呋喃和苯多烯醛分子中的共轭效应和共轭基干

呋喃和苯多烯醛系列的CNDO/2和微扰分子轨道法的计算表明, 共轭效应与共轭基干是两个不同的概念, 共轭效应包括了共轭基团之间的作用对分子性能全面的影响, 而共轭基干仅仅反映了共轭基团间的作用对前沿分子轨道的影响。这意味着, 相互之间有共轭作用的基团不一定属于同一个基干, 属于同一个共轭基干的基团之间, 必定有共轭作用。共轭基干更确切的反映了共轭基团间的作用对分子结构的依赖。     

基于中性铂炔基元的超分子有机金属凝胶研究进展

作为一类经典的软物质材料,超分子凝胶在催化、化学传感、药物释放等许多领域展示了广泛的应用前景.最近人们研究发现,在基元砌块中引入金属特别是过渡金属之后,所形成的有机金属凝胶在光电材料、催化、磁性等方面具有独特的物理化学性质.近年来,电中性铂炔基元因其独特的线性结构、易合成及丰富的光物理性质在超分子化学及材料科学中被广泛应用.总结了基于中性铂炔基元的超分子有机金属凝胶的构筑及其功能研究进展,主要包括以苯撑共轭结构为核心骨架的铂炔有机金属凝胶以及官能团修饰的铂炔有机金属凝胶.     

新型二氢卟吩类光敏剂的设计及理论计算研究

本文采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）方法对一系列具有π共轭结构的二氢卟吩类光敏剂进行了理论模拟研究,计算了此类衍生物的吸收光谱特征、分子内电荷分布特点以及三重激发态特性。结果显示,在二氢卟吩大环结构中共轭引入给电子芳香基团（对甲氧基苯基）,可使化合物（B2）的Q带吸收发生红移,分子内负电荷聚集增强,减小单重态-三重态能级差（ΔEST）,有利于发生系间窜越,使单线态氧产量增加,导致强效的肿瘤生长抑制。并且在B2分子大环中心配合Pd原子会进一步减小ΔEST。因此,对于二氢卟吩类光敏剂,引入给电子共轭基团并配合金属原子是提高其PDT治疗效果的有效改进策略。     

双二茂铁-钯配合物的合成，结构和电化学

本文讨论了由二茂铁的C-H…π作用组装的具有类环己烷结构的氨基硫脲钯金属配合物的结构和电化学性能。晶体结构中钯原子以顺式平面正方形的构型分别与两个氨基硫脲配体配位，两个配体中的二茂铁基团位于钯原子同一侧，每个二茂铁与相邻分子中的二茂铁基团通过环戊二烯基环间的C-H…π作用形成由类环己烷结构连结的二维网状结构。对钯的配合物及相关的镍和锌配合物的电化学研究表明，平面正方型的钯和镍可以有效的传递两个茂铁间的氧化-还原性能。     

具有电子给-受体结构的二茂铁衍生物的分子二阶非线性极化率

本文采用电场诱导二次谐波(EFISH)方法对所合成的10个金属有机分子的二阶非线性极化率进行了测试。这10个化合物是具有电子给体-受体共轭结构的二茂铁衍生物, 它们的非线性极化率大多未见报道。本文系统地研究了分子的给体-受体强度、共轭长度、共轭体系及共平面性等结构因素与分子二阶非线性极化率的关系。     

一个新的二茂铁-钴四核双螺旋配合物的合成，结构和电化学性质研究

利用1，1′-双羧酸二茂铁为配体设计合成了一个新的二茂铁-钴四核双螺旋配合物并研究了其电化学性能。该配合物具有一个垂直于其螺旋轴的C₂对称性，四个金属中心形成一个边长为5.4?菱形结构。二茂铁配体的两个羧基以顺式结构与两个金属中心配位。电化学研究表明作为桥联基团的金属钴配位中心能够有效传递二茂铁基团间的氧化还原性能。     

几个新型二茂铁衍生物的合成

二茂铁及其衍生物作为油类消烟剂、燃速催化剂等已得到应用,在药物、合成材料等方面亦具有应用前景。文献曾报道含二茂铁基β-二酮的合成及以它为配体的金属配合物。此类配合物均含两个以上金属原子,它们在有机合成中具有独特的催化活性。 我们将二茂铁甲酰丙酮分别与水扬酰肼、异菸肼、乙二胺及硫代氨基脲在甲醇或甲醇-水介质中进行缩合反应,合成了4个新型二茂铁衍生物,它们含有三个或四个配位功能基团,可作为多齿配体用于金属有机配合物的合成。衍生物的合成路线如下:     

