2个具有Sn4O4梯状结构二丁基锡羧酸酯的微波溶剂热合成、结构和体外抗癌活性

在甲醇微波溶剂热中,二丁基氧化锡分别与4-甲基苯甲酸、4-二甲氨基苯甲酸反应,合成了2个具有梯形结构的二丁基锡羧酸酯[（μ₃-O）（ μ₂-OMe）（n-Bu₂Sn）₂（O₂CR）]₂（R=4-Me-C₆H₄（1）,4-Me2N-C₆H₄（2））,并对其进行了元素分析、IR和（¹H,¹³C和¹¹⁹Sn）NMR光谱表征。X射线晶体衍射分析表明,化合物1、2具有Sn₄O₄构筑的3个四元环梯形骨架平面结构,μ₃-O桥联2个环内梯锡和1个环梯端锡原子,此外,甲醇氧还以μ₂-O桥联1个环内梯锡和1个环梯端锡原子,锡与配基原子构成畸形三角双锥六面体。化合物对人结肠癌（HT-29）、肝癌细胞（HepG2）、乳腺癌（MCF-7）、鼻咽癌（KB）和肺癌细胞（A549）均显示出比临床使用的顺铂还强的抗癌活性。     

两个二[氧合-二(取代苯甲酸二丁基锡)]的微波溶剂热合成、晶体结构和体外抗癌活性

在微波甲醇溶剂热中,二丁基氧化锡分别与4-叔丁基苯甲酸和3-甲基-4-氨基苯甲酸反应,合成了具有μ3-O桥联的有机锡化合物[(μ_3-O)(n-Bu_2Sn)_2(O_2CR)_2]_2(R=4-(t-Bu)-C_6H_5(1),(3-Me-4-NH_2)-C_6H_4(2)),并对它们的组成和结构进行了表征,X射线晶体衍射表明,化合物1、2的中心具有Sn2O2四元环平面结构,锡与配基原子构成畸形三角双锥六面体。人体外抗肿瘤活性的初步研究表明,化合物1、2对人结肠癌(HT-29)、肝癌细胞(HepG2)、乳腺癌(MCF-7)、鼻咽癌(KB)和肺癌细胞(A549)均显示出比临床使用的顺铂还强的抗癌活性。     

两个有机锡羟基苯甲酸酯配合物的合成、结构及抗癌活性

合成了2个有机锡羟基苯甲酸酯配合物:梯形结构的二(对氯苄基)锡邻羟基苯甲酸酯[(μ_3-O)(μ_2-OH)(p-Cl-C_6H_4CH_2Sn)_2(O_2CC_6H_4-OH-o)]_2(1)和三苯基锡二(对羟基苯甲酸)酯(2)。通过元素分析、红外光谱、差热分析、X射线单晶衍射等方法对配合物进行了结构表征,并对其进行了量子化学从头计算和体外抗癌活性研究。结果显示:配合物1为具有Sn_2O_2构筑的3个平面四元环组成的梯形骨架结构,配合物2为单锡核结构,锡原子均为五配位的畸变三角双锥构型;配合物对人结肠癌细胞(HT-29)、肝癌细胞(HepG2)、乳腺癌细胞(MCF-7)、宫颈癌细胞(Hela)和肺癌细胞(A549)均显示出比临床使用的顺铂更强的抗癌活性。     

四核簇状和一维链状丁基锡α-萘乙酸酯的合成、结构及抗癌活性

在相同条件下,α-萘乙酸分别与二丁基氧化锡、氧化双(三丁基锡)反应,合成了四核簇状二丁基锡α-萘乙酸酯{[n-Bu2Sn(O2CCH2C10H7)]2O}2(1)和一维链状三丁基锡α-萘乙酸酯[n-Bu3Sn(O2CCH2C10H7)]n(2)。经IR、1H和13C NMR、元素分析和X-射线单晶衍射表征结构。1具有核心结构为氧原子桥联锡构筑的Sn2O2四元环,且四元环二聚形成Sn4O4簇状,中间Sn2O2环的中心为整个分子的对称中心。1中,两相邻配合物分子间通过C-H…π作用、形成一维带状结构。配合物2中,锡原子通过羧基双齿桥联、组成一维链状配位聚合物。测试表明:1和2分别在250、175℃以下可以稳定存在;对人癌细胞Colo205、Hep G2、MCF-7、Hela、NCI-H460增殖均有较强的抑制作用,且2的活性高于1。     

