[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O超分子化合物的晶体结构、荧光性质及热稳定性

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C10H10N2O4,简作H3L)、1,10-菲啰啉C12H8N2,简作phen)与Eu(NO3)3·4H2O反应,首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O.该晶体属三斜晶系,P1空间群,晶胞参数a=1.378 6(12) nm,b=1.398 8(12) nm,c=1.759 7(16) nm,α=73.977(11)°,β=68.598(12)°,γ=71.224(12)°,V=29.42(4) nm3,Z=2,μ=2.208 mm-1,Dc=1.746 Mg/m3,F(000)=1 556,R=0.037 7,ωR=0.074 4,GOF=0.916.每个配合物晶体中均有两个相似的结构单元,每个结构单元中铕(Ⅲ)配位数为9,分别与两个2-羰基丙酸水杨酰腙和3个水分子配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和CN中的氮与Eu3+配位,形成两个共边的稳定的五元环,另3个配位原子则分别来自3个水分子中的氧原子,该结构单元在空间呈扭曲的单帽四方反棱柱,而在每两个铕的九配位单元周围还有一个游离的1,10-菲啰啉分子和4个水分子.IR,1H NMR及热分解结果佐证了配合物的组成.该配合物具有很好的荧光特性.     

镝(Ⅲ)与酰腙及1,10菲啰啉多元配合物的晶体结构及荧光性质

在水乙醇混合体系中,首次得到2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄),1,10-菲哕啉(C₁₂H₈N₂,简写作phen)与Dy(NO₃)3·3H₂O的配合物[Dy(C₁₀H₈N₂O₄)(phen)(NO₃)(H₂O)₂]·H₂O.该配合物属单斜晶系,空间群为P2₁/c,晶胞参数a=1.524(3)nm,b=1.1018(19)nm,c=1.468(3)nm,β=92.28(2)°,V=24.63(7)nm³,Z=4,μ=3.100 mm^-1,D_c=1.831g/cm³,F(000)=1340,R=0.0314,wR=0.0660,GOF=O.966.测试结果表明,该单晶结构为镝的9配位配合物,其中一个2-羰基丙酸水杨酰腙分子以羧基氧、酰胺基中的羰基氧和C=N中的氮与Dy³⁺三齿配位,形成两个稳定的共边五元环,一个1,10-菲哕啉分子以二齿方式配位、一个硝酸根和两个水分子也同时参与配位,在空间呈扭曲的单帽四方反棱柱,而在配合物周围还有一个游离的水分子.发光性能测试表明配合物具有很好的荧光性能.     

二水·2-羰基丙酸水杨酰腙合铜配(Ⅱ)合物的晶体结构及生物活性

在水中,以2-羰基丙酸水杨酰腙与硫酸铜反应,制得新配合物Cu(C10H8N2O4)(H2O)2(C10H8N2O42-为2-羰基丙酸水杨酰腙负离子),并以水为溶剂培养了单晶,测试了晶体结构,该单晶为深绿色,属单斜晶系,空间群为C2/c,晶胞参数a=1.1297(1)nm,b=0.9824(8)nm,c=2.1973(3)nm,β=91.91(8)°,V=2.43749(8)nm3,Z=8,μ=1.817mm-1,Dc=1.743Mg·m-3,F(000)=1304,R=0.0264,wR=0.0654,GOF=1.052。其测试结果表明在配合物中Cu2+处于五配位的四方锥配位环境,配位原子分别来自1个三齿配体2-羰基丙酸水杨酰腙负二价离子的2个O原子和1个N原子,2个水分子中的O原子,其中1个水分子的O原子处于四方锥的锥顶,锥底的配位原子基本处于同一平面上。对该配合物所作的皿内抑菌试验和盆栽活体实验表明,配合物对小麦条锈病、白菜黑斑病及辣椒疫霉菌等分别有96%、89%、100%的抑制率,且有一定的助长作用。     

