锡(Ⅳ)N,N-二取代荒酸配合物Ph3SnS2CN(CH3)C6H5、 Ph3SnS2CN(C4H8NH)和SnCl2(S2CNEt2)2的合成、表征及晶体结构

Three tin (Ⅳ) complexes with N,N-dialkyl dithiocarbamates Ph₃SnS₂CN(CH₃)C₆H₅ (1),Ph₃SnS₂CN(C₄H₈NH) (2) and Sn(Cl)₂(S₂CNEt₂)₂ (3) have been synthesized. The crystal structures have been determined by X-ray sin- gle crystal diffraction. A crystal of the complex 1 is triclinic with space group P1, a=0.9485(3)nm, b=1.0491(3)nm, c=1.3631(4)nm, α=70.996(4)°, β=72.294(4)°, γ=79.609(4)°, Z=2, V=1.2168(6)nm³, D_c=1.453g·cm^-3, μ=1.234mm^-1, R=0.0442, wR=0.0858. A crystal of the complex 2 is monoclinic with space group P2(1)/c, a=1.2214(2)nm, b=1.1651(2)nm, c=1.5769(3)nm,β=99.039(2)°, Z=2, V=2.2162(7)nm³, D_c=1.532g·cm^-3, μ=1.352mm^-1, R=0.0267, wR=0.0591. A crystal of the complex 3 is triclinic with space group P1, a=0.7179(2)nm, b=0.9256(3)nm, c=1.5327(5)nm,α=93.857(4)°,β=98.992(4)°, γ=109.481(4)°, Z=2, V=0.9405(5)nm³, D_c=1.717g·cm^-3, μ=2.076mm^-1, R=0.0263, wR=0.0662. In the complexes 1 and 2 the tin atoms rendered five-coordination in a distorted tigonal bipyramidal structure and in the complex 3 the tin atom rendered six-coordination in a distorted octahedron structure. CCDC: 1, 179918; 2, 180024; 3, 180004.     

三嗪吡唑类铜配合物的合成、结构及光谱研究

以三齿吡唑-三嗪(类蝎型)化合物2,4-二(3,5-二甲基吡唑)-6-二乙基胺-1,3,5-三嗪(bpz^*eaT)为配体,在无水乙醇和甲醇溶剂中,合成了2个配合物Cu₂(mpz^*eaT-EtO)₂(N₃)₂Cl₂(1)和Cu₂(mpz^*eaT-MeO)₂(N₃)₄(2)(mpz^*eaT-EtO：2-(3,5-二甲基吡唑)-4-乙醇-6-二乙基胺-1,3,5-三嗪;mpz^*eaT-MeO：2-(3,5-二甲基吡唑)-4-甲醇-6-二乙基胺-1,3,5-三嗪)。通过元素分析、红外光谱、紫外光谱、热重分析以及X-ray单晶衍射方法对配合物进行了表征,并分析了其光谱及结构特征。晶体结构表明,配合物1属于三斜晶系,P1空间群,a=0.9949(2)nm,b=1.0216(2)nm,c=1.1480(2)nm,α=115.11(3)°,β=106.99(3)°,γ=100.39(3)°,V=0.9460(3)nm³,Z=1;配合物2属于单斜晶系,P2₁/c空间群,a=1.5464(5)nm,b=1.4008(5)nm,c=0.8905(3)nm,β=103.227(5)°,V=1.8779(10)nm³,Z=2。配合物1和2中的中心铜原子均为五配位,形成扭曲的四角锥构型。     

K2CdSnS4的溶剂热合成与晶体结构

利用溶剂热法合成了层状硫代锡(Ⅲ)酸镉(Ⅱ)化合物K₂CdSnS₄。单晶X-射线衍射分析结果表明,化合物属单斜晶系,C2/c空间群,a=1.1021(5)nm,b=1.1030(5)nm,c=1.5151(10)nm,α=90°,β=100.416(12)°,γ=90°,V=1.8114(17)nm³,Z=8,D_c=3.209g·cm^-3,M_r=437.60,μ=6.853mm^-1,F(000)=1600,λ=0.071073nm,R=0.1042,wR=0.2008。该化合物由类金刚烷[Cd₂Sn₂S₁₀]^8-结构单元互相连接形成层状结构。紫外-可见漫反射光谱研究表明,化合物为半导体,带隙为2.2eV。     

