4-吡啶-NH-1,2,3-三唑构筑的两个Zn（Ⅱ）配合物的合成、结构和荧光性质

以4-吡啶-NH-1,2,3-三唑（L）为配体与ZnCl₂·H₂O分别在溶剂热和室温挥发条件下得到了配合物[Zn₂（L）₂Cl₄]（1）和[Zn（L）₂ Cl₂]·2H₂O（2）,并进行了红外、元素分析、单晶衍射、粉末衍射等表征。2个配合物中,超分子相互作用对于配合物的结构有很大影响。其中,配合物1由氢键和π-π相互作用形成3D堆积结构,配合物2通过氢键作用形成堆积结构。同时,在常温下研究了配体以及2个配合物的固体和液体荧光性质。     

基于3,5-二(3-吡啶)-4-氨基-1,2,4-三唑配体的Co(Ⅱ)和Cu(Ⅱ)配合物的合成与晶体结构

利用3,5-二（3-吡啶）-4-氨基-1,2,4-三唑（L）配体与Co（Ⅱ）/Cu（Ⅱ）盐室温下反应得到了一维的配位聚合物{[CoL（H₂O）₄]SO₄·H₂O}_n（1）和单核配合物[Cu（hfac）₂L₂]（2,hfac=hexafluoroacetylacetonate）。通过红外、元素分析及X射线单晶衍射等检测手段对所合成的配合物进行了表征。结构研究表明,配合物1中,配体L呈顺式构型,采取双齿配位方式桥联Co（Ⅱ）离子形成一维正弦链状结构,一维链通过多种氢键相互作用连接进一步形成三维网状结构;溶剂水分子和硫酸根阴离子通过氢键连接在框架上。配合物2中,配体L则采取单齿配位方式,与Cu（Ⅱ）离子形成离散型的单核结构,通过多重氢键作用进而连接成三维网状结构。     

基于π-共轭4-四硫富瓦烯-2，6-吡嗪吡啶配体的Fe（Ⅱ）配合物

设计、合成了功能化的4-四硫富瓦烯-2,6-吡嗪吡啶配体（L）,并以此为配体合成了具有电活性的配合物[Fe（Ⅱ）（L）₂]（BF₄）₂·2.75CH₃CN·0.25CH₂Cl₂ （1）,通过红外、元素分析及X射线单晶衍射等手段对所合成的化合物进行了表征。配体以三齿的方式参与配位,形成离散型的配合物1,该配合物中含有多种非经典氢键和π…π以及S…S作用。此外研究了该配合物的磁性、电化学性质和光谱电化学性质。     

两个4-[(8-羟基-5-喹啉)偶氮]苯磺酸配合物的合成、结构及性质研究

以4-[(8-羟基-5-喹啉)偶氮]苯磺酸(H₂L)为配体,采用溶剂热合成法合成了两个配合物[CuL(en)]·0.5H₂O (1)和[CuL₂][Cu(en)₂]·2H₂O (2)(en=乙二胺),并采用单晶X-射线衍射、红外光谱、元素分析、X-射线粉末衍射和热重分析对其进行表征。化合物1和2通过氢键和π…π相互作用连接形成了三维超分子网格。此外,还研究了两个化合物的荧光性质。     

基于3,5-二(3-吡啶)-4-氨基-1,2,4-三唑配体的Co(Ⅱ)和Cu(Ⅱ)配合物的合成与晶体结构

利用3,5-二（3-吡啶）-4-氨基-1,2,4-三唑（L）配体与Co（Ⅱ）/Cu（Ⅱ）盐室温下反应得到了一维的配位聚合物{[CoL（H₂O）₄]SO₄·H₂O}_n（1）和单核配合物[Cu（hfac）₂L₂]（2,hfac=hexafluoroacetylacetonate）。通过红外、元素分析及X射线单晶衍射等检测手段对所合成的配合物进行了表征。结构研究表明,配合物1中,配体L呈顺式构型,采取双齿配位方式桥联Co（Ⅱ）离子形成一维正弦链状结构,一维链通过多种氢键相互作用连接进一步形成三维网状结构;溶剂水分子和硫酸根阴离子通过氢键连接在框架上。配合物2中,配体L则采取单齿配位方式,与Cu（Ⅱ）离子形成离散型的单核结构,通过多重氢键作用进而连接成三维网状结构。     

