基于3,5-二((4'-羧基苄基)氧)苯甲酸和4'-(4-吡啶基)-2,2':6',2"-三联吡啶为混合配体的两个配合物的水热合成与晶体结构

在水热条件下,以3,5-二((4''-羧基苄基)氧)苯甲酸(H₃bcb)和4''-(4-吡啶基)-2,2'':6'',2"-三联吡啶(PYTPY)为混合配体构筑了2个过渡金属配合物[Co(H₂bcb)₂(PYTPY)]_n(1)和[Mn(H₂bcb)₂(PYTPY)]_n(2),利用元素分析、红外光谱以及单晶X射线衍射表征其结构。分析表明配合物1和2为一维链状结构。此外,2个配合物展示了优良的热稳定性。磁化率的测试结果表明,配合物1和2在2 K和8 K以下时展示了反铁磁相互作用。     

两个基于4-羧酸-2,2':6',2"-三联吡啶的铜配合物的合成、晶体结构及性质

水热法合成了2个配合物{[Cu₂(L)₂(tp)]·2H₂O}_n (1)和[CuL(ClO₄)]_n (2)(L=4-羧酸-2,2'':6'',2"-三联吡啶,H₂tp=对苯二甲酸)。对其晶体结构进行了分析,结果表明配合物1和2都通过配体和金属离子组装成一维链结构;配合物1属于三斜晶系,P1空间群,并通过链间的氢键作用形成三维的网状结构;配合物2通过链与链间的氢键作用形成二维的层状结构。对其热稳定性和荧光性质进行了研究。     

基于2，6-双(3'-吡啶)-四硫富瓦烯的Zn/Co配位聚合物的光电流响应特性

首次报道了以2,6-双(3''-吡啶)-四硫富瓦烯(3''-py-TTF-3-py)为配体得到的2个新型配位聚合物：[Zn(3''-py-TTF-3-py)₂(TPA)]_n(1)和[Co(3''-py-TTF-3-py)₂(TPA)]_n(2)(H₂TPA=对苯二甲酸)。X射线单晶衍射结果显示配合物1和2为异质同晶结构。光电流测试结果表明,S…S键的相互作用和配合物的配位中心金属离子都对光电流响应信号有着明显的影响。     

由4,4'-二甲基-2,2'-联苯二甲酸配体构筑的锌(Ⅱ)和镉(Ⅱ)双核配合物的合成、晶体结构、荧光及光催化性质

采用水热方法，用4，4''-二甲基-2，2''-联苯二甲酸配体（H₂dbda）和菲咯啉（phen）、2，2''-联吡啶（2，2''-bipy）分别与ZnCl₂或Cd-Cl₂·H₂O反应，合成了3个零维双核配合物[Zn₂（μ-dbda）₂（phen）₂（H₂O）₂]（1）、[Zn₂（μ-dbda）₂（2，2''-bipy）₂]（2）和[Cd₂（μ-dbda）₂（2，2''-bipy）₂（H₂O）₂]·2H₂O（3），并对其结构、荧光和光催化性质进行了研究。结构分析结果表明3个配合物分别属于三斜和单斜晶系的P1和P2₁/n空间群。配合物1~3都具有零维双核结构，而且这些双核单元通过O-H…O氢键作用进一步形成了三维超分子框架。研究表明，配合物1~3在室温下能发出蓝色荧光。另外，研究了3个配合物对有机染料亚甲基蓝的光催化降解性能，结果表明配合物3可以高效地降解亚甲基蓝。     

基于3,5-二((4'-羧基苄基)氧)苯甲酸和4'-(4-吡啶基)-2,2':6',2"-三联吡啶为混合配体的两个配合物的水热合成与晶体结构

在水热条件下,以3,5-二（（4''-羧基苄基）氧）苯甲酸（H3bcb）和4''-（4-吡啶基）-2,2''：6'',2"-三联吡啶（PYTPY）为混合配体构筑了2个过渡金属配合物[Co（H₂bcb）₂（PYTPY）]_n （1）和[Mn（H₂bcb）₂（PYTPY）]_n （2）,利用元素分析、红外光谱以及单晶X射线衍射表征其结构。分析表明配合物1和2为一维链状结构。此外,2个配合物展示了优良的热稳定性。磁化率的测试结果表明,配合物1和2在2 K和8 K以下时展示了反铁磁相互作用。     