全共轭型二茂铁基聚合物

由于二茂铁独特的夹心结构使含二茂铁基聚合物具有独特的电、磁、催化以及氧化还原性能。全共轭型二茂铁基聚合物由于其特殊的π-π电子结构,使其在电学、光学等方面的表现出优越的性质。本文从3个方面（主链型、侧链型和超支化型）介绍了近年来含有二茂铁基团全共轭聚合物的合成及其性能方面的研究进展,讨论了聚合物的结构对溶解性、氧化还原性等方面的影响,并探讨了这一领域存在的问题及可能的发展方向。     

基于二茂铁的金属阳离子识别受体的研究进展

由于工业的迅速发展,水体中的金属离子的浓度大幅度地增大,从而引起了一系列的危害.因此,离子识别受体和电化学传感器的研究深受科研人员的青睐.二茂铁具有稳定的氧化还原性能和易于化学修饰等特点,同时二茂铁衍生物的合成方法非常成熟,从而成为了一类非常重要的金属阳离子识别受体.按冠醚、多胺、共轭及杂环等不同分子识别中心进行分类,...     

基于配位自组装的全共轭三联吡啶-过渡金属环状超分子的构筑及其光、电化学性能*

2,2':6,2"-三联吡啶全共轭衍生物在与过渡金属离子配位络合后形成的全共轭配合物,因具有特殊的大π-π电子结构和金属-配体相互作用,成为构筑新型功能材料的重要基元,被广泛应用于光电转换、化学/生物检测、催化有机合成等领域。本文主要介绍近年来全共轭“三联吡啶-过渡金属离子（tpy-Mt）”环状超分子配合物的合成及其在光、电化学性能方面的研究进展,并探讨了该领域存在的问题及今后的发展方向。     

A novel π-donor–π-acceptor system: 1-(4,5-dimethyl-1,3-dithiol-2-ylidene)-1-ferrocenyl-3,3-dicyanopropene

The title compound was prepared by reacting the anion of malononitrile with the corresponding ethanal, and characterised by UV–vis absorption spectroscopy, cyclic voltammetry and X-ray crystallography. Attachment of an additional ferrocenyl donor group to the π-donor–π-acceptor system does not enhance intramolecular charge transfer, because its bulk distorts the planarity of the conjugated chain.     

磺化聚苯乙炔/多壁碳纳米管复合材料导电机理研究

将磺化聚苯乙炔(SPPA)与多壁碳纳米管(MWNT)超声共混制备得到SPPA/MWNT复合材料. 用四探针电阻率测试、场发射扫描电镜(FESEM)、XPS、UV-Vis、XRD等方法对复合材料导电机理进行研究. 结果表明, SPPA/MWNT的电导率发生两次突跃；掺杂剂MWNT具有低的临界阈值; 临界阈值附近, 复合材料中MWNT具有不连续分布的现象及复合材料电阻呈负温度系数(NTC)效应; SPPA/MWNT复合材料中MWNT的碳原子对SPPA 进行掺杂. 推测复合材料的导电机理为, 共轭聚合物SPPA不仅被导电粒子MWNT物理填充, 同时还被MWNT的碳原子掺杂, 使复合材料中存在两种导电通路而导电, 一是因被掺杂而成为高电导率主体的SPPA相互接触形成的导电通路, 二是MWNT相互接触形成的导电通路.     

Synthesis and Crystal Structure of N-Phenylbis（ferrocenecarboxyl）imide

The ferrocenyl compound,N-phenylbis(ferrocenecarboxyl)imide (C28H23NO2Fe2,Mr=517.17),was synthesized and structurally characterized by means of X-ray single-crystal dif-fraction. It crystallizes in monoclinic,space group C2/c with a=21.374(14),b=10.430(7),c= 10.741(7) ,β=114.184(8)°,V=2184(2) 3,Z=4,Dc=1.573 g/cm3,F(000)=1064,μ(MoKα)= 1.355 mm–1,T=291(2) K,the final R=0.0548 and wR=0.1437 for 1524 observed reflections with I > 2σ(I). In this compound,the nitrogen atom links two ferrocenyl groups and one phenyl group forming a novel imido derivative.     

E-苯甲酰二茂铁亚胺的合成、晶体结构和反应性

由苯甲酰二茂铁和一系列伯胺出发,用4A分子筛作为催化剂合成了6种相应的E-构型亚胺化合物,产率为50%～85%.该方法具有很好的通用性,同时适用于芳胺和脂肪胺,并且对杂原子具有耐受性.与文献中使用Al2O3作为催化剂的方法相比,该方法可使反应时间和催化剂的活化时间均大大缩短.所合成的席夫碱用于探索生物碱(一)-Sparteine促进的对映选择性地合成平面手性二茂铁中的反应性.根据所测定的化合物3d晶体结构数据,分析了这类化合物反应活性低的原因是空间位阻所致.而空间位阻较小的二茂铁醛亚胺用于该反应能够顺利进行.     