氰根桥联CrⅢ-CrⅡ一维配合物{[Cu(cyclam)] [Cr(bpb)(CN)2]2·2H2O}n的合成、结构与磁性

基于构筑单元K[Cr(bpb)(CN)₂] 和[Cu(cyclam)] (ClO₄)合成了一个氰根桥联的Cr^Ⅲ-Cr^Ⅱ一维化合物{[Cu(cyclam)] [Cr(bpb)(CN)₂]₂·2H₂O}_n[cyclam=1,4,8,11-四氮杂环十四烷;bpb^2-=1,2-二(2-吡啶甲酰胺基)苯] (1),并通过X-衍射单晶分析表征其结构特征.结果表明:化合物1是由氰根桥联的2种不同金属组成的聚合物,其结构属于三斜晶系, P1空间群,a=0.9667 3(19) nm,b=1.345 1(3) nm,c=1.382 0(3) nm,α=77.12(3)°,β=76.93(3)°,γ=82.02(3)°,V=1.699 1(6) nm³,Z=2,D_c=1.567 g·cm^-3,μ=1.086 mm^-1,F(000)=828,R₁=0.0413,wR₂=0.1200.磁性研究表明:配合物1中的Cr^Ⅲ离子和Cr^Ⅱ离子之间存在弱的铁磁耦合作用.     

四(邻氟苄基)锡及一维链状三苄基锡二茂铁甲酸酯的合成、结构及性质

合成了四(邻氟苄基)锡(1)和一维链状三苄基锡二茂铁甲酸酯(2),经X射线衍射方法测定了化合物的晶体结构。化合物1属四方晶系,空间群I4₁/a,晶体学参数a=1.96794(16)nm,b=1.96794(16)nm,c=0.59316(5)nm,V=2.2972(3)nm³,Z=4,D_c=1.605g·cm^-3,μ(MoKα)=11.58cm^-1,F(000)=1112,R₁=0.0208,wR₂=0.0576。化合物2属单斜晶系,空间群为P2₁/n,晶体学参数:a=1.59354(12)nm,b=1.00723(8)nm,c=1.70026(13)nm,β=91.001(10)°,V=2.7286(4)nm³,Z=4,D_c=1.521g·cm^-3,μ(MoKα)=14.74cm^-1,F(000)=1256,R₁=0.0384,wR₂=0.0952。晶体的中心锡原子分别呈四配位畸变四面体构型和五配位畸变三角双锥构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了配合物的热稳定性和体外抗癌活性。     

芳酰腙铜(Ⅱ)和锌(Ⅱ)配合物的合成、晶体结构及抗菌活性

合成了一对结构类似的双核铜和锌配合物,Cu₂(L¹)₂(1)和[Zn₂(L²)₂(CH₃OH)₂] (2),其中L¹和L²分别是2-溴-N''-(2-羟基-5-甲基苯亚甲基)苯甲酰肼(H₂L¹)和2-氯-N''-(2-羟基-5-甲基苯亚甲基)苯甲酰肼(H₂L²)的二价阴离子,通过元素分析、红外光谱以及单晶X射线衍射表征了它们的结构。配合物1以三斜晶系P1空间群结晶,其晶体学参数:a=0.91411(6) nm,b=1.18004(7) nm,c=1.35936(9) nm,α=101.928(2)°,β=91.399(2)°,γ=107.873(2)°,V=1.3593(2) nm³,Z=2,R₁=0.0540,wR₂=0.1189,GOF=0.970。配合物2以单斜晶系P2₁/c空间群结晶,其晶体学参数:a=1.21697(9) nm,b=1.21496(9) nm,c=1.21283(9) nm,β=110.939(1)°,V=1.6748(2) nm³,Z=2,R₁=0.0341,wR₂=0.0689,GOF=1.024。X射线分析表明2个化合物都是中心对称的双核配合物,其中配合物1中的Cu原子是平面正方形配位构型,配合物2中的Zn原子是四方锥配位构型。还通过MTT法研究了这两个配合物的抗细菌(大肠杆菌,金黄色葡萄球菌,枯草芽孢杆菌和铜绿色假单胞菌)和抗真菌(白假丝酵母菌和黑曲霉菌)活性。     

