4,5-二氮芴-9-酮Cu(II),Zn(II)配合物的合成、晶体结构、热分析及理论计算

合成了 4,5 二氮芴 9 酮 (dafo)的Cu(II) ,Zn(II)配合物 [Cu(dafo) 2 (H2 O) 2 ] (NO3 ) 2 和 [Zn(dafo) 2 (H2 O) 2 ] (NO3 ) 2 ,通过单晶X射线衍射法确定了它们的结构 .晶体结构分析表明 ,配合物分子中Cu(II) ,Zn(II)分别和来自两配体的四个氮原子及两个水分子中的氧原子配位 ,处于六配位的配位环境中 ,两配体基本处于同一平面 ,两水分子垂直于两配体所在平面 ,Cu(II)处于畸变八面体中心 ,Zn(II)处于正常八面体中心 ,对两种配合物进行了元素分析、红外和热分析表征 ,在实验的基础上 ,采用Gaussian 98w中的DFT B3LYP/LANL2DZ对两种配合物进行了全几何优化以及后续计算     

过渡金属离子与3-氟邻苯二甲酸和1,10-邻菲啰啉配合物的合成、结构及性质

过渡金属离子与3-氟邻苯二甲酸(H2Fpht)、1,10-邻菲啰啉(phen)通过水热反应得到了5个配合物:[M(Fpht)(phen)(H2O)3]·H2O(M=Ni 1,Co 2),[Cu(Fpht)(phen)(H2O)]·H2O(3),[M(Fpht)(phen)(H2O)]·H2O(M=Zn 4,Cd 5)。通过X-射线单晶衍射分析、元素分析、红外分析、荧光分析以及差热-热重分析对配合物进行了表征。配合物1和2为单核分子,中心离子Ni(Ⅱ)和Co(Ⅱ)与3-氟邻苯二甲酸根的1个氧原子,1,10-邻菲啰啉的2个氮原子以及3个配位水分子的3个氧原子配位,形成六配位的扭曲八面体构型。配合物3为Z字形一维链状结构。中心Cu(Ⅱ)离子与2个3-氟邻苯二甲酸根的2个氧原子,1个1,10-邻菲啰啉的2个氮原子以及水分子的1个氧原子配位,形成四方锥构型。配合物4和5具有相似的一维螺旋结构,中心Zn(Ⅱ)和Cd(Ⅱ)离子与2个3-氟邻苯二甲酸根的3个氧原子、1,10-邻菲啰啉的2个氮原子以及水分子中的1个氧原子配位,形成扭曲的八面体构型。     

新型含2,5-二-（3,5-二甲基吡唑-4-巯基）-1,3,4-噻二唑-M(M=Co2+,Cd2+,Mn2+)配合物的合成、晶体结构及其抑菌活性研究

将配体L[2,5-二-(3,5-二甲基吡唑-4-巯基)-1,3,4-噻二唑]与Co(NO3)2 6H2O,Cd(NO3)2 4H2O和MnCl2 4H2O进行配位反应,得到三个配合物[Co(L)2(H2O)4](NO3)2 4(CH3CH2OH)(1),[Cd(L)2(H2O)4](NO3)2 4(CH3CH2OH)(2),[Mn(L)2(Cl)2(CH3OH)2]2(CH3OH)(3),并用元素分析,FT-IR和X射线单晶衍射进行了表征.分析结果表明,配体L呈"U"形,配合物1～3呈"S"形.配合物中Co(II),Cd(II),Mn(II)的配位环境均为扭曲八面体,每个金属离子同时和两个配体进行配位.配体和配合物体外抑菌活性研究结果表明,配体及其配合物都有一定的抑菌活性.     

