杯[4]芳烃修饰的钌(Ⅱ)配合物的合成与性质

合成了一种新颖的杯[4]芳烃修饰的钌（Ⅱ）配合物[Ru₂（bpy）₄（H₂L）]（ClO₄）₄（1）（bpy=2,2''-联吡啶,H₂L=11,23-双（2-咪唑[4,5-f]-1,10-菲啰啉）-25,27-二羟基-26,28-二乙酯基丙基-5,17-二-对叔丁基-杯[4]芳烃）,并通过红外光谱、核磁共振氢谱和碳谱、电喷雾质谱和元素分析对该配合物进行了表征。在乙腈/Britton-Robinson缓冲溶液（1：100,V/V）中研究了配合物1的pH光开关性质。发现随着溶液pH值的变化,配合物1经历两步质子化/去质子化过程,是一个很好的"off-on-off"型pH诱导的分子光开关,其开关比分别为1.42和96.0。通过加入不同阴离子引起配合物1溶液的吸收光谱、发射光谱和核磁共振氢谱的变化研究了其对阴离子的传感性能,发现该配合物可以通过荧光淬灭来识别F^-和OAc^-。另外初步细胞成像实验显示配合物1可以在短时间内穿过细胞膜对细胞质进行染色,而且在成像浓度范围内对Hela细胞体现出低毒性。     

一种含咔唑基团的混配型钌(II)配合物的合成、表征和酸碱性质研究

合成了钌(II)配合物cis-[Ru(HL)(Hdcbpy)(NCS)₂]^－•[N(C₄H₉)₄]^＋ (HL＝2-(9-乙基-9H-3-咔唑基)-1H-咪唑[4,5-f] [1,10]邻菲啰啉, H₂dcbpy＝4,4'-二羧酸-2,2'-联吡啶). 采用元素分析、核磁共振氢谱、红外光谱、紫外-可见吸收光谱、质谱(MS)对配合物进行了表征. 通过紫外-可见吸收光谱和稳态荧光光谱, 研究了该配合物的基态和激发态酸碱性质. 结果表明该配合物在基态时能发生5步质子化/去质子化反应, 表现出基于光致发光强度和激发态能量转移途径的质子化/去质子化诱导的分子开关性质.     

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。     

靶向DNA的刚性配体的双核芳基钌配合物

以刚性配体1,3-bib（1,3-二（1H-咪唑-1-基）苯）与[Ru（η⁶-p-bip）Cl₂]₂（p-bip,联苯基团）为原料,合成了3种双核芳基钌配合物[Ru₂（η⁶-p-bip）₂（1,3-bib）₂XY]X₂（X=Y=Cl^-（1）,X=Y=Br^-（2）,X=I^-和Y=Cl^-（3）,并用核磁和质谱等对配合物进行了表征。配合物1的单晶衍射结果表明其具有一种刚性双核M₂L₂碗状结构,空腔中心有一个阴离子Cl^-。配合物3对A549细胞有较高的抗癌活性（IC₅₀=13.9 μmol·L^-1）,与顺铂细胞毒性（IC₅₀=15.2 μmol·L^-1）相当。紫外吸收光谱、圆二色谱、凝胶电泳法研究表明配合物1~3与DNA发生强烈的相互作用并且诱发DNA发生解旋。     

基于四核金属单元的锌/镉配合物的合成、晶体结构及荧光性质

在水热条件下合成了2个金属配合物Zn₄(Hhpa)₄(phen)₄(1)和{[Cd₈(cnam)₂(bpy)₄(C₂O₄)₆(H₂O)₈]·2H₂O}_n(2)(H₂hpa=2-羟基间苯二甲酸,phen=菲咯啉,H₂cnam=4-氧代-4H-吡喃-2,6-二甲酸,bpy=2,2'-联吡啶),通过元素分析、红外光谱、X-射线单晶衍射、荧光、热重分析和X-射线粉末衍射对其进行表征。配合物1为环状四核锌结构,相邻的四核锌单元通过π…π堆积作用扩展为三维超分子结构;配合物2是基于四核镉单元通过C₂O₄^2-离子和cnam^2-配体连接而成的三维网状结构。在配合物1和2中Hhpa^2-,cnam^2-和C₂O₄^2-离子表现了丰富的配位模式。此外还研究了配合物1和2的荧光性质和热稳定性。     

