短程有机电子给体-受体体系的合成

设计合成了一类以蒽为电子给体,带不同吸电子取代基的苯为电子受体的新型短程有机电子给体-受体体系。光谱实验研究发现,该短程给体-受体体系内存在非常强的荧光淬灭现象。实验结果分析表明强荧光淬灭的本质在于体系分子内快速的电子转移,同时表明缩短电子给体-受体之间的距离将加快电子转移过程。     

NBT基陶瓷中相变致电子发射的研究

在无铅铁电阴极钛酸铋钠（NBT）中获得了20 A/cm2的电流发射密度。在施加激励电压过程中,观察到了和其他阴极材料不同的3个发射电流峰。通过考虑相变因数对电流发射的影响,修正了基于极化反转致电子发射模型的电流发射公式,由此定量解释了在NBT基陶瓷中观察到的不同电流发射现象,揭示了电流发射不仅仅由已有文献中提出的快极化反转产生,也可以由极化的变化(比如相变)产生。为进一步验证该结论和弄清不同种类铁电阴极电子发射的机理,进行了NBT与锆钛酸铅（PZT）的电子发射比较实验。在电子发射前后观察到NBT的压电常     

Self-organization of supramolecular helical dendrimers into complex electronic materials

The discovery of electrically conducting organic crystals and polymers has widened the range of potential optoelectronic materials, provided these exhibit sufficiently high charge carrier mobilities and are easy to make and process. Organic single crystals have high charge carrier mobilities but are usually impractical, whereas polymers have good processability but low mobilities. Liquid crystals exhibit mobilities approaching those of single crystals and are suitable for applications, but demanding fabrication and processing methods limit their use. Here we show that the self-assembly of fluorinated tapered dendrons can drive the formation of supramolecular liquid crystals with promising optoelectronic properties from a wide range of organic materials. We find that attaching conducting organic donor or acceptor groups to the apex of the dendrons leads to supramolecular nanometre-scale columns that contain in their cores pi-stacks of donors, acceptors or donor-acceptor complexes exhibiting high charge carrier mobilities. When we use functionalized dendrons and amorphous polymers carrying compatible side groups, these co-assemble so that the polymer is incorporated in the centre of the columns through donor-acceptor interactions and exhibits enhanced charge carrier mobilities. We anticipate that this simple and versatile strategy for producing conductive pi-stacks of aromatic groups, surrounded by helical dendrons, will lead to a new class of supramolecular materials suitable for electronic and optoelectronic applications.     

Structure and second-order NLO property of the molecules bridged through n-vertex bis-substituted carborane （n=5, 6, 7）

Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalism to calculate the second-order NLO properties. The results indicate that the structures of n-vertex bis-substituted carborane (n=5, 6, 7) are changed due to bridged donor and acceptor moieties. The distances between two C atoms are becoming longer. And the stability and dipole moment are in- fluenced by changing substituted positions of C atoms. The isomers with the substituents connecting with C atoms of lower coordination number have better stability and larger values of polarizability. One-dimensional structure of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) is in favor of intramolecular charge-transfer. Meanwhile, the isomer with a larger change of dipole moment has larger value of second-order NLO properties during the charge-transfer process.     

Electronic structures and nonlinear optical properties of XAuPH<Subscript>3</Subscript>

The studies on model systems XAuPH3(X-H,F,Cl,Br,I,CN,CH3)have been carried out by using ab intiol HF and DFT B3LYP methods at pseudopotential and double-zeta LANL2DZ level.The results are compared with those of MP2,The properties of the models.i.e.the atomic net charge populations.the frontier molecular orbitals and nonlinear optical(NLO)properties have been investigated under an applied electric field on the basis of optimized structures.The computational results show that for these models characterized as electron acceptor-metal-electron donor(A-M-D)system,the NLO properties are due to intramolecular charge-transfer interaction between the acceptor and the donor.The more charges transfer gives,the better NLO properties.In the selected model systems,IAuPH3 has the biggest βvec and γof 1184.1942 a.u.and 17341.9214 a.u.,whereas IC6H4PH3^ ,A TYPICAL a-π-D organic conjugated system,has βvec and γof 710.7697 and 11664.1405 a.u.respectively.In comparison.IAuPH3 has significant NLO properties.     

Electrical conduction through DNA molecules

The question of whether DNA is able to transport electrons has attracted much interest, particularly as this ability may play a role as a repair mechanism after radiation damage to the DNA helix. Experiments addressing DNA conductivity have involved a large number of DNA strands doped with intercalated donor and acceptor molecules, and the conductivity has been assessed from electron transfer rates as a function of the distance between the donor and acceptor sites. But the experimental results remain contradictory, as do theoretical predictions. Here we report direct measurements of electrical current as a function of the potential applied across a few DNA molecules associated into single ropes at least 600 nm long, which indicate efficient conduction through the ropes. We find that the resistivity values derived from these measurements are comparable to those of conducting polymers, and indicate that DNA transports electrical current as efficiently as a good semiconductor. This property, and the fact that DNA molecules of specific composition ranging in length from just a few nucleotides to chains several tens of micrometres long can be routinely prepared, makes DNA ideally suited for the construction of mesoscopic electronic devices.     