两个含3，3'-硫代二丙酸配体的锰和铜配合物的合成、晶体结构与性质

使用3,3''-硫代二丙酸、4,4''-联吡啶和硝酸锰在水热条件下反应合成了1个锰配合物,即{[Mn（DPA）（4,4''-bipy）]·H₂O}_n（1）（DPA=3,3''-硫代二丙酸,4,4''-bipy=4,4''-联吡啶）;然后又利用3,3''-硫代二丙酸、1,3-双（4-吡啶基）丙烷和硝酸铜在水热条件下反应合成了1个铜配合物,即{[Cu（DPA）（bpp）（H₂O）]·H₂O}_n（2）（DPA=3,3''-硫代二丙酸,bpp=1,3-双（4-吡啶基）丙烷）。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和2分别由3,3''-硫代二丙酸配体和不同氮杂环分子以及金属离子构筑,形成了二维层状的结构。氢键和π-π作用进一步将二维结构拓展成三维超分子网络。     

两个含3,3'-硫代二丙酸配体的锰和铜配合物的合成、晶体结构与性质

使用3,3''-硫代二丙酸、4,4''-联吡啶和硝酸锰在水热条件下反应合成了1个锰配合物,即{[Mn（DPA）（4,4''-bipy）]·H₂O}_n（1）（DPA=3,3''-硫代二丙酸,4,4''-bipy=4,4''-联吡啶）;然后又利用3,3''-硫代二丙酸、1,3-双（4-吡啶基）丙烷和硝酸铜在水热条件下反应合成了1个铜配合物,即{[Cu（DPA）（bpp）（H₂O）]·H₂O}_n（2）（DPA=3,3''-硫代二丙酸,bpp=1,3-双（4-吡啶基）丙烷）。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和2分别由3,3''-硫代二丙酸配体和不同氮杂环分子以及金属离子构筑,形成了二维层状的结构。氢键和π-π作用进一步将二维结构拓展成三维超分子网络。     

辅助配体导向合成两个锌金属配位聚合物:结构,稳定性和荧光性质

以二苯-4,4''-二羧酸和六水硝酸锌为原料,在相同反应条件下,通过改变不同的辅助配体(2,2''-二甲基-4,4''-联吡啶和三乙烯二胺),合成出2个金属有机配位聚合物:{[Zn(DBA)(dmbpy)_0.5]·2H₂O}_n (1)和[Zn₂(DBA)₂(dabco)]_n (2)(H₂DBA=二苯-4,4''-二羧酸,dmbpy=2,2''-二甲基-4,4''-联吡啶,dabco=三乙烯二胺)。通过元素分析、红外光谱、差热分析、X射线粉末衍射和X射线单晶衍射等手段对配合物进行了结构表征。结果显示,化合物1为二维(4,4)网络结构,2个二维结构在平行方向上通过互锁进一步形成2D→2D的互锁网络结构。化合物2为一维带状结构。热稳定性表明化合物1能够稳定到370℃;而化合物2稳定性差。荧光分析表明常温固态下配合物1和2均发射蓝色荧光,荧光寿命分别为231.4 ns和2.33 ns。     

4,4'-联吡啶桥联的三个铜有机膦酸配合物的合成、结构及磁性

在水热条件下,以N-氧化-2-吡啶膦酸(H₂L)为主配体,4,4’-联吡啶(bpy)为桥联配体,合成了3个铜有机膦酸配合物：{[Cu(L)(bpy)_0.5(H₂O)]·2H₂O}_n(1),{[Cu(HL)₂(bpy)]·4H₂O}_n(2)和{[Cu₂(L)₂(bpy)]·3H₂O}_n(3)。配合物1中,相邻的铜离子由2个膦酸根连成二聚体,二聚体之间通过bpy桥联成一维链。配合物2中,单核[Cu(HL)₂]被bpy连接成一维链。配合物3中,四聚体[Cu₂(L)₂]₂被bpy连接成“砖块状”结构的二维层。磁性研究表明,配合物1和3中铜离子之间存在反铁磁性耦合。     