四个基于间苯二(取代水杨醛酰腙)的有机锡配合物的溶剂热合成、结构和荧光性能

采用间苯二（取代水杨醛酰腙）（H₄L）与R₃²SnOH溶剂热反应,或间苯二甲酰肼、3-叔丁基水杨醛和三环己基氢氧化锡一锅溶剂热法反应,合成了4个新的有机锡配合物（SnR²）₂L（1~4）,其中,H₄L=m-Ph（CONH—N=CH（o-OH） PhR¹）₂;R¹=NEt₂,R²=Ph（1）;R¹=3,5-di-tert-butyl=3,5-t-2Bu,R²=Ph（2）;R¹=3,5-t-2Bu,R²=Cy（3）;R¹=3-tert-butyl=3-t-Bu,R²=Cy（4）。经元素分析、红外光谱和（¹H、¹³C、¹¹9Sn）核磁共振谱表征,并用X射线衍射方法确证配合物1~4的结构。配体H₄L的2个取代水杨醛酰腙链向内取向并与锡原子配位形成3个内向E型配合物1~3,取代水杨醛酰腙链向外取向并与锡原子配位形成外向E型配合物4。配合物1、2和4属于三斜晶系P1空间群,配合物3属于单斜晶系P2₁/c空间群。中心锡与配位原子构成畸形双角三锥构型。配体、配合物-三氯甲烷溶液的荧光性能表明,当具有弱荧光的配体m-Ph（CONH—N=CH（o-OH） PhNEt₂）₂（H₄L¹）和无荧光的配体m-Ph（CONH—N=CH（o-OH） Ph（3,5-t-2Bu））₂（H₄L²）分别与苯基锡、环己基锡配位后,配合物-三氯甲烷溶液发出强荧光。     

以苯四甲酸和双(咪唑基甲基)苯为配体的三维Cd-MOF材料的合成、结构及荧光性质

选择刚性的1,2,4,5-均苯四甲酸（H₄L）为主配体,以1,3-双（1H-咪唑-1-基甲基）苯（1,3-bib）为辅助配体,在水热条件下,与过渡金属离子Cd²⁺配位合成了配合物[Cd（L）_0.5（1,3-bib）（H₂O）]·H₂O（1）。利用元素分析、红外光谱、X射线单晶衍射、热重和X射线粉末衍射对其结构进行了表征,并研究了化合物的荧光性质。结果表明：配合物1属正交晶系,空间群Pbca,a=0.857 08（4）nm,b=1.912 23（10）nm,c=2.451 60（12）nm。配合物1中Cd²⁺与L^4-配体的羧基通过双齿螯合配位,通过1,3-bib连接形成三维网状结构。配合物1具有较强的荧光,其对丙酮溶剂、MnO₄^-、Hg²⁺离子有一定的荧光猝灭。     

基于苯四酸和双咪唑甲基苯构筑的Co(Ⅱ)和Ni(Ⅱ)配合物的合成、晶体结构及光催化活性

在水热条件下，得到了2例新的配位聚合物[Co（L）_0.5（1，3-bib）] （1）和[Ni₂（L）（1，4-bib）₃（H₂O）₂]·2H₂O （2），其中H₄L=1，2，4，5-苯四酸，1，3-bib=1，3-双（（1H-咪唑1-基）甲基）苯，1，4-bib=1，4-双（（1H-咪唑1-基）甲基）苯。并利用元素分析、红外光谱、单晶X射线衍射等对其进行了结构表征。结果表明：1和2均为三维网状结构，完全去质子化的配体（L^4-）在1和2中分别采取了μ₄-к²：к¹：к²：к¹和μ₂-к¹：к⁰：к¹：к⁰的配位方式。进一步的研究表明，配合物1在H₂O₂和可见光照射的条件下，在水溶液中对染料甲基橙（MO）和亚甲蓝（MB）有很好的降解效果：在180 min时，降解率分别达到83.2%和84.5%。配合物2在同样的条件下，在水溶液中对染料MB和罗丹明B（RhB）也有较好的降解作用：在180 min时，降解率分别为87.0%和77.4%。此外还详细探讨了1和2对染料光催化降解的机理。     

一种高灵敏、多响应的Zn-MOF荧光传感器对Fe3+、2，4，6-三硝基苯酚和奥硝唑的检测

在水热条件下基于H₄bta(1,2,3,5-苯四酸)和bpy(4,4''-联吡啶)配体设计、合成了一个锌的金属有机骨架(Zn-MOF){[Zn₂(bta)(bpy)(H₂O)₂]·H₂O}_n(1),并用元素分析、红外光谱、X射线单晶衍射等对其进行了结构表征。MOF 1为三维网状结构。完全去质子化的(bta)^4-配体采用了μ₆-η¹-η²-η²-η¹螯合桥联配位方式。有意思的是,MOF 1是一种高灵敏度、选择性好、多响应的荧光传感器,可用于Fe³⁺、2,4,6-三硝基苯酚和奥硝唑的快速检测。此外还研究了1的热稳定性。     

由芳香羧酸和含氮配体构筑的两个金属锌配合物的合成、晶体结构和荧光性质

以1-（4-咪唑基）-4-（四氮唑）苯（HL）与对苯二甲酸（H₂pbda）或间苯二甲酸（H₂mbda）作为混合配体,与硫酸锌进行水热合成反应,构筑了2个新的金属配位配合物[Zn₂（L）₂（pbda）]_n（1）和[Zn₂（L）₂（mbda）]_n（2）,并进行了元素分析、红外、热重、X射线粉末衍射及单晶衍射等表征。晶体结构分析表明：配合物1结构中,去质子化的L^-与锌离子结合成[Zn₂（L）₂]²⁺的二维结构,相邻的二维层由pbda^2-配体连接成二重贯穿层柱状的具有dmc拓扑的三维结构,拓扑符号为（4·8²）（4·8⁵）;配合物2是由2个羧酸基团与锌离子形成的双核[Zn₂（COO）₂]为基本单元连结而成的单一6连结具有（4¹²·6³）-pcu拓扑的三维结构。同时,对配合物1和2在室温下的固体荧光性质进行了研究。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.