基于π-共轭4-四硫富瓦烯-2,6-吡嗪吡啶配体的Fe(Ⅱ)配合物

设计、合成了功能化的4-四硫富瓦烯-2,6-吡嗪吡啶配体（L）,并以此为配体合成了具有电活性的配合物[Fe（Ⅱ）（L）₂]（BF₄）₂·2.75CH₃CN·0.25CH₂Cl₂ （1）,通过红外、元素分析及X射线单晶衍射等手段对所合成的化合物进行了表征。配体以三齿的方式参与配位,形成离散型的配合物1,该配合物中含有多种非经典氢键和π…π以及S…S作用。此外研究了该配合物的磁性、电化学性质和光谱电化学性质。     

基于2-苯基-1H-1，3，7，8-四-氮杂环戊二烯并[l]菲的Pb（Ⅱ）、Co（Ⅱ）配合物的晶体结构与发光

采用水热法合成2种配合物[Pb₂（ptcp）₂（DDA）]（NO₃）₂·2H₂O（1）和[Co（ptcp）₂（DDA）（H₂O）]·0.5H₂DDA·H₂O（2）（ptcp=2-苯基-1H-1,3,7,8-四-氮杂环戊二烯并[l]菲,H₂DDA=1,12-十二烷二酸）,并采用单晶X-射线衍射、元素分析、红外光谱、X-射线粉末衍射和理论计算对其进行了结构表征。配合物1和2分别呈现双核和单核结构,通过π-π和氢键作用形成二维和三维结构。此外,配合物1具有较好的发光性质。利用Gaussian09W程序,采用B3LYP/LANL2DZ方法对配合物1进行自然键轨道（NBO）分析。结果表明配位原子与Pb（Ⅱ）离子之间存在明显的共价相互作用。     

基于双吡啶脲类Cd(Ⅱ)、Zn(Ⅱ)、Hg(Ⅱ)配合物的合成及晶体结构

间苯二胺和3-吡啶异氰酸酯在甲苯中加热回流得到双吡啶脲类配体L,然后将配体分别与CdSO₄·8H₂O,ZnI₂,HgI₂,HgCl₂进行配位反应,得到4个配合物{[Cd（L）（SO₄）（H₂O）₃]·H₂O}_n（1）,{[Zn（L）I₂]·2C₂H₅OH}_n（2）,{[Hg（L）I₂]·C₂H₅OH}_n（3）,[Hg（L）Cl₂]·H₂O（4）,并用元素分析、FT-IR、X射线单晶衍射、粉末衍射对其进行了表征。配合物1形成一维螺旋链结构,配合物2和3形成一维“之”字链结构,配合物4形成32元环状结构。     

1,10-邻菲啰啉和四氟对苯二甲酸构建的两个镍（Ⅱ）的配合物：合成和晶体结构

以醋酸镍、四氟对苯二甲酸（H₂tfbdc）及1,10-邻菲啰啉（phen）为原料在不同的反应条件下合成了2个镍(Ⅱ)的配合物{[Ni（phen）₂（Htfbdc）]2（μ-tfbdc）}·3H₂O（1·3H₂O）和[Ni（phen）₃]2（tfbdc）₂·13H₂O（2·13H₂O）。单晶结构分析显示配合物1·3H₂O中3D超分子结构在C-H…O/F和C-F…π弱相互作用下而成;在配合物2·13H₂O中,水分子和羧酸离子构建的三维氢键框架中含有金属有机离子链客体。此外,在这些3D超分子结构中强氢键作用、C-H…O和C-H…F等弱氢键作用,π…π及C-F/H…π作用均起到了稳定结构的作用。     

3-(2-吡啶基)-1,2,4-三唑配体Co(II)Cu(II)和Cd(II)配合物的合成、结构及荧光性质

利用3-（2-吡啶基）-1,2,4-三唑配体（HL）和不同的金属盐设计合成了5个配合物[Co（HL）₂（H₂O）₂]（NO₃）₂（1）、[Cu₂（L）₂（NO₃）₂（H₂O）₄] （2）、[Cu₂（L）₂（AcO）₂（H₂O）₂]·6H₂O （3）、[Cu₂（L）₂（HL）₂（ClO₄）₂]·2CH₃CN （4）和[Cd₂（L）₂（HL）₂（NO₃）₂]·2H₂O （5）,并通过X射线单晶衍射、红外、元素分析、X射线粉末衍射和热重对配合物结构进行了表征。测试结果表明配合物1具有单核结构,并且可以通过氢键的相互作用形成二维超分子结构。配合物2~5为双核结构。配合物2和5可以通过氢键的相互作用形成二维超分子结构。配合物3通过氢键的相互作用形成三维超分子结构。研究了配合物中HL配体的配位模式。此外,研究了配体HL和配合物1和5的固态荧光性质及荧光寿命。     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.