2-氨基对苯二甲酸根及2-咪唑烷酮构筑的镉(Ⅱ)配位聚合物的合成、晶体结构及荧光性质

以一种尿素的衍生物2-咪唑烷酮为溶剂,采用脲热法合成了一个新的配位聚合物[Cd(NH2bdc)(e-urea)]n(1)(H2NH2bdc为2-氨基对苯二甲酸,e-urea为2-咪唑烷酮),并对其结构和荧光性质进行了研究。单晶结构分析结果表明,标题化合物的中心镉(Ⅱ)离子分别与2-氨基对苯二甲酸根配体的羧基氧原子和溶剂氧原子配位形成七配位的变形五角双锥结构。相邻的中心镉(Ⅱ)离子通过溶剂氧原子和配体羧基基团的连接,形成无限的一维链。这些一维的链进一步通过2-氨基对苯二甲酸根配体的连接最终形成了具有一维孔道的三维框架结构。研究表明,该化合物在室温下能发出较强的蓝色荧光。     

刚性配体2,2-联吡啶诱导的双咪唑金属超分子配合物的合成与晶体结构

合成了3种新的超分子配合物[Cd(H2biim)(2,2'-bipy)(NO3)2] (1), [Cu(H2biim)(2,2'-bipy)(H2O)](NO3)2 (2)和[Zn(H2biim)(2,2'-bipy)(H2O)](NO3)2 (3) (H2biim＝双咪唑; 2,2'-bipy＝2,2'-联吡啶), 并通过X射线单晶衍射测定了其结构. 配合物1～3均为单斜晶系, 属于P2(1)/c空间群, 在1中, Cd(II)为六配位, 它与双咪唑的2个氮原子, 联吡啶的2个氮原子和2个硝酸根的2个氧原子配位. 在2和3中, Cu(II)和Zn(II)均为五配位的, 它们与双咪唑的2个氮原子、2,2'-联吡啶的两个氮原子和一个水分子配位. 1～3的对称单元均通过双咪唑、硝酸根和水之间形成的氢键R21(7), R21(4) 和R44(18)构筑了1D链状超分子.     

铕(Ⅲ)/镝(Ⅲ)苯并咪唑-5,6-二羧酸配位聚合物的合成和晶体结构

水热法合成了配合物{[Ln(Hbmdc)(bmdc)(H2O)3].3H2O}n(Ln=Eu,1;Dy,2;H2bmdc=苯并咪唑-5,6-二羧酸),用X-射线单晶衍射分析确定了配合物的晶体结构。配合物为单斜晶系,P21/c空间群。配合物1和2具有相似的一维链状结构。配体H2bmdc以2种不同的类型与Ln3+离子配位:完全去质子化的bmdc配体和咪唑环上的氮原子被质子化的Hbmdc配体。bmdc配体的2个羧基采取双齿螯合/双齿螯合方式配位;Hbmdc配体的1个羧基采取双齿螯合方式配位,另1个羧基未参与配位。每个Ln3+离子与6个羧基氧原子和3个水分子中氧原子配位,形成9配位的扭曲单帽四方反棱柱体。相邻的Ln3+离子通过bmdc配体桥联形成螺旋链状结构。链和链之间通过π-π堆积和氢键进一步连接成三维超分子结构。配合物1和2分别显示Eu3+和Dy3+离子的特征荧光。     

基于1-丁基苯并咪唑和对苯二甲酸混合配体的锌(Ⅱ)和铜(Ⅱ)一维配位聚合物:晶体结构和弱相互作用(英文)

用1-丁基苯并咪唑和对苯二甲酸与Zn(NO3)2.6H2O或Cu(NO3)2.3H2O反应合成了两个锌(Ⅱ)和钴(Ⅱ)的一维配位聚合物[Zn(L)2(TP)]n(1)和[Cu(L)2(TP)]n(2)(L=1-丁基苯并咪唑,TP=对苯二甲酸根)。配位聚合物1和2通过C-H…O或O-H…O氢键形成了二维超分子层。测定了L,1和2的荧光发射光谱。     

