9,9-二(十六烷基)芴基二聚炔铂、金和汞配合物的合成与性质

用Hagihara脱氢卤代法合成了三种新的9,9-二(十六烷基)芴基二聚炔铂(d⁸)、金和汞(d¹⁰)化合物反式- [Pt(Ph)(PEt₃)₂C≡CRC≡CPt(Ph)(PEt₃)₂, [(PPh₃)AuC≡CRC≡CAu(PPh₃)]和[MeHgC≡CRC≡CHgMe] [R＝9,9-二(十六烷基)芴基]. 用¹H NMR, ¹³C NMR, ³¹P NMR, FT-IR, FAB-MS, UV-Vis, 荧光和磷光光谱对其进行了表征. 结果表明, 体系中的铂、金和汞产生的重原子效应可以有效地促进单线激发态S₁与三线激发态T₁的系间跃迁, 使标题化合物产生有机三线态发光.     

极谱法研究金属络合物时滴汞电极表面络合剂浓度的表达式

在极谱学中,各作者得到的从半波电位E_1/2求络合物稳定常数的公式中,都要用到半波电位E_1/2和汞滴表面络合剂X^b-的平衡浓度[X]₀这两个最基本的量^[1-11].其中,E_1/2这个量不但可以从实验上直接测定,而且它与标准电极电位、稳定常数、活度系数、扩散系数以及汞滴表面络合剂的平衡浓度等的关系式已由许多学者^[1-6]从理论上进行了推导.     

碱式碳酸锌对[UO2(CO3)3]4-吸附机理的研究

用吸附法从海水中提铀的研究已引起了广泛的注意,碱式碳酸锌则是常用的吸附材料之一。本文报道用碱式碳酸锌对[UO₂(CO₃)₃]^4-吸附机理的研究结果。从不同碱度的碱式碳酸锌吸附[UO₂(CO₃)₄]^4-中铀的实验,得出在一定的—OH浓度范围内,碱式碳酸锌中—OH含量越高,对[UO₂(CO₂)₃]^4-中铀吸附率越大的结果。同时使用X射线衍射法与红外光谱法,亦对吸附机理进行了初步研究,由此扩大了研制新吸附剂的线索。     

一个嫁接有羧酸羟基乙基酯的二吡啶吩嗪Ru(II)配合物的合成、与DNA的相互作用以及溶剂变色性质的研究

合成并表征了一个新的Ru(II)配合物[Ru(bpy)₂(hedppc)](ClO₄)₂ {bpy＝2,2'-联吡啶, hedppc＝二联吡啶[3,2-a: 2',3'-c]吩嗪-11-羧酸(2-羟乙基)酯}. 通过紫外-可见吸收光谱、与溴化乙锭竞争实验、粘度测量和DNA裂解实验研究了配合物与小牛胸腺DNA的相互作用性质. 结果表明配合物以插入模式与DNA键合,键合常数K_b＝(6.99±1.34)×10⁶ mol^－1•L (s＝2.03±0.04)与母体配合物[Ru(bpy)₂ (dppz)]^2＋相近,但光致发光和溶剂变色等光学性质与[Ru(bpy)₂ (dppz)]^2＋有明显的差别.     

一系列Ru(II)配合物电致化学发光性质的比较研究

比较研究了以C₂O₄^2－为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)₂L¹]^2＋, [Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋, [Ru(phen)₂L¹]^2＋和[Ru(phen)₂L²]^2＋(其中bpy＝2,2′-联吡啶, phen＝1,10-邻菲啰啉, L¹＝4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L²＝3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L³＝3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋和[Ru(phen)₂L²]^2＋的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)₃]^2＋相差不大.     

