以二茂铁二羧酸为配体的锌配位聚合物[Zn(Py)2L]n的合成与晶体结构

具有金属有机框架的配位聚合物与以往的以硅酸盐、硅铝酸盐和磷铝酸盐作为骨架的沸石和分子筛微孔晶体材料不同，是利用具有多齿配位能力的有机多酸或多碱和金属离子作为结构单元构筑的无机-有机杂化微孔晶体材料。这类新结构在选择性催化、分子识别、可逆性主客体分子(离子)交换、超高纯度分离、光电材料和磁性材料等新型功能材料的开发中显示了广阔的应用前景。     

羧酸类金属有机框架材料的合成及应用

金属-有机框架材料(Metal-Organic?Frameworks,简称MOFs)是由金属离子（簇）与有机桥接配体通过配位共价键或弱相互作用自组装形成的一类具有分子内孔隙的有机-无机杂化材料。羧酸类MOFs材料中金属中心和有机羧酸配体的可变性导致了其结构和功能的多样性,在气体的吸附与分离、荧光、传感、药物传输以及电催化等多个领域展现了独特的应用前景,并被认为是当今科学上最有前途的材料之一。对于有机配体的选择,从早期易坍塌的含氮杂环类配体过渡到了如今稳定性好的羧酸类配体,解决了不少以前出现的MOFs材料结构单一易坍塌问题。     

动态化学与材料和非晶物理新关联——金属有机框架玻璃的挑战、进展与新机遇

金属有机框架(简称MOF)玻璃为传统玻璃世界和非晶物理研究带来崭新成员,被视为下一代多孔化学及新型MOF衍生功能材料关键发展方向.作为金属离子或簇核与有机配体通过配位键连接形成的多孔网络,绝大多数MOF还未达到高温熔融态就不可避免地发生热分解,很难通过传统的熔融-淬冷法制备玻璃.面对相关挑战,本综述系统梳理MOF玻璃发展历程及最新进展,提出基于动态化学串联扰动的全新策略用于普适化制备MOF玻璃.基于新的玻璃化方法,发现更多MOF玻璃、阐明结构转变本质并拓展新颖性质功能是从动态化学到材料和非晶物理的重大学科交叉前沿.相关研究孕育系列新机遇,包括从框架/动态化学的设计和调控到MOF玻璃可控制备,从晶态MOF本征性质到其玻璃态的各种潜在性能及新功能应用,以及从MOF多物相多层次结构转换出发更好理解玻璃本质.     

MOFs在催化有机分子转化中的应用

金属有机框架化合物（MOF）,又称多孔性配位聚合物,是有机配体与金属离子自组装而成的一类新型有机-无机杂化多孔材料,是纳米材料的重要组成部分。与其他多孔材料相比,MOFs具有较大的比表面积、高的孔隙率以及结构和性质可调等特性,使其在非均相催化领域具有良好的应用前景。本文首先对MOFs催化的背景进行简述,然后对近年来报道的MOFs用于有机分子催化转化反应的进展进行了综述及展望,以期为MOFs催化有机反应的设计和开发提供参考。     

金属有机框架基复合材料的制备及其光热性能研究

金属有机框架材料(metal-organic frameworks, MOFs)是一类新型的有机-无机杂化材料, 具有可功能化的骨架结构、高比表面积、可调控的孔径尺寸等优势. 将MOFs与性质多样的有机/无机功能纳米材料复合, 不仅有可能充分发挥组分各自的优势, 而且有可能产生“1+1>2”的协同效应, 因而引起了人们的广泛关注. 具有光热效应的MOF复合物作为一类重要的MOF复合材料, 在生物诊疗、催化等领域展现出了良好的应用前景. 作者首先综述了近年来MOF复合材料的主要可控制备方法, 随后讨论了光热MOF复合材料的应用研究, 最后对该类材料的未来研究方向和挑战进行了展望.     