基于2-氨基对苯二甲酸的镉配位聚合物的合成、晶体结构和性质研究

以2-氨基对苯二甲酸根离子(AT)为配体,合成了3个结构新颖的镉配位聚合物:[Cd(AT)(H2O)]n(1)、[Cd(AT)(Py)]n(2)和[Cd(AT)(BPP)]n(3)(AT=2-氨基对苯二甲酸根离子,Py=吡啶,BPP=1,3-二(4-吡啶基)丙烷)。晶体结构表明,随着辅助配体的改变,AT表现出3种不同的配位模式,分别形成rtl(1)、ths(2)和sql(3)3种不同的拓扑结构。由于分子内/分子间氢键、芳香环之间的π…π堆积与C-H…π相互作用,使得3个化合物展现出较好的热稳定性。     

两个一维镁配位聚合物的合成、晶体结构和荧光性质

本文以Mg(NO3)2.6H2O分别与4,5-咪唑二羧酸(4,5-imidazoledicarboxylic acid,H3imdc)和3,5-吡唑二羧酸(3,5-pyrazoled-icarboxylic acid,H3pdc)通过水热反应合成了2个新型镁的一维配位聚合物[Mg(Himdc)(DMF)(H2O)]n(1)和[Mg(Hpdc)(H2O)2]n(2),并对配位聚合物1和2进行了元素分析、FTIR、热重分析和X-射线单晶结构解析等表征。X-射线单晶结构解析表明配位聚合物1和2的晶体分别属于正交晶系与单斜晶系,空间群分别为P212121和P21/c。配合物1为一维Z字型链状结构,配合物2为一维线型链状结构,2个配合物中的链与链之间均通过氢键相互作用堆积成三维结构。对1和2进行固态荧光光谱分析,结果显示,1和2的荧光发射峰与各自的配体的荧光发射峰峰形一致,说明2个配合物的荧光发射峰应归属于各自配体内的π→π*电子跃迁。     

[Ag(4，4′-bpy)]+及[Zn(phen)2(H2O)2]2+两种配合物的合成、结构与荧光性质

用水热法和溶液法分别合成了2个新的配合物{[Ag(4,4′-bpy)]·3-HSBA.H2O}n(1)和[Zn(phen)2(H2O)2]·(A-2,5-DSA)·3H2O(2)(3-HSBA=3-羧基苯磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,4,4′-bpy=4,4′-联吡啶,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了其晶体结构。配合物1是一维链状结构。在1个不对称单元中包含1个[Ag(4,4′-bpy)]+阳离子,1个3-羧基苯磺酸根阴离子和1个晶格水分子。Ag髣离子与2个4,4′-联吡啶的2个氮原子配位。配合物2是单核结构。在1个不对称单元中包含1个[Zn(phen)2(H2O)2]2+阳离子,1个苯氨-2,5-二磺酸根阴离子和3个晶格水分子。Zn髤离子与2个1,10-邻菲咯啉的4个氮原子和2个水氧原子配位。配合物1和2中,配位阳离子、抗衡阴离子以及晶格水分子之间存在丰富的氢键,进而构筑成超分子网络结构。配合物的荧光均来自于配体的π-π*电子跃迁。     

Synthesis,psychotropic and anticancer activity of 2,2‐dimethyl‐5‐[5′‐trialkylgermyl(silyl)‐2′‐hetarylidene]‐1,3‐dioxane‐4,6‐diones and their analogues

A series of 2,2‐dimethyl‐5‐(5′‐R‐hetarylidene)‐1,3‐dioxane‐4,6‐diones has been synthesized for examing a structure–activity relationship. Furyl and thienyl derivatives of Meldrum's acid possess neurotropic activity comprising both depriming and activating components. Comparison of acute toxicity of carbon, silicon and germanium analogues in the furan series of the compounds has demonstrated that the germanium derivative is 11.5 times less toxic than the carbon analogue and four times less toxic than the silicon derivative. 2,2‐Dimethyl‐5‐(5′‐triethylsilyl‐2′‐thenylidene)‐1,3‐dioxane‐4,6‐dione has moderate toxicity with the highest neurotropic and cytotoxic activity Copyright © 2003 John Wiley & Sons, Ltd.     