簇合物裂解法合成二硫纶化合物

以[Me₄N]₂[M₄(SPh)₁₀]和[Me₄N]₄[S₄M₁₀(SPh)₁₆](M=Cd,Zn)为前驱体,采用簇合物裂解法合成了配合物(Bu₄N)₂[Cd(mnt)₂]、(Bu₄N)₂[M(dmit)₂](M=Cd,Zn)以及双核配合物(Me₄N)₂[Zn₂(Sph)₂·(S₂TTF(SCH₂)₂)₂].运用PM3计算方法得到了各种二硫纶盐配体中硫负离子的静电荷大小关系:mnt^2->SPh^->dmit^2->[(MeS)₂TTFS₂]^2-≈[(CH₂S)₂TTFS₂]^2-.在理论计算及实验结果的基础上,探讨了配体上硫负离子的静电荷大小与反应产物间的关系.     

以5-(6-羧酸-2-萘基)-间苯二羧酸为配体构筑的两个镉的金属-有机骨架化合物的合成、晶体结构及荧光性质

在溶剂热条件下,以不对称三羧酸5-（6-羧酸-2-萘基）-间苯二羧酸（H3L）为配体合成了2个镉的金属-有机骨架化合物:{[Cd₃L₂（H₂O）₃]·6DMF}_n（1）和{[Cd₃L₂（H₂O）₄]·3DMA}_n（2）。通过X射线单晶衍射,粉末衍射,热重和红外光谱进行了结构表征。结构分析表明,1和2形成3,6-连接的三维结构,其拓扑符号分别为:（4⁵.6⁴.8⁶）（4³）₂和(6¹².8³)（6³）₂。此外,还对2个化合物进行了荧光分析。     

具有不同电荷和手性的Co(Ⅲ)配合物跨人红细胞膜的动力学研究

研究了4种不同电荷的Co(Ⅲ)金属配合物跨人红细胞膜的动力学,并测定了它们跨人红细胞膜的一级反应动力学速率常数,发现[Co(C₂O₄)₃]^3-的跨膜速率明显高于[Co(en)₃]³⁺,[Co(en)₂(C₂O₄)]⁺和[Co(en)(C₂O₄)₂]^-,后3种配合物的跨膜速率常数随正电荷的减少略有增加,跨膜机制为简单扩散.[Co(C₂O₄)₃]^3-的跨膜速率受阴离子通道抑制剂DIDS明显抑制,抑制率为51.95%,推测其跨膜机制为部分经阴离子通道协同简单扩散过膜.人红细胞摄入L-[Co(C₂O₄)₃]^3-的速率明显大于D-[Co(C₂O₄)₃]^3-,显示了一定的手性选择性.     

二维钨-钒簇聚物[Cu(en)2]2·[VⅤO44{Cu(en)2(H2O)}2]·3H2O的合成与表征

采用水热法合成了一个钨-钒簇聚物[Cu(en)₂]₂[V^Ⅴ{Cu(en)₂(H₂O)}₂]·3H₂O(1, en=乙二胺), 并通过X射线单晶衍射、 元素分析、 傅里叶变换红外光谱、 X射线粉末衍射、 热重分析、 价键计算、 X射线光电子能谱、 电子顺磁共振和磁性分析对其结构和性能进行了表征. 结果表明, 化合物1是以双支撑的四帽Keggin结构 [(V^ⅤO₄){Cu(en)₂(H₂O)}₂]^4- 钨-钒簇合物阴离子为基本结构单元, 与4个[Cu(en)₂]²⁺配合物阳离子以共价键和弱键相连接形成二维层状结构, 相邻层又通过氢键连接成三维超分子网络. 研究了化合物1的磁性及光催化降解罗丹明B的活性.     