基于2-(4-甲基苯甲酰基)苯甲酸及2，2'-联吡啶的双核铜(Ⅱ)配合物的晶体结构、荧光和磁性

以2-(4-甲基苯甲酰基)苯甲酸(HL)及2,2'-联吡啶(2,2'-bipy)为配体合成了一个双核铜(Ⅱ)配合物[Cu₂(L)₄(2,2'-bipy)₂]·H₂O(1),并对其进行了晶体结构测定。测定结果表明,该配合物晶体属于三斜晶系,空间群为P1,晶胞参数：a=1.01257(15)nm,b=1.3125(2)nm,c=1.3170(2)nm,α=82.985(2)°,β=76.437(2)°,γ=88.290(2)°,V=1.6887(4)nm³,D_c=1.391g·cm^-3,Z=2,F(000)=732,GooF=1.027,最终偏离因子R₁=0.0375,wR₂=0.0914。在配合物分子中相邻的2个铜(Ⅱ)离子通过2个2-(4-甲基苯甲酰基)苯甲酸根桥联配位连接起来,其端位各与1个2-(4-甲基苯甲酰基)苯甲酸根和1个2,2'-联吡啶分子配位,整个分子形成了双核结构。测定了标题配合物的荧光和磁性,结果表明：当激发波长为608nm时,配合物在472和476nm处有2个较强的荧光发射峰;在2~100K,配合物具有顺磁性。     

两个具stp三维拓扑构型的稀土配位聚合物{[Ln2（pda）3（H2O）2]2H2O}n（Ln=Nd/La）

本文利用水热合成方法,将稀土氧化物与邻苯二乙酸（H₂pda）反应得到了2个新颖的稀土配位聚合物{[Ln₂（pda）₃（H₂O）₂]·2H₂O}_n（Ln=Nd（1）,La（2））。测定了它们的晶体结构,并进行了X-射线单晶衍射、红外光谱、荧光光谱和热重分析等性质的表征。晶体结构测定表明这2个化合物为异质同晶化合物。属单斜晶系,C2/c空间群。晶体学参数分别为配合物1：a=2.62906（18）nm,b=1.61172（11）nm,c=0.78327（5）nm,β=93.173（5）°,V=3.3139（4）nm³,Z=4,F（000）=1840,μ=3.173mm^-1,D_c=1.878g·cm^-3,R₁=0.0226,wR₂=0.0609;配合物2：a=2.6271（14）nm,b=1.6149（8）nm,c=0.7966（4）nm,β=92.850（9）,V=3.375（3）nm³,Z=4,F（000）=1816,μ=2.570mm^-1,D_c=1.823g·cm^-3,R₁=0.0466,wR₂=0.1416。化合物中邻苯二乙酸配体连接相邻的稀土金属离子,形成复杂的具有stp拓朴构型的三维网络结构。     

以三唑农药为配体的两个铜配合物的合成、晶体结构与抑菌活性

由三唑农药烯效唑和多效唑合成了2个铜配合物[CuL₄¹Cl₂](1)和[CuL₄²Cl₂·4H₂O](2)(L¹=uniconazole,L²=paclobutrazol)。通过元素分析、红外光谱和X-ray单晶衍射对其结构进行了表征。结构分析表明,1属三斜晶系,P1空间群,晶胞参数为a=0.8956(3)nm,b=1.3267(4)nm,c=1.4918(4)nm,α=94.828(3)°,β=97.774(3)°,γ=105.280(3)°,V=1.6808(9)nm³。2属三斜晶系,P1空间群,晶胞参数为a=1.02189(19)nm,b=1.329(3)nm,c=1.3664(3)nm,α=81.564(2)°,β=79.508(2)°,γ=79.185(2)°,V=1.7853(7)nm³。在2个配合物中,六配位的铜离子都采取扭曲的八面体配位构型,分别来自三唑配体的4个氮原子和2个氯原子配位。1和2都由分子间氢键连接成一维链结构。与相应的配体相比,1和2的抑菌活性明显增强。     

DBBD及其Cu(I)配位聚合物[CuI(DBBD)2]n的合成

In this article we report the synthesis of (R,S)-4,4′-biquinoline-6,6′-dimethyl-3,3′-dicarboxylate (DBBD) (1) and the formation of copper(I) coordination polymer [CuI(DBBD)₂]_n (2) by inducing a bidentate organic ligand (DBBD). The crystal 1 belongs to monoclinic system with space group P2₁, and a=0.881 30(19) nm, b=1.966 0(6) nm, c=1.478 1(4) nm, β=119.429(12)°, V=2.230 5(10) nm³, D_c=1.276 g·cm^-3. The crystal 2 belongs to orthogonal system with space group Fmm2, and a=2.044 41(17) nm, b=1.543 06(13) nm, c=1.652 45(13) nm, V=5.212 9(7) nm³, D_c=1.669 g·cm^-3, Z=8. CCDC: 292931, 1; 292934, 2.     