基于3，3′，4，4′-四羧基偶氮苯构筑的三个金属配合物的合成、晶体结构及性质

在水热条件下利用H₄ddb配体合成了3个过渡金属配合物[Co₂（ddb）（phen）₂（H₂O）₆]·3H₂O（1）,[Co（ddb）_0.5（bpy）_0.5（H₂O）₃]_n（2）和{[Ag（dpe）]·0.5（H₂ddb）·H₂O}_n（3）（H₄ddb=3,3'',4,4''-四羧基偶氮苯,bpy=4,4''-联吡啶,dpe=1,2-二（4-吡啶基乙烯））,并用元素分析、红外光谱、X射线粉末衍射、X射线单晶衍射对其进行了表征。配合物1为双核结构,基于丰富的氢键作用扩展形成三维超分子网结构。配合物2为基于钴离子通过ddb^4-配体以μ₄：η¹,η¹,η¹,η¹的配位模式连接而成的二维网结构。配合物3是由Ag（Ⅰ）离子与dpe配体形成的直链结构,客体分子H₂ddb^2-通过氢键作用将其扩展为三维超分子结构。此外还研究了配合物1~3的荧光性质和热稳定性。     

三个有机锡2，2′-联苯二甲酸酯的微波溶剂热合成、结构及体外抗癌活性

以2,2′-联苯二甲酸(H2DPA)分别与双(三(2-甲基-2-苯基丙基)锡)氧化物、三环己基氢氧化锡和二丁基氧化锡反应,合成了3个有机锡2,2′-联苯二甲酸酯：[((Ph C(Me)₂CH₂)₃Sn)₂(DPA)](1)、[(Cy)₃Sn(DPA)]_n (2)和[(n-Bu)₂Sn(DPA)]_n (3)。通过IR、NMR、元素分析、热重及X射线单晶衍射对配合物进行表征分析。配合物1、2、3均属单斜晶系,配合物1为双核结构,配合物2、3为一维链状结构,锡原子的配位数依次增大,分别为4、5、6。体外抗癌活性实验表明,配合物1、2、3对人肺癌细胞(NCI-H460)、人乳腺腺癌细胞(MCF-7)、人肝癌细胞(Hep G2)的增殖具有较强的抑制作用。     

Synthesis,characterization, biological activities,crystal structure and DNA binding of organotin(IV) 5-chlorosalicylates

New organotin(IV) carboxylates, R₂SnL₂ (R=n-Bu: 1), R₂Sn(Cl)L (R=n-Bu: 2), and R₃SnL (R=Me: 3; n-Bu: 4; Ph: 5) have been synthesized by stirring 5-chloro-2-hydroxybenzoic acid HL with KOH and R₂SnCl₂ (R=n-Bu)/R₃SnCl (R=Me, n-Bu, Ph) in methanol at room temperature. The complexes along with ligand have been characterized by FTIR, (¹H, ¹³C) NMR, EI-MS, and single-crystal XRD crystallography. FTIR data indicated bidentate coordination of carboxylate. NMR data suggested six- or five-coordinate geometry of organotin(IV) carboxylates. Single-crystal XRD of 1 demonstrated skew-trapezoidal geometry around the tin center, with the basal plane occupied by four oxygens and the two butyl groups lying in distorted axial position. Complexes 1, 2, and 5 exhibited interaction with SS-DNA (salmon sperm) and suggests intercalating mode of binding. The complexes displayed significant antimicrobial activities against bacterial and fungal strains as compared to free ligand. The hemolytic activity of the complexes was lower compared to Triton-X 100 (positive control, 100% lysis) and higher than phosphate-buffered saline (negative control, 0% lysis). Complex 4 was the most potent inhibitor of bacterial/fungal growth.     

