Control of conformational and interpolymer effects in conjugated polymers.

The role of conjugated polymers in emerging electronic, sensor and display technologies is rapidly expanding. In spite of extensive investigations, the intrinsic spectroscopic properties of conjugated polymers in precise conformational and spatial arrangements have remained elusive. The difficulties of obtaining such information are endemic to polymers, which often resist assembly into single crystals or organized structures owing to entropic and polydispersity considerations. Here we show that the conformation of individual polymers and interpolymer interactions in conjugated polymers can be controlled through the use of designed surfactant poly(p-phenylene-ethynylene) Langmuir films. We show that by mechanically inducing reversible conformational changes of these Langmuir monolayers, we can obtain the precise interrelationship of the intrinsic optical properties of a conjugated polymer and a single chain's conformation and/or interpolymer interactions. This method for controlling the structure of conjugated polymers and establishing their intrinsic spectroscopic properties should permit a more comprehensive understanding of fluorescent conjugated materials.     

导电聚合物的电化学性质

综述了几种有代表性的导电聚合物——聚吡咯、聚苯胺、聚噻吩等的电化学特性及其电化学掺杂／脱掺杂反应的机理,介绍了聚对苯撑乙烯(PPV)等光电活性共轭聚合物的循环伏安特性及其HOMO和LUMO能级的电化学表征方法;还对导电聚合物的电化学稳定性以及取代基对共轭聚合物电子结构的影响进行了讨论．     

含共轭三键的聚合物的掺杂机理和导电特性的研究

以聚丁（对甲苯硫酸）－２,４－己炔－１,６－二醇酯（ＰＤＡ－ＴＳ）为例,探讨了含共轭三键的聚合物的掺杂和导电特性的研究,对其微观掺杂机制,在比较现有的掺杂模型的基础上,提出了新的掺杂模型。     

The amplified fluorescence quenching of heteroatomic conjugated polymers based on the “molecular wire”effects

One of the most important components of chemicalsensor is sensing material, which selectively binds ananalyte and signals the binding. In conventional sensorresearch, the sensitivity and reversibility of sensor arelargely determined by the association constant of thebinding. An approach to enhancing the association con-stant can be benefit for sensitivity, but disadvantageous to reversible response. Therefore, the search for new sensing materials with the high sensitivity, good selectivity and…     

Synthesis and Characterization of Fluorene-based Polymers Containing Electron-withdrawing Thiazolo Thiazole Unit

1 Results Low bandgap polymers can be used for pure red light emitting materials or solar cell materials.To make low bandgap polymers,we designed conjugated polymers with alternating sequences of the appropriate donor/acceptor units in the main chain.3-hexyl thiophene was used as a electron donating unit.For the electron accepting unit,we selected thiazolothiazole and bithiazole units having electron withdrawing property.Polyfluorene(PF) is the preferred conjugated polymer in light-emitting applications...     

Highly sensitive biosensors based on water-soluble conjugated polymers

Conjugated, conductive polymers are a kind of important organic macromolecules, which has found applications in a variety of areas. The application of conjugated polymers in developing fluorescent biosensors represents the merge of polymer sciences and biological sciences. Conjugated polymers are very good light harvesters as well as fluorescent polymers, and they are also “molecular wires”.Through elaborate designs, these important features, i.e.efficient light harvesting and electron/energy transfer, can be used as signal amplification in fluorescent biosensors. This might significantly improve the sensitivity of conjugated polymer-based biosensors. In this article, we reviewed the application of conjugated polymers, via either electron transfer or energy transfer, to detections of gene targets, antibodies or enzymes. We also reviewed recent efforts in conjugated polymer-based solid-state sensor designs as well as chip-based multiple target detection. Possible directions in this conjugated polymer-based biosensor area are also discussed.     

手性联二萘侧基聚(3,3'-联咔唑对苯二腈)的合成及其聚集诱导发光和圆偏振发光性能研究

以手性联二萘(BINOL)取代的2, 3-二氟对苯二腈和3, 3'-联咔唑为单体,通过碳-氮偶联反应得到一对共轭聚合物(R)-P1和(S)-P1,并且通过1H NMR与13C NMR、凝胶渗透色谱(GPC)、热重分析(TGA)、荧光发射光谱(PL)、圆二色谱(CD)和圆偏振发光(CPL)光谱等对聚合物的化学结构、分子量、热稳定性以及光物理性质等进行了表征.结果表明:该聚合物具有明显的聚集诱导发光(AIE)性质;手性联二萘侧基能有效地诱导共轭主链的微环境,使该聚合物具有手性活性,且表现出CPL特性.     