芳基亚胺-脒基稀土烷基化合物的合成及其催化异戊二烯聚合研究

制备了芳基亚胺-脒基稀土二烷基化合物[NNN]Ln(CH₂SiMe₃)₂ {[NNN]=[2-C(H)NDippC₆H₃NHC(Ph)NDipp], Dipp=2,6-i-Pr₂C₆H₃, Ln=Y (2), Sm (3)}, 2和3通过了¹H NMR, ¹³C NMR, IR和元素分析测试, 通过X-ray确定了化合物2的晶体结构. 加入[Ph₃C][B(C₆F₅)₄]和烷基铝, 两个化合物均能高效催化异戊二烯聚合, 具有较好的3,4-选择性(88%), 中等的立体选择性(rr=50%), 较高的分子量(M_n=6.8×10⁴)和较窄的分子量分布(M_w/M_n=1.15). 同时发现, 烷基铝和[Ph₃C][B(C₆F₅)₄]的比例影响催化聚合的区域选择性.     

Synthesis,properties and molecular modeling of functional hyperbranched polymers and dendrimers

The design, synthesis, properties and molecular modeling of fully conjugated dendritic molecules and conjugated hyperbranched polymers are described. It has been shown that conjugated hyperbranched molecules are much more soluble than their linear analogues while maintaining all the properties characteristic of conjugated polymers. It was found that the use of polymeric solid support in hyperbranched polymerization allows to control molecular weight and degree of branching (DB). The molecular modeling of hyperbranched conjugated molecules reveals that hyperbranched structure of conjugated molecules affects significantly neither their stability nor the conjugation. On the other hand the terminal groups affect appreciably the electronic structure of conjugated hyperbranched molecules.     

荧光共轭聚合物在生物大分子检测中的应用*

共轭聚合物因其具有π-电子体系及共轭离域结构,一般都具有优异的发光性能,其发光强度和发射波长会随被检测化合物结构的不同而发生特异性响应,特别是在与被检测物相互作用过程中所产生电荷和能量能够沿共轭分子链进行有效传递,成倍放大这种作用,从而有效提高了检测灵敏度,这比相应的小分子化合物更具有优越性。目前共轭聚合物已被用于开发新型化学、生物传感器,尤其是在生物分子检测方面的应用得到迅速的发展。本文总结了近年来荧光共轭聚合物在生物传感方面的研究进展,主要讨论共轭聚合物在蛋白质、核酸及毒素检测中的应用。     

Crystalline Cooperativity of Donor and Acceptor Segments in Double‐Cable Conjugated Polymers toward Efficient Single‐Component Organic Solar Cells

The crystalline cooperativity of the donor and acceptor segment in double‐cable conjugated polymers plays an important role in the nanophase separation and photovoltaic performance in single‐component organic solar cells (SCOSCs). Two double‐cable conjugated polymers with the same conjugated backbone and perylene bisimide (PBI) side units were designed in which PBIs were positioned symmetrically and perpendicularly ( P1 ) and asymmetrically and slantingly ( P2 ) along the conjugated backbones. After thermal annealing, both conjugated backbones and PBI side units in P1 tend to form ordered nanostructures, while PBI side units in P2 dominated the crystallization and hamper the crystallization of conjugated backbones. P1 showed good crystalline cooperativity between conjugated backbones and PBI side units, resulting in improved power conversion efficiencies (PCEs) up to 3.43 % in SCOSCs, while P2 with poor crystalline cooperativity exhibited PCEs below 2.42 %.     

Conformation Control of Conjugated Polymers

In the past few decades, conjugated polymers have aroused extensive interest in organic electronic applications. The electrical performance of conjugated polymers has a close relationship with their backbone conformation. The conformation of the polymer backbone strongly affects the πelectron delocalization along polymer chains, the energy band gap, interchain interactions, and further affects charge transport properties. To realize a rigid coplanar backbone that usually possesses efficient intrachain charge transport properties and enhanced π–π stackings, such conformation control becomes a useful strategy to achieve high-performance (semi)conducting polymers. This minireview summarizes the most important polymer structures through conformation control at the molecular level, and then divides these rigid coplanar conjugated polymers into three categories: 1) noncovalent interactions locked conjugated polymers; 2) double-bond linked conjugated polymers; 3) ladder conjugated polymers. The effect of the conformation control on physical nature, optoelectronic properties, and their device performance is also discussed, as well as the challenges of chemical synthesis and structural characterization.     