铜(Ⅱ)与咪唑及2-羰基丙酸水杨酰腙混配体配合物的合成、晶体结构及热分解研究

以2-羰基丙酸水杨酰腙、咪唑与五水硫酸铜在水中反应,首次制得混配体配合物Cu(C10H8N2O4)(C3H4N2)(H2O)[C10H8N2O42-为2-羰基丙酸水杨酰腙负离子;C3H4N2为咪唑],并在甲醇溶剂中培养出单晶.该单晶为深绿色,属单斜晶系,空间群为P2(1)/c,晶胞参数a=1.50583(5)nm,b=1.08411(3)nm,c=0.94366(2)nm,a=90°,β=101.5583(11).,γ=90°,V=1.50927(7)nm3,Z=4,μ=1.479 mm-1,Dc=1.628 Mg/m3,F(000)=756.00,R=0.0340,ωR=0.0777,GOF=1.025.晶体测试结果表明,配合物中Cu(Ⅱ)的配位数为5,处于四方锥配位环境,其中配体2-羰基丙酸水杨酰腙的羧基以单齿配位,腙基上C=N的N配位以及羰基(C=O)的O配位,咪唑的3位N参与了配位,这四个配位原子处于四方锥的锥底,另一个配位原子来自H2O中的O,它处于四方锥的锥顶.在晶胞中,除分子内存在氢键外,分子间也存在氢键.根据TG-DTG曲线研究了配合物的热分解过程,利用Kissinger公式计算了配合物主要分解阶段的表观活化能.     

稀土与2-羰基丙酸水杨酰腙及1,10-菲啰啉配合物的合成及其光学性质

合成了12个新型的稀土(RE)与2-羰基丙酸水杨酰腙(H3L)和1,10-菲啰啉(phen)的三元配合物[RE2(H2L)2(HL)2·(phen)·n H2O(RE=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb,Lu和Y)(1La~1Y)],其结构经1H NMR,IR和元素分析表征。利用UV-Vis和FL研究了1La~1Y的光学性质。结果表明,1La~1Y的λmax均位于322 nm~326 nm和297 nm~301 nm。     

[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C_(10)H_(10)N_2O_4)、2,2-联吡啶(C_(10)H_8N_2,简写bipy)与Eu(NO_3)_3·4H_2O反应,首次培养出黄色单晶[Eu(C_(10)H_9N_2O_4)(C_(10)H_8N_2O_4)(H_2O)_3]·0.5bipy·3H_2O.该晶体属三斜晶系,空间群为P-1,晶胞参数a=0.93392(16)nm,b=1.3100(2)nm,c=1.3895(2)nm,α=97.205(3)°,β=105.411(2)°,γ=106.364(2)°,V=15.35(2)nm~3,Z=2,μ=2.118mm~(-1),Dc=1.686Mg/m~3,F(000)=786,R=0.0116,wR=0.0507,GOF=0.995.晶体测试结果表明,该单晶结构为铕的9配位配合物,两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位;每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C=N中的氮与Eu~(3+)配位,形成两个共边的稳定五元环,另三个配位原子则分别来自三个水分子中的氧原子,该配合物在空间呈扭曲的单帽四方反棱柱,而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子,这些游离分子与配位分子之间存在大量分子内和分子间氢键,整个分子在空间呈三维网状结构.发光性能测试表明该配合物具有很好的荧光性质.     

铜〔Ⅱ)与咪唑及2-羰基丙酸水杨酰腙混配体配合物的合成、晶体结构及热分解研究

以2-碳基丙酸水杨酰腙、咪唑与五水硫酸铜在水中反应，首次制得混配体配合 物Cu(C10H8N2O4）（C3H4N2）（H2O）[C10H8N2O4^2-为2-羰基丙酸水杨酰腙负离子 ；C3H4N2为咪唑]，并在甲醇溶剂中培养出单晶．该单晶为深绿色，属单斜晶系， 空间群为P2（1）/c，晶胞参数a=1.50583(5)nm,b=1.08411(3)nm,c=0.94366(2)nm, α=90°，β=101.5583(11)°,γ=90°,V=1.50927(7)nm^3,Z=4,μ=1.479mm^-1, Dc=1.628Mg/m^3,F(000)=756.00,R=0.0340,ωR=0.0777,GOF=1.025。晶体测试结果 表明，配合物中Cu(Ⅱ)的配位数为5，处于四方锥配位环境，其中配体2—羰基丙酸 水杨酰腙的羧基以单齿配位．腙基上C≡N的N配位以及碳基(C≡0)的0配位，咪唑的 3位N参与了配位，这四个配位原子处于四方锥的锥底，另一个配位原子来自H20中 的0，它处于四方锥的锥顶．在晶胞中，除分子内存在氢键外，分子间也存在氢键 ．根据TG-DTG曲线研究了配合物的热分解过程，利用Kissinger公式计算了配合物 主要分解阶段的表观活化能．     