有机锡1,1′-亚甲基双(1H-吡唑-4-甲酸酯)的合成、结构与抗肿瘤活性

通过1,1′-亚甲基双(1H-吡唑-4-甲酸)(CH2(PzCO2H)2)与R3SnOH或(R3Sn)2O的反应,合成了4个有机锡1,1′-亚甲基双(1H-吡唑-4-甲酸酯)衍生物(CH2(PzCO2SnR3)2,R=Ph(1),环己基(2),Et(3),n-Bu(4))。通过红外和核磁对这些配合物进行了详细的结构表征。配合物1和3的X射线单晶衍射分析表明,这2个配合物中的吡唑氮原子均没有参与配位,但它们的羧酸根却表现出明显不同的配位方式。配合物1中羧酸根为单齿配体,且该配合物表现为简单双核结构;配合物3中羧酸根为双齿配体,其通过羧基的桥式双齿配位方式形成具有32元大环结构单元的二维配位高分子。初步的生物活性测试表明,这些有机锡衍生物对MCF-7和A549细胞具有很好的体外细胞毒性。     

Synthesis,spectroscopic characterization,crystal structure,and anti-bacterial activity of diorganotin(IV) complexes with 5-bromo-2-hydroxybenzaldehyde-N(4)-ethylthiosemicarbazone

Three new diorganotin(IV) complexes, [Me₂Sn(BDET] (2), [Bu₂Sn(BDET)] (3), and [Ph₂Sn(BDET)] (4), were synthesized by reacting R₂SnCl₂ (R = Me, Bu, and Ph) with 5-bromo-2-hydroxybenzaldehyde-N(4)-ethylthiosemicarbazone [H₂BDET, (1)] in the presence of KOH in absolute methanol. The newly synthesized complexes were characterized by elemental analysis, molar conductivity, UV–vis, FT-IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopies. The molecular structure of 4 was confirmed by X-ray crystallography. X-ray crystallography revealed that the doubly deprotonated O,N,S-tridentate thiosemicarbazone coordinates to tin(IV), resulting in a distorted trigonal bipyramidal geometry. Their ¹H, ¹³C, and ¹¹⁹Sn NMR spectra support a five-coordinate tin(IV) in solution for all complexes, in accord with the solid-state X-ray structure determined for 4. Compounds 1–4 were evaluated for their antibacterial activities against Staphylococcus aureus, Enterobacter aerogenes, Escherichia coli, and Salmonella typhi. The results exhibited that 2–4 were active with comparable potency compared to the standard drug. Antibacterial studies also indicated that the complexes have potential for biological evaluation.     

Chlorodiphenyltin(IV) and triphenyltin(IV) complexes of N-alkylated 2-amino-1-cyclopentene-1-carbodithioic acids: synthesis, spectroscopic characterization and X-ray studies

Four new complexes, [Ph₃Sn(isopropylACDA)] (1), [Ph₂SnCl(isopropylACDA)] (2), [Ph₃Sn(secbutylACDA)] (3), and [Ph₂SnCl(secbutylACDA)] (4), have been prepared from reaction between N-alkylated 2-amino-1-cyclopentene-1-carbodithioic acids (ACDA) with Ph₂SnCl₂ and Ph₃SnCl in 1:1 ratio. All complexes are characterized by FTIR, multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn) and mass spectrometry. In all complexes, the S–H proton has been removed and coordination takes place through the carbodithioate moiety. The ¹¹⁹Sn NMR data are consistent with five coordination of tin atom in solution. Complexes 2, 3, and 4 have also been confirmed by single X-ray crystallography. All three crystals are triclinic with space group P − 1. In complexes 2 and 4, the geometry around tin atom is distorted trigonal bipyramidal while in 3 the geometry is in between distorted tetrahedral and trigonal bipyramid. In all three structures, ligands are asymmetrically coordinated to tin atom. In addition, crystal structures are further stabilized by N–H···S hydrogen bonding.     