Solvent extraction separation of In/III/-Tl/III/ and Hg/II/-Cd/II/-Co/II/ with sulphoxides

Solvent extraction studies have been made on some metals: In/III/-Tl/III/ and Hg/II/-Cd/II/-Co/II/, from ammonium thiocyanate solutions by dialkyl sulphoxides. Separation of these metals from one another can be achieved by suitable choice of the extracted conditions. The nature of the extractable metal species has been elucidated.     

Synthesis of chlorobis/β-diketonato/oxotechnetium/V/ and tris/β-diketonato/technetium/III/ complexes

Chlorobis/-diketonato/ oxotechnetium/V/ complexes [TcOCl/-dik/₂, -diketone=acetylacetone, benzoylacetone and dibenzoylmethane] were newly synthesized using macroamount of⁹⁹Tc. These complexes were further separated into geometrical isomers. Furthermore, an improvement of the yields for the syntheses of tris/-dike-tonato/technetium/III/ complexes [Tc/-dik/₃, -diketone=acetylacetone, benzoylacetone and 2-thenoyltrifluoroacetone] was examined using Tc/III/-thiourea complexes as a starting material.     

An investigation of the promotional effect of propylene or propane traces on the activity of sulfatedPt/g-Al2O3andPt-Sn/g-Al2O3inCH4combustion

Summary A strong promoting effect of the presence of C₃H₈or C₃H₆was determined for the combustion of CH₄in excess oxygen, over pre-sulfated 1%Pt/g-Al₂O₃and pre-sulfated 1%Pt-2%Sn/g-Al₂O₃catalysts.</o:p>     

LixZryOz三元化合物的制备及表征

采用高温固相法制备了4种高纯度晶相组成的LixZryOz三元化合物,研究了焙烧温度、时间、反应物的种类和初始反应物物质的量比对产物组成的影响,进一步用XRD、SEM及BET分析方法对产物的晶相结构、表面形貌及比表面积进行了表征.实验结果表明,Li2CO3与ZrO2在适当条件下可以合成得到单斜相Li3ZrO3;以LiOH替代Li2CO3,在适当条件下可以分别合成得到四方相Li2ZrO3和三斜/单斜相Li6Zr2O7;进一步以Zr(NO3)4·5H2O代替Zr02,可将单斜相Li6Zr2O7的制备时间由96 h缩短至24 h.SEM照片显示产物硬团聚明显,粒径分布在1～10μm间,BET分析表明样品比表面积处于1.0～9.0 m2·g-1间分布,反应过程中锂的过量以及长时间高温焙烧是引起产物粒径长大和产生硬团聚的主要原因.     

Separation of Tl/III/ from Tl/I/

A method for the separation of Tl/III/from Tl/I/ is reported employing 1-/2-pyridylazo/-2-naphthol /PAN/ and Rhodamine-B as extracting agents.     

LixNi0.8-yCo0.2ZnyOp的合成及电化学性能研究

A series of single-phase Li_xNi_0.8-yCo_0.2Zn_yO_p(0.96 ≤x≤ 1.10， 0 ≤y≤ 0.05， 2 ≤p≤ 2(1+y) ) (different in the y values) were synthesized by a two-step solid state reaction method， in which LiOH·H₂O， Zn-doped spherical Ni(OH)₂ and Co₂O₃ were used as the precursors. The ICP-AES analyses proved that the Zn-doped compounds synthesized had the nonstoichiometric form. The results of the XRD， SEM identified that the uniform particles of the as-prepared materials having a good layered structure were fine， narrowly distributed and well crystallized. The electrochemical performance test was carried out and the results showed that the as-prepared Zn-doped materials had not only a high capacity， but also a better cycling stability characterization than the un-doped one. The Li_1.06Ni_0.75Co_0.22Zn_0.03O_2.03 material has an initial reversible capacity as high as 160.5mAh·g^-1; and a first discharge efficiency 89.2%， and exhibits satisfactory cyclic stability with 90% retainable capacity after 50 cycles.     