配合物二乙基锡N-[(2-氧苯基)亚甲基]甘氨酸酯的合成、结构表征和生物活性

合成了5个新的二乙基锡N-[(2-氧苯基)亚甲基]甘氨酸酯(CH3CH2)2Sn(2-O-3-X-5-YC6H2CH=NCH2COO)(X,Y=H,H,1;H,Cl,2;H,Br,3;Cl,Cl,4;Br,Br,5),利用元素分析、IR、1H和129Sn NMR表征了其结构.通过X-射线单晶衍射测定了1和4的晶体结构.化合物1的晶体属单斜晶系,P21空间群;化合物4的晶体属三斜晶系,P1空间群.2个化合物均为由羧基桥联形成的[Sn3O6C3]十二元大环三聚体结构,锡原子的配位构型为六配位[SnC2NO3]畸变八面体.生物活性测试结果表明,化合物5对3种人癌细胞HeLa、CoLo205和MCF-7及大肠杆菌均有抑制活性.     

一维链状配位聚合物乙醇合二丁基锡-3,5-二硝基-2-氧苯甲酸酯的合成、结构和性质

利用二丁基氧化锡和3,5-二硝基水杨酸在苯-乙醇中反应合成了新配合物乙醇合二丁基锡3,5-二硝基-2-氧苯甲酸酯(n-C4H9)2Sn(2-O-3,5-(NO2)2C6H2COO)(C2H5OH)(1),通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1属单斜晶系,P21/c空间群,a=1.363 33(10)nm,b=1.861 90(14)nm,c=0.841 51(6)nm,β=93.311(1)°,Z=4,V=2.132 5(3)nm3,R1=0.033 6,wR2=0.090 0。该化合物为由羧基桥联配位和分子间氢键形成的新型一维链状有机锡配合物,锡原子具有六配位[SnC2O4]畸变八面体构型。化合物1对2种人癌细胞A549和CoLo205增殖均有强的抑制作用,对乙酰乙酸乙酯与醇的酯交换反应具有高选择性和良好的催化活性。     

双氧桥联四核二丁基锡(2，4，6-三甲基)苯甲酸酯配合物的合成、结构、量子化学及热稳定性研究

2,4,6-三甲基苯甲酸(TMBA)与(n-Bu)2SnO反应,合成氧桥联的四核二丁基锡(2,4,6-三甲基)苯甲酸酯配合物{[(n-Bu)2Sn(2,4,6-TMBA)]2O}2,经元素分析、1H NMR、13C NMR、IR和X-射线衍射表征分子结构,该配合物晶体属三斜晶系,空间群P1,晶体学参数:a=1.272 56(2)nm,b=1.322 73(2)nm,c=1.437 25(3)nm,α=111.197 0(10)°,β=99.691 0(10)°,γ=111.790 0(10)°,Z=1,V=1.962 35(6)nm3,Dc=1.368 g.cm-3,μ(Mo Kα)=1.308 mm-1,F(000)=828,R=0.040 9,wR=0.109 1。配合物以Sn2O2平面四元环中心对称,每个桥联氧原子还连接一个环外锡,形成双氧桥联四核二丁基锡结构。环上与环外Sn原子均呈现五配位畸变三角双锥构型。利用量子化学G03W软件,在Lanl2dz基组对配合物的稳定性、分子轨道能量、原子净电荷布居及前沿分子轨道组成进行了研究。并通过热重分析对配合物进行了热稳定性研究。     