含肽键芳酰腙镧(Ⅲ)配合物的合成、表征及对四种作物病害的抑制作用

合成了未见文献报道的镧(Ⅲ)与含肽键芳酰腙配体(2-羰基丙酸水杨酰腙)的配合物,经化学分析、元素分析及摩尔电导率等表征推测其组成为:La(H2L)(HL)·H2O(H3L为2-羰基丙酸水杨酰腙C10H10N2O4)。通过红外、紫外及荧光的研究表明配体以羧基氧、羰基氧和亚氨基氮与La3+三齿配位,形成了两个共边五元环的稳定结构。盆栽活体试验表明该配合物对四种作物病害都有不同程度的抑制作用,其中对小麦条锈病的防治效果最好,防治效果达80.8%。     

两个单核镍含氮配体配合物的合成、晶体结构及荧光性质(英文)

采用回流法在水溶剂中合成了2个含氮配体单核镍配合物[Ni(phen)2(H2O)2](1,6-nds)·2H2O(1)和[Ni(phen)3](1,6-nds)·10H2O(2)(1,6-nds=1,6-萘二磺酸根离子,phen=1,10-邻菲罗啉)。配合物1中,镍离子与2个1,10-邻菲罗啉和2个水分子配位,形成[Ni(phen)2(H2O)2]2+阳离子。2个没有配位的水分子通过氢键与[Ni(phen)2(H2O)2]2+和1,6-萘二磺酸根离子相互连接形成二维层状结构。配合物2中,镍离子与3个1,10-邻菲罗啉配位,形成[Ni(phen)3]2+阳离子。大量的氢键将自由的水分子和1,6-萘二磺酸根离子连接形成三维网状结构。2个配合物中1,6-萘二磺酸根离子均没有与镍离子配位,只是起到平衡电荷的作用。室温下,配合物显示了较大的荧光发射峰,其最大发射峰分别在443和438 nm。     

二维网状结构双核配合物[Ca_2(C_(10)H_8N_2O_4)_2(DMSO)_2(H_2O)_4]·2DMSO的合成、热分解及晶体结构

以2-羰基丙酸水杨酰腙(C_(10)H_(10)N_2O_4)作为配体与碳酸钙在水中反应， 在DMF(N,N'-二甲基甲酰胺)和DMSO（二甲基亚砚）的混合溶剂中培养了单晶，其组 成为 [Ca_2(C_(10)H_8N_2O_4)_2(DMSO)_2(H_2O)_4]·2DMSO [C_(10)H_8N_2O~2- _4为2-羰基丙酸水杨酰腙负离子]。测字了单晶的结构，该单晶为黄色，属单斜晶 系，空间群为P2(1)/C，晶胞参数a=1.0634(3)nm, b=1.7035(5)nm, c=1.2183(3) nm, β=106.180(5)°, V=2.1192(10)nm!, Dc=1.412Mg·m~(-3), Z=2, F(000) =944, μ=0.534m~(-1)，GOF=0.867。所测单晶是以2-卷曲在丙酸水杨酰腙羧基上 的一个氧原子作为桥联的双核钙（II）配合物，两个Ca~(2+)均处于五角双锥的七 配位环境中，锥底为配体2-羰基丙酸水杨酰腙中的三个配位原子，以及另一2-羰基 丙酸水杨酰腙羧基上的桥联氧原子和一个水分子的配位氧原子，锥顶为一配位水和 一想位的DMSO分子，即溶剂DMSO也参也了配位，从晶胞结构看，晶体中除配位的 DMSO分子外，还有自由的DMSO溶剂分子，它们与配位水以氢键连接存在于晶格之中 ，在空间形成的二维网状结构。通过TG-DTG还测定了配合物的热稳定性。     

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.