Editor’s note

The past several decades have witnessed great progress in the research on coordination polymers since the conception of supramolecular chemistry was advanced by Prof. Lehn, especially after the report of Prof. Robson on coordination polymers. Thanks to the development in several related fields, such as crystal engineering, supramolecular chemistry, material chemistry and solid state chemistry, the rational design and construction of coordination polymers with multiple functions has become one of the most active arenas in inorganic and material chemistry.     

Self-Assembled Conjugated Polymer Nanometer Scale Devices

1 Introduction Nanometer scale devices, as the next generation devices of electronics, have got a worldwide attention and rapid development recently. Simultaneously, conjugated polymers have been applied in organic electronics successfully because of their outstanding electronic-photonic properties. However, as far as we know few reports have dealt with the fabrication of nanometer scale devices by using conjugated polymers, although the combination of nanometer scale devices and polymers will…     

微孔有机聚合物

微孔有机聚合物是一种新型的多孔材料,在非均相催化、吸附、分离和气体存储等方面具有潜在的应用.它是最近几十年发展起来的,全部由有机分子的构建块组装而成的微孔（孔径小于2.0nm）固体.依据设计策略的不同,主要可以分成以下4种：（1）通过交联反应阻止链密堆积的超交联聚合物;（2）通过刚性和扭曲基团阻止链密堆积的自具微孔聚合物;（3）通过大共轭？-体系刚性结构组建的共轭微孔聚合物;（4）通过适宜的官能团发生可逆地缩合反应来制备的共价有机骨架聚合物.本文根据国内外的研究背景,重点介绍自具微孔聚合物和共轭微孔聚合物.     

论共轭聚合物的合成方法及其应用

π共轭聚合物因具有独特的光、电性能而引起了科学界的广泛关注。由富电子单元和缺电子单元构成的给一受电子模型聚合物由于其在太阳能电池、发光二极管、传感器等领域有着诱人的应用前景而受到科学界和商业界的青睐。本论文介绍共轭聚合物的特性及其合成方法,论述共轭聚合物在太阳能电池和发光材料中的应用。     

Synthesis and photocurrent response of porphyrin-containing conjugated polymers

In recent years conjugated polymers have attracted considerable attention because of their potential appli- cations in the fields of light emitting diodes, photo- voltaic devices, and sensors[1―7]. In the fabrication of semiconductor photovoltaic devices…     

Carbazole—containing light—emitting polymers：Properties of excited states

A series of light-emitting conjugated polymers alternatively involving carbazole and bivinylene arylene moieties in the main chain were synthesized via Wit-tig-Horner type copolymerization.The photoinduced charge transfer process relating to these polymers was investigated by using the technique of fluorescence spectroscopy.The interaction between excited copolymers and C60 in benzene solution was studied.The fluorescence quenching can be well described by the “sphere-of-action” mechanism.It is be-lieved that two basic steps are involved in the quenching process,i.e. the diffusion of excitation within the comjugated polymers and the dissociation of the exctions trapped by fullerene,The radius of the sphere-of-action can be related to the excitation diffusion length,which depends on the lifetime of the exciton.The dynamic fluorescence quenching of the copolymers by another quencher,1,4-dicyanobenzene(DCB) was also surveyed.Copolymers with different chain confor-mations show different temperature effects in the dynamic quenching.A planar conformation is beneficial for the quenching via bimolecular collision.     

Collapse of stiff conjugated polymers with chemical defects into ordered, cylindrical conformations

The optical, electronic and mechanical properties of synthetic and biological materials consisting of polymer chains depend sensitively on the conformation adopted by these chains. The range of conformations available to such systems has accordingly been of intense fundamental as well as practical interest, and distinct conformational classes have been predicted, depending on the stiffness of the polymer chains and the strength of attractive interactions between segments within a chain. For example, flexible polymers should adopt highly disordered conformations resembling either a random coil or, in the presence of strong intrachain attractions, a so-called 'molten globule'. Stiff polymers with strong intrachain interactions, in contrast, are expected to collapse into conformations with long-range order, in the shape of toroids or rod-like structures. Here we use computer simulations to show that the anisotropy distribution obtained from polarization spectroscopy measurements on individual poly[2-methoxy-5-(2'-ethylhexyl)oxy-1,4-phenylenevinylene] polymer molecules is consistent with this prototypical stiff conjugated polymer adopting a highly ordered, collapsed conformation that cannot be correlated with ideal toroid or rod structures. We find that the presence of so-called 'tetrahedral chemical defects', where conjugated carbon-carbon links are replaced by tetrahedral links, divides the polymer chain into structurally identifiable quasi-straight segments that allow the molecule to adopt cylindrical conformations. Indeed, highly ordered, cylindrical conformations may be a critical factor in dictating the extraordinary photophysical properties of conjugated polymers, including highly efficient intramolecular energy transfer and significant local optical anisotropy in thin films.     