昆虫性信息素共轭二烯的合成进展

许多昆虫性信息素具有共轭二烯的结构,它们的双键位置和几何构型是决定其生物活性的重要因素。立体选择性和区域选择性地合成共轭二烯是有机合成中十分有意义的研究课题。文章综述了昆虫性信息素共轭二烯的合成进展。     

Advanced materials by functionalization of conjugated polymers

Applications of conjugated polymers to advanced materials are demonstrated with fabrications of functional molecular materials and devices by incorporation of functional molecules to conjugated and/or conducting polymer, ultrahigh anisotropic conducting polymer materials by topological polymerizations of LB multilayers of amphiphilic pyrrol, artificial conjugated polymer superlattice by the potential-programmed electro-polymerization and/or electrocopolymerization, and 1-dimensional and 2-dimensional porphyrin arrays connected with conjugated and/or insulating molecular wires with P(V) porphyrin and others, for molecular photonics and electronics.     

有机共轭分子自组装方法

本文综述了有机共轭分子自组装方法的最新研究进展,从有机共轭分子的合成、自组装方法、光电性质及应用等方面进行了阐述,着重阐述了适用于有机共轭分子的各种自组装方法。认为它们的自组装在有机光电材料或器件方面具有广阔的应用前景及潜在的应用价值。     

共轭烯烃的共轭极化势

Based on the conjugated polarization theory,it is expressed as the conjugated polarizability potential （CPP）that the discrepancy between the average electrostatic energy of dipolar state and the electrostatic energy of non-polar state in the conjugated polarizability procedure for the conjugated alkenes. The correlation between CPP and the energy of ultraviolet absorption maximum,and the correlation between the energy of frontier molecular orbital obtained by ab initio calculation of quantum chemistry and the energy of ultraviolet absorption maximum have been carried out for the conjugated alkenes. Both correlation equations show a similar estimated precision. Further, the contribution of alkyl polarizability effect to the stability of dipolar state for the alkyl substituted alkenes with the effective polarizability effect index（PEI（ef））was quantified. Relating the above two parameters CPP and PEI（ef）to the energy of ultraviolet absorption maximum of the substituted alkenes in a two-parameter expression with a good prediction ability was obtained:v=1.1746+5.0187CPP-0.43204PEI （ef）,R=0.9995,s=0.0403,F=10853.28,n=23. The investigated results also indicate that it is less effective to reduce the energy of ultraviolet absorption maximum by means of increasing the alkyl substituent groups than lengthening the conjugated backbone chain in the conjugated alkenes.     

Biocidal activity of a light-absorbing fluorescent conjugated polyelectrolyte

Herein we describe studies that indicate a cationic conjugated polyelectrolyte shows biocidal activity against gram-negative bacteria (Escherichia coli, E. coli, BL21, with plasmids for Azurin and ampicillin resistance) and gram-positive bacterial spores (Bacillus anthracis, Sterne, B. anthracis, Sterne). These studies were carried out with aqueous suspensions of the conjugated polyelectrolyte, with the polyelectrolyte in supported formats and with samples in which the conjugated polyelectrolyte was coated on the bacteria. The results are interesting in that the biocidal activity is light-induced and appears effective due to the ability of the conjugated polyelectrolyte to form a surface coating on both types of bacteria. The effects observed here should be general and suggest that a range of conjugated polyelectrolytes in different formulations may provide a useful new class of biocides for both dark and light-activated applications.     

Resonance energy of very large benzenoid hydrocarbons

The resonance energy of conjugated benzenoid systems is expressed as contributions arising from independent conjugated circuits. The scheme has been applied to numerous very large conjugated systems. In many cases, it was possible to find regularities in the increments for the resonance energy within a family of benzenoid systems as the number of benzene rings is increased.