橙红色荧光粉Ca_(1-x-y)Sm_xBi_ySiO_3的制备及其发光性能

以Sm3+作为激活剂,Bi3+作为辅助激活剂,采用水热法合成Ca1-x-ySmxBiySi O3前驱体,然后在1 100℃焙烧得到系列橙红色荧光粉。用X-射线衍射仪、扫描电镜和荧光分光光度计和傅里叶变换红外光谱等手段对样品的组成、结构和形貌及其发光性质进行分析和表征。分析结果表明:产物都为三斜晶系结构的Ca1-x-ySmxBiySi O3和四方结构的方石英Si O2共熔体。在405 nm近紫外光激发下,产物的发射光谱由3个峰组成,发射峰值位于566、606和650 nm处,分别归属于Sm3+的4G5/2→6HJ/2(J=5,7,9)跃迁。产物的激发光谱在405 nm有很强的发射带,与近紫外LED芯片匹配。随着Sm3+掺量的增加,样品发光强度先增强后减弱,当Sm3+的物质的量分数为3%时发光强度达到最大,浓度猝灭机理为电偶极-电偶极相互作用。当Bi3+的物质的量分数在0.3%~1.5%时,对产物Ca0.97Sm0.03Si O3的荧光强度起敏化作用。Sm3+和Bi3+的最佳物质的量分数分别为3%和0.5%。     

Zr1-xMxWMoO8-x/2和Zr1-xMxW2O8-x/2固溶体的晶胞参数与晶格畸变的关系

合成了Zr1-xMxWMoO8-x/2(M=Er,Tm,Yb,Sc,In,Ga,Al)和Zr1-xMxW2O8-x/2(M=Eu,Er,Yb,Sc,In,Ga,Al)2个系列的固溶体,前者具有β-ZrW2O8结构类型(简称β相);后者具有α-ZrW2O8结构类型(简称α相)。建立了相和相的晶胞参数与M3+离子浓度的Vegard方程,测定了上述固溶体的固溶度。讨论了M3+离子的化学性质与Vegard斜率SV的关系。分析了α相的SαA与β相的SβA的关系;揭示了α-Zr1-xMxW2O8-x/2晶格中2[WO4]四面体对的取向有序程度对晶格畸变的贡献。提出上述固溶体的晶胞参数随溶质浓度增加而减小,主要是由于氧空位缺陷相互作用的结果。     

Synthesis and characterization of Ti1−2xNbxNixO2−x/2 solid solutions

Doped-rutile has been traditionally used in ceramic pigments for its intense optical properties. In this paper, we compare the classical ceramic synthesis of Ti_1−2xNb_xNi_xO_2−x/2 system with the sol-gel methodology, which allows a reduction of the anatase-rutile transformation temperature. The composition was optimised in order to obtain a unique rutile phase with the minimum amount of pollutant Ni(II) and enhanced chromatic coordinates. Incorporation of the doping ions in the rutile structure was corroborated by XRD and Rietveld refinements. The species responsible for the colour mechanism were studied by different techniques. UV-VIS spectroscopy showed the characteristic features of Ni²⁺ ions, whose existence was corroborated by EPR and magnetic measurements. From these results, (Ni,Nb)doped-TiO₂ powder samples can be now shaped as thin films, monoliths, etc. by using sol-gel methodology without modifying their properties. This study introduces new possibilities of coloured TiO₂-based solid solutions in new combined advanced applications (colouring agent and photocatalyst, etc.).     

Analysis of nonvalent interactions in the crystals of conformational polymorphs of the composition CaHbNcOdSe by means of molecular voronoi-dirichlet polyhedra

Nonvalent interactions in crystals of compounds of the composition C _a H _b N _c O _d S _e that exhibit conformational polymorphism and have no fewer than four structurally characterized modifications are analyzed using molecular Voronoi-Dirichlet polyhedrals. A unique combination of the types of occurring intra- and intermolecular nonvalent contacts is shown to correspond to each conformational polymorph. Nonvalent interactions involving hydrogen atoms are found to occur most often in crystal structures, and least often those involving S, N, and O atoms.