基于[Dy4（μ4-O）]四面体结构单元的八核和十核镝簇合物的合成、结构及其单分子磁体行为研究

通过溶剂热法合成了两个稀土簇合物,其组成分别为:[Dy8(bpt)8(μ4-O)2(μ-OMe)8(μ1,1,3,3-N3)(μ1,3-N3)(N3)2]11H2O 9MeOH(1)和[Dy10(bpt)6(μ4-O)4(μ3-OMe)4(μ-OMe)8(μ-OAc)2(OAc)2]40H2O(2)(Hbpt=3,5-双(2-吡啶基)-1,2,4-三氮唑).1的簇核结构由两个[Dy4(μ4-O)]四面体通过罕见的μ1,1,3,3和μ1,3叠氮桥连接而成,2则由四个共边连接的[Dy4(μ4-O)]四面体组成.两个簇合物都表现出单分子磁体行为,其中2是核数最高的纯稀土单分子磁体.     

梯形四核有机锡氧簇合物的合成、表征、量子化学、热稳定性及荧光性质研究(英文)

在甲醇中三苄基氯化锡与3,4-二甲氧基苯甲酸发生脱烃基反应,合成了梯形四核有机锡氧簇合物[(μ-O)(μ-OMe)(L)Sn2(CH2Ph)4]2(HL=(MeO)2C6H3CO2H),经UV、IR、元素分析及X-射线单晶衍射表征结构。该晶体属三斜晶系,空间群P1,晶体学参数:a=1.225 6(5)nm,b=1.229 4(5)nm,c=1.378 0(5)nm,α=69.784(7)°,β=68.568(7)°,γ=72.926(7)°,V=1.780 1(12)nm3,Z=1,Dc=1.549 g·cm-3,μ(Mo Kα)=1.447 mm-1,F(000)=832,R1=0.0261,wR2=0.060 6。晶体结构分析表明:整个分子是以Sn2O2四元环为中心的对称结构,中心锡原子呈五配位畸变三角双锥构型。晶体中,两相邻的配合物分子经C-H…π作用组成一维带状结构。利用量子化学G03W软件,在LANL2DZ基组对配合物的稳定性、前沿分子轨道组成及能量进行研究。热重分析表明,配合物在128℃以下能稳定存在。此外,还研究了该配合物的荧光性质。     

二[氧合-二(4-二茂铁基苯甲酸二烷基锡(Ⅳ))]配合物的合成、谱学表征和晶体结构研究

合成了{[(n-Bu)2Sn(4-Fc-C6H4COO)]2O}2 (1)和{[(n-Oct)2Sn(4-Fc-C6H4COO)]2O}2(2)(Fc=ferrocenyl)两种新的配合物, 对其进行了元素分析, 并用IR, NMR(1H, 13C, 119Sn)进行了谱学表征. 单晶X射线衍射法测定表明, 配合物1的晶体属单斜晶系, P21/c空间群, 晶胞参数a=1.298 8(1) nm, b=2.465 5(1) nm, c=3.450 6(1) nm, β=91.556(2)°, V=11.045 4(1) nm3, Z=4, 最终可靠因子Rf=0.071, Rw=0.070. 分子1为具有一个Sn2O2四元中心内环的二聚结构, 桥氧原子又各连接一个外环Sn原子, 呈三配位. 内环锡和外环锡采用略有不同的加帽三角双锥配位几何. 4个羧酸酯基具有两种不同的配位方式, 其中两个羧酸酯基通过其两个氧原子以桥式双齿分别跨接于一个内环锡和一个外环锡, 而另外两个羧酸酯基则以单齿配位方式各与一个外环锡相连接. Sn2O2中心内环与苯甲酸酯基、茂环等共轭体系之间相互未能共平面. 整个分子结构中无对称中心.     