铁电颗粒的尺寸效应

应用具有长程相互作用的横场伊辛模型模拟了铁电颗粒,考察了尺寸和长程相互作用对铁电颗粒的极化和相变的影响．我们得到的结论是：1．随着铁电颗粒尺寸的减小和长程相互作用的增强．铁电颗粒的相变温度降低,同时发现铁电颗粒存在一个临界尺寸,当铁电颗粒的尺寸小于临界尺寸时,铁电颗粒将不会有铁电相到顺电相的相变．且此临界尺寸随长程相互作用的增强而变大．2随着长程相互作用的增强,铁电颗粒的极化强度增大,在相同的条件下,晶格中心点的极化强度总是大于晶格边上的格点的极化强度．     

Synergetic enhancement of photoconductivity in chlorodiane blue /oxotitanylphthalocyanine composites

The nonlinear enhancement of photosensitivity in chlorodiane blue azo (CBA)/ oxotitanylphthalocyanine composites (TiOPc) has been found. Neither evident electronic interaction nor interpenetration between chlorodiane blue and TiOPc molecules is indicated by electronic spectra and X-ray diffraction patterns. Xerographic discharge experiments suggest that the synergetic enhancement of photosensitivity results from contribution of the transition of gap states, which are induced by photoexcitation upon composite photoreceptors. Electron Spin Resonance (ESR) and X-ray Photoelectron Spectroscopy (XPS) data imply that oriented partial charge transfer between TiOPc and CBA molecules occurs when the composites are excited by incident light. This synergetic effect observed in the composite systems with weak electron donor and acceptor provides a novel strategy to design high quality photoconductive materials and devices.     

温度梯度铁电薄膜的极化偏移特性研究

采用平均场近似下的横场伊辛模型理论,同时考虑了遂穿频率与温度的相互关系,重点研究了BaTiO3温度梯度铁电薄膜的极化偏移特性.研究表明:量子起伏效应对于温度梯度铁电薄膜的性质有重要的影响,在低温区量子起伏效应尤其显著；温度梯度的存在导致了薄膜内部的极化强度的梯度分布；对于下温度梯度铁电薄膜来说,当量子起伏效应达到足够强时,可以改变极化梯度和极化偏移的方向.     

Excitation energy transfer mechanisms in allophycocyanin (I)

The mechanisms of excitation energy transfer within allophycocyanin monomer with the theory of generalized master equation (GME) and the technique of time-resobed fluorescence anisotropic spectroscopy are studied. In the case of known information of its structure and spectra, the theory applied is based on the assumption that the coupling interaction between two chromophores is fairly weak. The theory correctly predicts the experimentlly observed rate for excitation energy transfer in allophycocyanin monomer. Based on the results, the energy transfer mechanism can be described as Förster and these processes cannot take place from the high vibrational levels of donor to acceptor.     

Excitation energy transfer mechanisms in allophycocyanin (Ⅰ)——Energy transfer mechanisms in monomer

The mechanisms of excitation energy transfer within allophycocyanin monomer with the theory of generalized master equation (GME) and the technique of time-resolved fluorescence anisotropic spectroscopy are studied. In the case of known information of its structure and spectra, the theory applied is based on the assumption that the coupling interaction between two chromophores is fairly weak. The theory correctly predicts the experimentlly observed rate for excitation energy transfer in allophycocyanin monomer. Based on the results, the energy transfer mechanism can be described as Forster and these processes cannot take place from the high vibrational levels of donor to acceptor.     

光电功能型超分子聚合物的研究进展

超分子聚合物是重复单元经超分子弱键作用链接而形成的聚集体,是功能软物质中一种新的组织方式。文中基于众多超分子聚合物的分类,重点论述主链式光电功能型超分子聚合物(optoelectronic supramolecular poly-mer,OSP)在太阳能电池、有机电致光、电致变色等得到深入研究领域的应用进展;通过调控能量转移、电荷转移、载流子迁移率等可以实现OSP的白光、光电转换、电致变色等性质和相关器件,并使OSP日渐成为超分子化学与有机电子等学科交叉领域研究的新热点;最后展望了OSP的研究趋势。     

Single crystals of an ionic anthracene aggregate with a triplet ground state

Crystalline supramolecular aggregates consisting of charged organic molecules, held together through metal-cluster-mediated Coulomb interactions, have attracted interest owing to their unusual structural, chemical and electronic properties. Aggregates containing metal cation clusters 'wrapped' by lipophilic molecular anions have, for example, been shown to be kinetically stable and soluble in nonpolar liquids such as saturated hydrocarbons. The formation of supramolecular aggregates can even be exploited to generate aromatic hydrocarbons that carry four negative charges and crystallize in the form of organic poly(metal cation) clusters or helical polymers. Here we report the anaerobic crystallization of an ionic organic aggregate--a contact ion septuple consisting of a fourfold negatively charged 'tripledecker' of three anthracene molecules bridged by four solvated potassium cations. Its electronic ground state is shown experimentally, using temperature-dependent electron paramagnetic resonance spectroscopy, to be a triplet. Although the spins in this biradical ionic solid are separated by a considerable distance, density functional theory calculations indicate that the triplet ground state is 84 kJ mol(-1) more stable than the first excited singlet state. We expect that the successful crystallization of the ionic solid we report here, and that of a covalent organic compound with a triplet ground state at room temperature, will stimulate further attempts to develop new triplet-ground-state materials for practical use.     