锰钒氧无机-有机杂化材料

氧化锰、钒氧簇构筑块经与有机组分组合可形成新型结构的锰钒氧无机-有机杂化材料。人们预测锰钒氧无机-有机杂化材料将兼有金属锰配合物和钒氧无机-有机杂化材料结构的多样性、独特的物理性质和广阔的应用前景。本文综述了近年来锰钒氧无机-有机杂化材料的合成、组成、结构及有关性质的研究与进展。     

多金属氧酸盐有机-无机杂化材料

本文总结并评述了多金属氧酸盐 (POMs)有机 无机杂化材料领域的研究进展 ,包括POM有机或有机金属衍生杂化材料 ,电荷转移 (CT)盐和有机 无机复合膜。POM有机或有机金属衍生杂化材料分为四类 ,即 ( 1 )配体作抗阳离子 ,( 2 )配体直接与POM骨架配位 ,( 3)配体与杂金属配位 ,和 ( 4)有机金属作配体。此外 ,本文还描述了POMCT杂化材料 ,它们含有不同的有机p 电子给体 ,例如取代酰胺、芳香胺或富含电子的四硫富瓦烯 (TTF)、双 (乙烯二硫基 )四硫富瓦烯 (BEDT TTF或ET)及二茂铁 ;以及POM装法和电化学生长法。最后 ,本文对这些杂化材料的理性合成与潜在应用进行了展望     

Lindqvist型多酸亚胺衍生物的理论研究及设计

多金属氧酸盐的修饰化学是近年发展起来的一个热点研究领域,其中多酸的亚胺化是一种非常有效的使多酸有机官能化的方法.有机胺能够将其π电子扩展到无机框架,产生较强的d-π相互作用,从而多金属氧酸盐有机胺衍生物和远程有机官能团可以作为构筑单元构建更为复杂的多金属氧酸盐-有机杂化材料.本文综述了作者研究小组运用密度泛函理论方法研究系列Lindqvist型多酸亚胺衍生物的稳定性、成键特征和非线性光学性质,深入探讨该类有机-无机杂化衍生物非线性光学性质的起源.     

多孔配位聚合物:发展历程及研究进展

多孔配位聚合物(PCP)(包括金属有机框架)是一类由金属节点和配体通过配位键连接形成的晶态多孔材料.作为一类新兴的无机-有机杂化材料, PCP具有丰富且可调节的结构和功能,因此其在气体吸附分离、催化、传感等诸多领域展现出巨大的应用潜力,是多学科交叉的研究热点.本文依据PCP的结构及性质特点,总结了第一至第四代多孔配位聚合物PCP研究的发展历程,介绍了该领域的主要研究内容和典型研究进展,进而基于该领域未来面临的挑战和发展趋势分析了材料的实用化前景.     

三维无机-有机杂化骨架微孔化合物[Co3(BDC)3(EG)4]·2DMF的合成与结构

传统的微孔晶体材料是以硅酸盐、硅铝酸盐、磷铝酸盐和无机金属磷酸盐等作为结构的骨架[1,2]. 近几年来, 出现了一类新型的无机-有机杂化微孔晶体材料, 这类晶体材料是用刚性和热稳定性较好的有机分子(如芳香多酸和多碱)和金属离子作为骨架的结构单元. 它们能够在去除孔道中的溶剂分子后仍然保持骨架的完整性, 而且其孔道的直径在0.4～1.0 nm之间, 比表面积远大于相似孔道的分子筛. 因此, 这类材料具有许多潜在的特殊性能, 在选择性催化、分子识别和可逆性主客体分子(离子)交换等方面具有诱人的应用前景. Yaghi等[3～11]利用不同的有机分子和各种金属制备出了许多这类晶体材料. 对苯二酸是常见的有机配体, 以它和金属离子为结构骨架所形成的无机-有机杂化微孔晶体有Zn3(BDC)3*(CH3OH),Zn(BDC)*(DMF)(H2O),(TPT)(Py)Cd和Zn4O(BDC)3*(DMF)8(C6H5Cl)等[12～15], 但在对苯二酸与金属构成的骨架中, 由于有多个乙二醇分子配位, 很少形成稳定的三维骨架结构的无机-有机杂化微孔晶体.     

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.