The Synthesis of 2‐(Chromon‐2/3‐yl)‐3‐(5‐thione‐4‐hydro‐1,3,4‐thiadiazol‐2‐yl)‐4‐oxo‐thiazolidine

2‐Formylchromones and 3‐formylchromones as the first materials singly reacted with 2‐amino‐5‐mercapto‐1,3,4‐thiadiazole to give the corresponding Schiff bases, which on cyclocondensation with mercapto‐acetic acid in 1,4‐dioxane yielded target compounds named 4‐oxo‐thiazolidines. The structures of all the synthetic compounds were confirmed by elemental analysis and IR, ¹H NMR, LC‐MS (ESI) spectral data.     

Heterocyclic Systems Containing Bridged Nitrogen Atom: Synthesis and Antibacterial Activity of 3‐(2‐Phenylquinolin‐4‐yl)/3‐(1‐p‐Chlorophenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazine Derivatives

The condensation of 4‐amino‐5‐mercapto‐3‐(2‐phenylquinolin‐4‐yl)/3‐(1‐p‐chlorophenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,2,4‐triazoles 1a‐b with chloroacetaldehyde 2a‐b , ω‐bromo‐ω‐(1H‐1,2,4‐triazol‐1‐yl)acetophenone 3a‐b , chloranil 4a‐b , 2‐bromocyclohexanone 5a‐b , 2,4′‐dibromoacetophenone 6a‐b and 2‐bromo‐6′‐methoxy‐2′‐acetonaphthone 7a‐b are described. The structures of the compounds synthesized were confirmed by elemental analyses, IR, 1H NMR and mass spectra. The antibacterial activities were also evaluated.     

Syntheses of 4‐(5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones and 4‐(4‐arylamino‐5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones from Sydnone Derivatives and Their Fragments

4‐(5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones 11 and 4‐(4‐arylamino‐5‐oxo‐1,2,4‐triazol‐3‐yl)‐sydnones 13 have been obtained from a‐chloroformylarylhydrazine hydrochloride 2 . Moreover, the intermediates, including 3, 4 , 9 and 10 , in this study are synthetically informative and valuable. It is also noteworthy that three reactants, 1, 2 and sydnonecarbaldehydes, were prepared from sydnone derivatives and their fragments. The oxidative cyclizations of sydnonecarbaldehyde semicarbazones 9 and carbazones 10 with two different oxidizing agents (Cu(ClO₄)₂ and Fe(ClO₄)₃) have been extensively examined. The reaction time and the yields of cyclizations were affected by the substituents of semicarbazones 9 and carbazones 10.     

Synthesis of Substituted 4‐Aroyl‐1‐indanone and 5‐Aroyl‐1‐tetralone

Several substituted 4‐aroyl‐1‐indanones 2 and 5‐aroyl‐1‐tetralones 3 were prepared in good yields from 1‐indanones 1 via a series of reasonable transformations.     

Synthesis of 3‐[5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐yl]‐6‐substituted‐s‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles

Several 3‐[5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐yl]‐6‐substituted‐1,3,4‐triazolo[3,4‐b]‐1,3,4‐thiadiazoles have been synthesized and the structures of these compounds were established by elemental analysis, MS, IR and ¹H NMR spectral data.     

Chain composition dependence of luminescence properties for copolymers of 2‐methoxy‐5‐2′‐ethyl‐hexyloxy‐1,4‐phenylenevinylene and 2,3‐diphenyl‐5‐octyl‐1,4‐phenylenevinylene

The copolymers of 2‐methoxy‐5‐2′‐ethyl‐hexyloxy‐1,4‐phenylenevinylene (MEH‐PV) and 2,3‐diphenyl‐5‐octyl‐1,4‐phenylenevinylene were prepared via the Gilch route with their chain compositions and the reactivity ratios of the monomers estimated by ¹H NMR spectroscopy. The results indicated that the copolymers tended to form an alternative copolymer as the feed ratio of the monomers closed to one‐half. When an individual copolymer solution in tetrahydrofuran was spun‐cast to form a film, the MEH‐PV units were able to attract the like units from the adjacent chains. As a result, the ultraviolet–visible absorption spectrum of the alternative copolymer in film form was broader than the spectra of those with different compositions. The photoluminescence spectra of the copolymers in film form exhibited the characteristic shoulder of poly(2‐methoxy‐5‐2′‐ethyl‐hexyloxy‐1,4‐phenylenevinylene), even though the content of MEH‐PV units was not great enough for the formation of repeat units in sequence. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2180–2186, 2003     