分子平面性对其双光子吸收特性影响

利用基于密度泛函理论水平下的响应场方法，研究了新近合成的双光子有机分子的非线性光学性质．计算结果表明，该类分子具有较好的双光子吸收特性，分子的官能团供需电子的能力、分子的平面性都是影响分子双光子吸收特性的重要因素．     

Electronic structures and nonlinear optical properties of XAuPH_3

Since the discovery that organic conjugated system shows good NLO properties, such as fast optical responses, high threshold value for injury, much attention has been put on the theoretical and experimental study and considerable progress has been achieved[1—9]. Recently, the studies on transition-metal organometallic compounds, which have been extensively applied in conductivity, luminescence and catalysis, have been performed system-atically due to its potential application as NLO …     

铁电相变的简谐子软模图像

在自由边界条件下计算了立方钛酸钡有限尺寸晶体中原子的简谐振动模 ,发现许多简谐子软模。用这些软模花样说明了晶体冷却时发生具有a畴和c畴结构的铁电相变。理论表明铁电相变过程涉及屏蔽电荷的激发及其在界面的缓慢扩散 ,以最后得出各个电畴内部的均匀自发极化。铁电相变过程的这些细节 ,都得到了实验的有力证明     

Helical self-assembled polymers from cooperative stacking of hydrogen-bonded pairs

The double helix of DNA epitomizes this molecule's ability to self-assemble in aqueous solutions into a complex chiral structure using hydrogen bonding and hydrophobic interactions. Non-covalently interacting molecules in organic solvents are used to design systems that similarly form controlled architectures. Peripheral chiral centres in assemblies and chiral side chains attached to a polymer backbone, have been shown to induce chirality at the supramolecular level, and highly ordered structures stable in water are also known. However, it remains difficult to rationally exploit non-covalent interactions for the formation of chiral assemblies that are stable in water, where solvent molecules can compete effectively for hydrogen bonds. Here we describe a general strategy for the design of functionalized monomer units and their association in either water or alkanes into non-covalently linked polymeric structures with controlled helicity and chain length. The monomers consist of bifunctionalized ureidotriazine units connected by a spacer and carrying solubilizing chains at the periphery. This design allows for dimerization through self-complementary quadruple hydrogen bonding between the units and solvophobically induced stacking of the dimers into columnar polymeric architectures, whose structure and helicity can be adjusted by tuning the nature of the solubilizing side chains.     

铁电体的极化疲劳和历史记忆效应

电滞回线是研究铁电性的重要方法,但其中非线性电导,非线性顺电电容等非铁电性的影响难以消除.为此提出了微分电滞回线方法以取代传统的电滞回线.基于该方法,可将回线中各种非铁电性的贡献定量地分离出来,从而得到纯铁电性的贡献.对锆钛酸铅(PZT)和钛酸钡(BST)陶瓷样品的测量结果表明,纯铁电微分回线可用若干个高斯函数精确拟和,铁电体的极化疲劳就表现为高斯函数个数、峰位、峰高、半高宽等参数在外加作用下持续变化.实验还进一步证明,疲劳效应与铁电体所经历的热力学历史密切相关.     

β-环糊精/萘酚对有机小分子识别作用研究

有机小分子甲醇、乙醇、丙醇、异丙醇、丁醇、丙酮、丁酮、乙腈、乙二醇在Britton-Robison三酸缓冲液中,不仅改变了β-环糊精(CD)空腔的微环境,而且使β-CD/萘酚超分子包合物的离解常数发生改变.文章用荧光法研究了主客体分子间的诱导契合和几何互补等方面β-环糊精/萘酚对小分子的结合能力和分子选择性.结果表明:β-环糊精/萘酚作为一种光谱探针可用于指示分子键合能力和分子识别能力.     

Structural Changes of Water Molecules Upon the Reduction of Quinones in The Reaction Center from Rhodobactery Sphaeroides

1 Results The photosynthetic bacterial reaction center (RC) is a membrane protein complex.The RC is composed of three protein subunits and redox components such as bacteriochlorophylls, bacteriopheophytins,and quinones.The RC performs the photochemical electron transfer from the bacteriochlorophyll dimer through a series of electron donor and acceptor molecules to a secondary quinone,QB.QB accepts electrons from a primary quinone,QA,in two sequential electron transfer reactions.The second electron trans...