[Pt2(P2O4H2)4]4-和[Pt2(P2O4CH4)4]4-基态和激发态性质的理论研究

采用从头计算MP2和CIS方法分别优化等电子双核d⁸配合物[Pt₂(P₂O₄H₂)₄]^4-和[Pt₂(P₂O₄CH₄)₄]^4-的基态和激发态结构。结果表明基态Pt-Pt距离分别为0.290 5和0.298 7 nm，与实验的0.292 5和0.298 0 nm符合。NBO计算的Pt-Pt键级以及Pt原子间伸缩振动说明Pt-Pt相互作用具有吸引本质。CIS计算揭示电子激发到Pt-Pt的σ(p_z)成键轨道使得相互作用增强。保持激发态几何，含时密度泛函理论(TD-DFT)计算的溶液发射分别为449和475 nm，与实验值512和510 nm接近。     

Chromium(III) Hydroxide Solubility in The Aqueous Na+-OH?-H2PO?4-HPO2?4-PO3?4-H2O System: A Thermodynamic Model

Chromium(III)-phosphate reactions are expected to be important in managing high-level radioactive wastes stored in tanks at many DOE sites. Extensive studies on the solubility of amorphous Cr(III) solids in a wide range of pH (2.8–14) and phosphate concentrations (10^–4 to 1.0 m) at room temperature (22±2)°C were carried out to obtain reliable thermodynamic data for important Cr(III)-phosphate reactions. A combination of techniques (XRD, XANES, EXAFS, Raman spectroscopy, total chemical composition, and thermodynamic analyses of solubility data) was used to characterize solid and aqueous species. Contrary to the data recently reported in the literature,⁽¹⁾ only a limited number of aqueous species [Cr(OH)₃H₂PO^–₄, Cr(OH)₃(H₂PO₄)^2–₂), and Cr(OH)₃HPO^2–₄] with up to about four orders of magnitude lower values for the formation constants of these species are required to explain Cr(III)-phosphate reactions in a wide range of pH and phosphate concentrations. The log K^o values of reactions involving these species [Cr(OH)₃(aq)+H₂PO^–₄⇌Cr(OH)₃H₂PO^–₄; Cr(OH)₃(aq)+2H₂PO^–₄⇌Cr(OH)₃(H₂PO₄)^2–₂; Cr(OH)₃(aq)+HPO^2–₄⇌Cr(OH)₃HPO^2–₄] were found to be 2.78±0.3, 3.48±0.3, and 1.97±0.3, respectively.     

Synthesis and characterization of trans -Mo(CO)4( p -C5NH4SO3Na)2

Reaction between Mo(CO)₆ and p-C₅NH₄SO₃Na (1:2 (Mo: p-C₅NH₄SO₃Na) stoichiometric ratio) gave the trans-Mo(CO)₄(p-C₅NH₄SO₃Na)₂ complex, (1), in 80% yield. Complex (1) has been characterized by FTIR, ¹H and ¹³C NMR spectroscopy. Complex (1) has most likely an idealized D_4h geometry with trans N-bound p-C₅NH₄SO₃Na ligands.     

B-frame supported bimetallics. [(PMe2ph)2PtB9H11Ru(η-PrC6H4Me)] and [(PMe2ph)2PtB9H9Ru(η-PrC6H4Me)]; an interesting pair of electron-deficient nido and closo geometries

[7,7-(PMe₂Ph)₂-9-(η⁶-^isoPrC₆H₄Me)-7,9-PtRuB₉H₁₁] has a formal closo Wadian cluster-electron count, but a nido geometry, whereas [1-(η⁶-^isoPrC₆H₄Me)-4,4-(PMe₂Ph)₂-1-4-RuPtB₉H₉], which does have a closo geometry, has a formal sub-closo cluster electron count; both compounds are formed in the reaction between [6-(η⁶-^isoPrC₆H₄Me)-nido-6 RuB₉H₁₃], KH and [PtCl₂(PMe₂Ph)₂].     