Report on an Unusual Cascade Reaction between Azulenes and 2,3‐Dichloro‐5,6‐dicyano‐1,4‐benzoquinone (=4,5‐Dichloro‐3,6‐dioxocyclohexa‐1,4‐diene‐1,2‐dicarbonitrile; DDQ)

The oxidation of 1‐(3,8‐dimethylazulen‐1‐yl)alkan‐1‐ones 1 with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (=4,5‐dichloro‐3,6‐dioxocyclohexa‐1,4‐diene‐1,2‐dicarbonitrile; DDQ) in acetone/H₂O mixtures at room temperature does not only lead to the corresponding azulene‐1‐carboxaldehydes 2 but also, in small amounts, to three further products (Tables 1 and 2). The structures of the additional products 3 – 5 were solved spectroscopically, and that of 3a also by an X‐ray crystal‐structure analysis (Fig. 1). It is demonstrated that the bis(azulenylmethyl)‐substituted DDQ derivatives 5 yield on methanolysis or hydrolysis precursors, which in a cascade of reactions rearrange under loss of HCl into the pentacyclic compounds 3 (Schemes 4 and 7). The found 1,1′‐[carbonylbis(8‐methylazulene‐3,1‐diyl)]bis[ethanones] 4 are the result of further oxidation of the azulene‐1‐carboxaldehydes 2 to the corresponding azulene‐1‐carboxylic acids (Schemes 9 and 10).     

One‐Pot Synthesis of 4‐(Alkylamino)‐1‐(arylsulfonyl)‐3‐benzoyl‐1,5‐ dihydro‐5‐hydroxy‐5‐phenyl‐2H‐pyrrol‐2‐ones via a Multicomponent Reaction

An effective route to novel 4‐(alkylamino)‐1‐(arylsulfonyl)‐3‐benzoyl‐1,5‐dihydro‐5‐hydroxy‐5‐phenyl‐2H‐pyrrol‐2‐ones 10 is described (Scheme 2). This involves the reaction of an enamine, derived from the addition of a primary amine 5 to 1,4‐diphenylbut‐2‐yne‐1,4‐dione, with an arenesulfonyl isocyanate 7 . Some of these pyrrolones 10 exhibit a dynamic NMR behavior in solution because of restricted rotation around the C? N bond resulting from conjugation of the side‐chain N‐atom with the adjacent α,β‐unsaturated ketone group, and two rotamers are in equilibrium with each other in solution ( 10 ? 11 ; Scheme 3). The structures of the highly functionalized compounds 10 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS), by elemental analyses, and, in the case of 10a , by X‐ray crystallography. A plausible mechanism for the reaction is proposed (Scheme 4).     

Photocycloaddition Reactions of 5,5‐Dimethyl‐3‐(3‐methylbut‐3‐en‐1‐ynyl)cyclohex‐2‐en‐1‐one

The title cyclohexenone 1d undergoes photodimerization selectively at the exocyclic C?C bond to give a 1 : 1 mixture of 1,2‐dialkynyl‐1,2‐dimethylcyclobutanes 6 and 7 . On irradiation in the presence of 2,3‐dimethylbuta‐1,3‐diene, 1d affords bicyclo[8.4.0]tetradeca‐1,2,3,7‐tetraen‐11‐one 9 . This – formal – (6+4)‐cycloadduct undergoes quantitative isomerization to 3‐cycloheptadienyl‐2,5,5‐trimethylcyclohex‐2‐enone 11 on treatment with basic silica gel.