Carbonyl polymeric electrode materials for metal-ion batteries

This review presents the recent progress in carbonyl polymeric electrode materials for lithium-ion batteries, sodium-ion batteries and magnesiumion batteries. This comprehensive review is expected to be helpful for arousing more interest of organic materials for metal-ion batteries and designing novel battery materials with high performance.     

Pt(II)-activated coupling of aminoethylferrocene with benzonitrile. A facile access route to a new redox-active bis(ferrocenyl-amidine) anion sensor

A new heterometallic electroactive compound having the ferrocenyl moiety attached to the platinum atom through an amidine functionality has been prepared via Pt(II)-mediated nucleophilic addition of β-aminoethylferrocene to a benzonitrile ligand. This neutral receptor shows remarkable electrochemical anion-sensing redox response to H(2)PO(4)(-).     

Synthesis and characterization of novel polymeric organic–inorganic complex framework based on sodium 2,4-dioxo-6-aryl-3-oxa-bicyclo[3.1.0]hexane-1,5-dicarboxylate (SDAOBDC) with three-dimensional hybrid networks

Synthesis and characterization of novel polymeric organic–inorganic complex based on sodium 2,4-dioxo-6-aryl-3-oxa-bicyclo[3,1,0]hexane-1,5-dicarboxylate with three-dimensional hybrid networks were reported. The polymeric complex was crystallizing in the triclinic, space group P1. As determined by X-ray single-crystal analysis, in this compound each Na ion is coordinated by six O atoms: two from different carbonyl oxygen atom of carboxylic acid groups, two from bridged carbonyl oxygen atom of carboxylic acid groups, one from the carbonyl oxygen atom of cyclic anhydride and one from water molecule. The structure characterization was done by means of IR, ¹H, ¹³C NMR, UV–Vis spectroscopies, Tg, flame photometry and X-ray crystallographic analysis.     

Polymeric Schiff Bases as Low‐Voltage Redox Centers for Sodium‐Ion Batteries

The redox entity comprising two Schiff base groups attached to a phenyl ring (? N?CH? Ar? HC?N? ) is reported to be active for sodium‐ion storage (Ar=aromatic group). Electroactive polymeric Schiff bases were produced by reaction between non‐conjugated aliphatic or conjugated aromatic diamine block with terephthalaldehyde unit. Crystalline polymeric Schiff bases are able to electrochemically store more than one sodium atom per azomethine group at potentials between 0 and 1.5 V versus Na⁺/Na. The redox potential can be tuned through conjugation of the polymeric chain and by electron injection from donor substituents in the aromatic rings. Reversible capacities of up to 350 mA h g^?1 are achieved when the carbon mixture is optimized with Ketjen Black. Interestingly, the “reverse” configuration (? CH?N? Ar? N?HC? ) is not electrochemically active, though isoelectronic.     

Radical and Atom Transfer Halogenation (RATH): A Facile Route for Chemical and Polymer Functionalization

This work demonstrates a new halogenation reaction through sequential radical and halogen transfer reactions, named as “radical and atom transfer halogenation” (RATH). Both benzoxazine compounds and poly(2,6‐dimethyl‐1,4‐phenylene oxide) have been demonstrated as active species for RATH. Consequently, the halogenated compound becomes an active initiator of atom transfer radical polymerization. Combination of RATH and sequential ATRP provides an convenient and effective approach to prepare reactive and crosslinkable polymers. The RATH reaction opens a new window both to chemical synthesis and molecular design and preparation of polymeric materials.

     

Synthesis, crystal structure and luminescence properties of one inorganic-organic hybrid compound [FTMA]2[Co(NCS)4] (FTMA = ferrocenylmethyltrimethylammonium cation)

A new inorganic-organic hybrid compound [FTMA](2)[Co(NCS)(4)] (FTMA = ferrocenylmethyltrimethylammonium cation) has been synthesized and characterized by IR, UV, elemental analysis and X-ray crystallography. Co(II) atom has a distorted tetrahedral environment with four N atoms of four NCS(-) anions. In the solid state there are C-H?π interactions between adjacent ferrocenyl cations, which generate one-dimensional (1-D) supramolecular chain, and C-H?S hydrogen bonds between [FTMA](+) cations and cobalt thiocyanate anions. The title compound shows strong purple fluorescence emission in the solid state at room temperature.