Template synthesis and structural characterization of new diorganotin(IV) tetraazamacrocyclic complexes: precursors to produce pure phase nanosized SnO2

This article describes the synthesis and characterization of several new diorganotin(IV) tetraazamacrocyclic complexes. The template condensation of anthranilic acid and diethylenetriamine with 1,2-dibromoethane or 1,3-dibromopropane in the presence of diorganotin(IV) dichlorides yielded macrocyclic complexes. The geometry and the mode of bonding of the resulting complexes were inferred from elemental analysis, UV-Vis, IR, Direct Analysis in Real Time-mass, (¹H, ¹³C and ¹¹⁹Sn) NMR, and ^119mSn Mössbauer spectral studies. These studies suggested that the macrocyclic ligands are tetradentate, coordinating through four nitrogens giving a skew-trapezoidal bipyramidal environment around tin in the [R₂Sn(L-1)/(L-2)] (R = Me, n-Bu and Ph; H₂L-1/H₂L-2 = macrocyclic ligands) complexes. Thermal studies of the complexes were carried out in the temperature range 25–1000°C using thermogravimetry, derivative thermogravimetry, and differential thermal analysis techniques which provided a simple route to nanosized semi conducting SnO₂ grains, identified by X-ray diffraction analysis. The particle size of the residue, obtained by pyrolysis of 2, 3, 4 and 5, determined by X-ray line broadening and transmission electron microscope were in the range ～38–48 nm and ～3–20 nm, respectively. The surface morphology of these residues was determined by scanning electron microscopy.     

1，1'-二羟基-5，5'-联四唑的镧系金属配合物的合成、表征及热行为

以1,1′-二羟基-5,5′-联四唑(H_2BTO)为配体,镧系金属离子作为金属中心,采用溶剂热法制备了5种金属配合物:[La_2(BTO)_3(H_2O)_8]·2H_2O (1)、[Ce_2(BTO)_3(H_2O)_8]·2H_2O (2)、[Pr_2(BTO)_3(H_2O)_8]·2H_2O (3)、[Sm_2(BTO)_3(H_2O)_8]·2H_2O (4)和[Nd_2(BTO)_3(DMF)_4]·6H_2O (5)。通过单晶X射线衍射和元素分析对5种配合物的结构进行了表征。结果表明,5种配合物均属于单斜晶系,P2_1/n空间群。利用差示扫描量热法研究了配合物1～4的热稳定性,采用Kissinger法和Ozawa法分别计算了其热分解动力学参数。     

Syntheses and crystal structures of polymeric ionic triorganotin esters of 3,5-pyridinedicarboxylic acid and 5-nitroisophthalic acid

The triethylammonium dicarboxylatotriorganostannates, [(C₂H₅)₃NH][R₃Sn(3,5-pdc)]?·?mH₂O (3,5-pdc?=?3,5-pyridinedicarboxylate) (m?=?1, R?=?Me 1; m?=?0, R?=?Ph 2, PhCH₂ 3, n-Bu 4), [(C₂H₅)₃NH][R₃Sn(5-nip)] (5-nip?=?5-nitroisophthalate) (R?=?Me 5, Ph 6, PhCH₂ 7, n-Bu 8) have been prepared from triethylamine, 3,5-pyridinedicarboxylic acid, 5-nitroisophthalic acid and triorganotin chloride. Complexes 1–8 have been characterized by elemental, IR, ¹H, ¹³C and ¹¹⁹Sn NMR analyses. Complexes 1, 2, 5 and 6 are also determined by single crystal X-ray diffraction. For 1, 2, 5 and 6, each carboxylate moiety is involved in coordination to a tin center via only one O atom showing that the Sn atoms are five-coordinate and exist in trigonal bipyramidal geometries. Moreover, for 2, 5 and 6, the nitrogen atoms of ammonium are hydrogen bonded to the pendant carboxyl oxygen. In 1, adjacent polymeric chains and triethylammonium are linked by hydrogen bonds through the co-crystallized water molecule, thus a 2D network is formed.