7用于2 460个可观测点。在晶体结构中,锌离子通过吡嗪-2,3-二甲酸和1,4-双(咪唑基1-甲基)-苯)配体桥联成二维层状结构。而且该配合物通过氢键和π-π堆积作用扩展成三维超分子网状结构。此外还研究了它的荧光性质。     

Synthesis, Crystal Structure and Luminescence of a Novel One-dimensional Silver(I)Sulfonate Complex with Pyrazine Ligand

The title complex,[Ag2(L1)2(Pyr)·2.5H20]1(L1=6-amino-1-naphthalenesulfonate anion,Pyr=pyrazine),has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1,with a=7.339(5),b=13.105(5),c=14.097(5)(A),α=84.377(5),β=76.921(5),γ=79.628(5)°,V= 1296.7(11)(A°)3,C48H50Ag4N8O17S4,Mr =1570.68,Z=1,Dc=2.011 g/cm3,/μ= 1.732 mm-1,F(000)=782,S=1.148,the final R=0.0436 and wR=0.1181 for 4130 observer reflections(I＞20(I)).Compound 1 shows a rare one- dimensional(1D)double chain, and the chains are further connected through secondary bonding,hydrogen bonds, and π-π interactions to generate a three-dimensional(3D)supramolecular structure.The luminescent property of 1 was also studied in the solid state at room temperture.     

Preparation and Crystal Structure of 15α-Hydroxyl-oleanolic Acid

The compound 15α-hydroxyl-oleanolic acid was biotransformed from oleanolic acid with Colletotrichum lini AS3.4486,and its structure was characterized by 1H NMR,13C NMR,HR-ESI-MS and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group R3 with a=34.255(5),b=34.255(5),c=6.8671(14),β=90°,Z=9,V=6978(2)3,Mr=490.70,Dc=1.051 mg/m3,μ=0.069 mm-1,F(000)=2430,R=0.0375 and wR=0.0808.The title compound is stacked into a three-dimensional network through hydrogen bonds.     

Synthesis and Crystal Structure of Novel Sn-O Clusters Generated from nBu2SnO and Esters

A facile and credible strategy was demonstrated to synthesize two new Sn-O clusters 1 and 2 by the reactions of nBu2SnO with esters directly under mild conditions.Cluster 1 crystallizes in the triclinic system,space group P1 with a = 13.054(3),b = 13.137(3),c = 15.077(3) ,α = 80.009(9),β = 77.187(10),γ = 76.075(11)°,Z = 2,V = 2427.3(9) 3,Dc = 1.565 g/cm3,μ(MoKα) = 2.076 mm-1,F(000) = 1152,the final R = 0.0335 and wR = 0.0664 for 9416 observed reflections(I 2σ(I)).Cluster 2 belongs to the monoclinic system,space group P21/c with a = 13.673(3),b = 13.342(3),c = 16.296(4) ,β = 104.385(5)o,Z = 4,V = 2879.7(10) 3,Dc = 1.347 g/cm3,μ(MoKα) = 1.751 mm-1,F(000) = 1176,the final R = 0.0306 and wR = 0.0706 for 6390 observed reflections(I 2σ(I)).The crystal structures of the clusters consist of cen-trosymmetric [RCOOSnnBu2OSnnBu2OH)]2 molecules with an almost planar Sn4O4 framework.Each pair of exo-and endo-cyclic tin atoms was linked by one bridge-OH only.In addition,a novel structure of nBu2SnO different from the previous reports was proposed on the basis of 1H-NMR,TG analysis and X-ray diffraction.