新型超支化发光聚合物合成与表征

以具有高荧光量子效率的二（4-羟基苯乙烯基）苯（PV）为A₂发光单体,以四官能度的对甲基苯磺酸季戊四醇酯为B₄支化单体,采用A₂＋B₄的路线,合成了一类新型的具有三维结构的部分共轭型超支化电致发光聚合物;为了改善聚合物中载流子的平衡注入能力,又分别在分子的骨架和外围引入具有良好电子传输功能的噁二唑(OXD)基团;利用核磁共振、DSC、紫外 可见分光光度计、荧光光谱仪等分析测试手段对单体及聚合物进行了结构与性能表征。结果表明：具有超支化结构的聚合物热稳定性明显改善;噁二唑基团的引入有利于提高聚合物的玻璃化温度;将噁二唑基团引入到分子中后,其紫外吸收光谱和荧光光谱均出现蓝移现象,降低了电子注入势垒。     

Gate-induced superconductivity in a solution-processed organic polymer film

The electrical and optical properties of conjugated polymers have received considerable attention in the context of potentially low-cost replacements for conventional metals and inorganic semiconductors. Charge transport in these organic materials has been characterized in both the doped-metallic and the semiconducting state, but superconductivity has not hitherto been observed in these polymers. Here we report a distinct metal-insulator transition and metallic levels of conductivity in a polymer field-effect transistor. The active material is solution-cast regioregular poly(3-hexylthiophene), which forms relatively well ordered films owing to self-organization, and which yields a high charge carrier mobility (0.05-0.1 cm2 V(-1) s(-1)) at room temperature. At temperatures below approximately 2.35 K with sheet carrier densities exceeding 2.5 x 10(14) cm(-2), the polythiophene film becomes superconducting. The appearance of superconductivity seems to be closely related to the self-assembly properties of the polymer, as the introduction of additional disorder is found to suppress superconductivity. Our findings therefore demonstrate the feasibility of tuning the electrical properties of conjugated polymers over the largest range possible-from insulating to superconducting.     

用于中间弹道测量的闪光X射线发生器研究

研究了用于中间弹道测量的闪光Ｘ射线的产生原理和测量方法，以研制的多次脉冲Ｘ射线产生器来作为对中间弹道区段弹丸姿态进行闪光Ｘ射线变管分幅摄影的脉冲Ｘ线射源，其主要技术性能满足了中间弹道测量的要求。     

Heck偶联反应在有机单分子膜上的应用

利用Heck偶联反应成功地改变了自组装单分子有机薄膜的化学结构以及末端基团,薄膜末端的碘苯基团与对卤苯乙烯在标准的Heck反应条件下成功发生了偶联反应.这些薄膜经过了接触角、膜厚以及X射线光电子能谱的详细表征.这种表面修饰的方法有效地改变有机薄膜的表面化学.     

紫外光聚合有机硅高分子聚合物的研究

以光化学和有机硅高分子化学为基础，对紫外光聚合的有机硅高聚物进行了探索性的研究，在理论上讨论了有机硅高聚物光聚合的反应机理，并通过实验证明了有机硅材料的紫外光固化的可行性，文中还讨论了影响光聚合速度的因素，分析了影响光聚合材料电性能的因素，并比较了光聚合和热固化材料的电性能，以及用于方片表面保护的结果。     

四噻吩与富勒烯(C60、C70、C84)间光致电子转移效率的研究

借助荧光猝灭可以观测和研究导电聚合物与富勒烯之间的电子转移效率及机理.文章通过对四噻吩/富勒烯相关原始数据的校正处理,排除了竞争吸收与重吸收对荧光谱值的影响,获得了能真实体现四噻吩与富勒烯(C60、C70、C84)之间荧光猝灭率的数据.