Inclusion compounds of cystostatic active (C5H5)2VCl2 and (CH3C5H4)2VCl2 with α-, β- and γ-cyclodextrines: Synthesis, EPR study and microbiological behavior toward Escherichia coli

The inclusion of vanadocene dichloride (VDC) and 1,1′-dimethyl vanadocene dichloride (MeVDC) into cyclodextrines (α-CD, β-CD and γ-CD) was studied by EPR spectroscopy. It was found that VDC and MeVDC with β-CD and γ-CD form true inclusion compounds, but with α-CD, VDC and MeVDC gave only fine dispersion mixtures. The inclusion was validated by anisotropic EPR spectra of solid samples. In addition, the antimicrobial was validated by anisotropic EPR spectra of solid samples. In addition, the antimicrobial behavior (against E. coli) of each of the complexes was determined. It was established that not only did VDC and MeVDC cause elongation of E. coli, but also the new vanadocene inclusion complexes were effective in this regard.     

Crystal structure and single crystal EPR of (NH4)2(15-crown-5)3[Cu(mnt)2] and (NH4)2(benzo-15-crown-5)4[Cu(mnt)2]·0.5H2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2- anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(Ⅱ) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

Eu3+离子在Ca2PbO4一维结构基质中的发光研究

A Eu³⁺-doped Ca₂PbO₄ with one-dimensional structure was prepared with a solid-state reaction method and its characteristics were investigated. The XRD results show that the substitution of Ca²⁺ by Eu³⁺ has no influence on the structure of Ca₂PbO₄. Under the excitation of ultraviolet light， the Ca₂PbO₄:Eu³⁺ phosphor exhibits strong red emission at about 618 nm which is assigned to the ⁵D₀- ⁷F₂ electric-dipole transition. The compounds Sr₂CeO₄ and Ca₂SnO₄ have the same crystal symmetry as that of Ca₂PbO₄ and it is found that the emission intensity of Ca₂PbO₄∶Eu³⁺ is higher than that of Sr₂CeO₄∶Eu³⁺ and lower than that of Ca₂SnO₄∶Eu³⁺. The excitation spectrum of Ca₂PbO₄∶Eu³⁺ appears to be a broad band with two peaks at about 289 nm and 340 nm. The former peak is attributed to the Eu³⁺-O₂- charge transfer transition， while the latter one may be related to the absorption of Ca₂PbO₄ host or its crystal defects.     

含有氮杂环的酰腙配合物Cu(C15H11BrN2O4)(C5H5N)的合成和晶体结构

0 引 言 Schiff碱及其金属配合物,因其具有较强的生物活性以及良好的催化作用而倍受人们的关注[1,2].     

Na4Sn9与一些配合物相互作用的119Sn和23Na NMR研究

以¹⁹⁹Sn和²³Na核磁共振研究了Na₄Sn₉-乙二胺体系中加入M(acacen)(M=Cu²⁺,Ni²⁺)和Ln(fod)₃(Ln=Pr³⁺,Yb³⁺,Eu³⁺)后的化学位移和偶合常数。结果表明,假接触和体积磁化率的变化是引起化学位移变化的主要原因,而Fermi接触的贡献可以忽略。     

三苯基锡(Ⅳ)N-烃基哌嗪氨荒酸酯配合物的合成、表征、性质和Ph3SnS2CN(C2H4)2NCH3的晶体结构

Six triphenyltin(Ⅳ)N-alkylpiperazinyldithiocarbamates have been synthesized by the reaction of triphenyltin chloride with N-alkylpiperazinyldithiocarbamates and characterized by elemental analysis, UV, IR and ¹H NMR. The crystal structure of Ph₃SnS₂CN(C₂H₄)₂NCH₃(1) has been determined by X-ray single crystal diffraction. The crystal of the compound 1 belongs to triclinic with space group P1, a=1.033 56(18) nm, b=1.148 8(2) nm, c=1.191 6(2) nm, α=66.282(2)°, β=78.756(2)°, γ=67.476(2)°， Z=2, V=1.195 2(4) nm³, D_c=1.460 g·cm^-3, μ=1.256 mm^-1, R=0.025 1, wR=0.058 3. The structure shows a distorted tigonal bipyramidal configuration with five-coordination for the central tin atom. CCDC: 240375.