基于交叉共轭结构的功能材料

近年来,人们对交叉共轭体系的制备、性能以及理论研究方面产生了极大的兴趣.本文综述了近期国内外在交叉共轭体系研究方面取得的一些最新进展,重点介绍了其在自组装、有机电致发光和离子检测等方面的最新发展动态.最后还对本课题组在交叉型p-n双嵌段寡聚物方面的研究作了详细的介绍,并对一些热点问题作了展望.     

基于交叉共轭结构的功能材料

近年来,人们对交叉共轭体系的制备、性能以及理论研究方面产生了极大的兴趣.本文综述了近期国内外在交叉共轭体系研究方面取得的一些最新进展,重点介绍了其在自组装、有机电致发光和离子检测等方面的最新发展动态.最后还对本课题组在交叉型p-n双嵌段寡聚物方面的研究作了详细的介绍,并对一些热点问题作了展望.     

含电子给体-受体的交叉共轭聚合物合成及其离子传感性能

在芴苯结构主链中引入苯并噻唑作为电子受体、侧链上引入N,N-二丁基苯胺作为电子给体,通过Suzuki反应制备了新型交叉共轭聚合物P1,同时合成主链中不含苯并噻唑的芴苯类共聚物P2作为对比;对两者的化学结构和光物理性质进行了表征,并研究了聚合物对离子的光学传感性能.实验和模拟计算结果均表明,P1中存在着强的分子内电荷转移效应;引入电子给体和受体(D-A)能够有效地调控交叉共轭聚合物的光学特性,这种D-A型交叉共轭聚合物是一类潜在的具有荧光增强性能的化学传感材料.     

有机磁体获取途径和分子设计

本文介绍和评价了潜在的有机磁体的理论研究进展,并指出了一些值得作更深研究的方向。     

有机单晶场效应晶体管

有机单晶场效应晶体管的研究对于探索电子的本质特性具有十分重要的意义。近几年来,不管是在制备技术还是在器件性能的研究方面,有机单晶场效应晶体管均取得了很大的进步,并由此引起了社会的广泛关注,成为场效应晶体管领域的一个重要研究方向。本文主要介绍了有机单晶的生长方法、有机场效应器件的各种制备技术、器件的迁移率及其影响因素,并对有机单晶场效应晶体管的发展前景和面临的一些问题作了简要的讨论。     

有机单晶场效应晶体管

有机单晶场效应晶体管的研究对于探索电子的本质特性具有十分重要的意义.近几年来,不管是在制备技术还是在器件性能的研究方面,有机单晶场效应晶体管均取得了很大的进步,并由此引起了社会的广泛关注,成为场效应晶体管领域的一个重要研究方向.本文主要介绍了有机单晶的生长方法、有机场效应器件的各种制备技术、器件的迁移率及其影响因素,并对有机单晶场效应晶体管的发展前景和面临的一些问题作了简要的讨论.     

有机单晶场效应晶体管

有机单晶场效应晶体管的研究对于探索电子的本质特性具有十分重要的意义。近几年来，不管是在制备技术还是在器件性能的研究方面，有机单晶场效应晶体管均取得了很大的进步，并由此引起了社会的广泛关注，成为场效应晶体管领域的一个重要研究方向。本文主要介绍了有机单晶的生长方法、有机场效应器件的各种制备技术、器件的迁移率及其影响因素，并对有机单晶场效应晶体管的发展前景和面临的一些问题作了简要的讨论。     

甲烷高温燃烧催化剂研究进展*

本文综述了甲烷高温燃烧催化剂的研究现状,对有代表性的催化剂体系尤其是六铝酸盐催化剂的研究进展作了介绍,阐述了近年来有关贵金属、钙钛矿型氧化物及六铝酸盐催化剂结构和制备方法方面的研究结果,并对六铝酸盐催化剂的制备提出了一些建议.     

钯或镍催化的有机镁及有机锌的不对称交叉偶联反应

综述了钯或镍的手性配合物催化的有机金属试剂与芳基及烯基卤化物的不对称交叉偶联反应,着重介绍了手性配体的发展及其对反应产物ee值的影响。对一些已研究得较清楚的反应的可能立体识别机理也作了介绍。     

有机膦酸铜化合物的合成、结构及性质

由于在分子识别、传感器、催化等方面的潜在应用前景，近年来金属有机膦酸化学研究引起了人们广泛的关注。本文介绍有机膦酸铜化合物的结构、合成及性质研究方面所取得的一些进展。     

Synthesis and Nonlinear Optical Property of a Series of New Chromophores Containing Furan Ring as the Only Conjugation Bridge

This paper reports the synthesis and the nonlinear optical property of a series of new chromophores which contain furan ring as the only conjugation bridge for the first time. They are characterized by UV-VIS, FT-IR, 1H NMR, MS and elemental analysis. Their dipole moment and the first-order molecular hyperpolarizability (β) are calculated and compared with those of the analogues containing either benzene or thiophene as the conjugation bridge.     

Unexpectedly Large Couplings Between Orthogonal Units in Anthraquinone Polymers

The unusual electronic properties of directly linked 1,4-polyanthraquinones (14PAQs) are investigated. The dihedral angle between the molecular planes of anthraquinones (AQs) is found to be close to 90°. Contrary to the prevailing notion that the interaction between orthogonal units is negligible due to broken π-electron conjugation, the coupling between neighboring AQ units does not have a minimum at 90° and is much larger than that expected. The unexpectedly large electronic coupling between orthogonal AQ units is explained by the interaction between the lone pairs of the carbonyl oxygen and the π system of the neighboring unit, which allows favorable overlap between frontier molecular orbitals at the orthogonal geometry. It is shown that this effect, which is described computationally for the first time, can be strengthened by adding more quinone units. The effect of thermal fluctuations on the couplings is assessed through ab initio molecular dynamics simulations. The distributions of the couplings reveal that electron transport is resilient to dynamic disorder in all systems considered, whereas the hole couplings are much more sensitive to disorder. Lone pair–π interactions are described, as a previously largely overlooked conjugation mechanism, for incorporation into a new class of disorder-resilient semiconducting redox polymers.     

含不同共轭桥的TCNQ开闭壳层体系NLO性质的DFT研究

采用密度泛函理论(DFT)结合有限场(FF)方法,对不同共轭桥连接的四氰代二甲基苯醌(TCNQ)开壳层和闭壳层电子态的非线性光学(NLO)系数进行计算,并以乙烯桥为例讨论共轭链长度与NLO性质的关系.结果表明:开壳层体系的极化率和二阶超极化率值都大于闭壳层体系,且共轭桥的共轭性越强,体系的极化率和二阶超极化率越大;在自由基体系中,单重态的二阶超极化率随双自由基成分y和自旋多重度的增加而增大.体系的共轭链增长,BLA(BondLength Alternation,共轭分子中相邻单、双键键长差的平均值)逐渐减小,双自由基成分y逐渐增大,体系的二阶超极化率也逐渐增大.     

Molecular electrostatic potential for exploring π-conjugation: a density-functional investigation

Molecular electrostatic potentials (MESP) of the most common building blocks of organic π-conjugated systems, viz. ethylene, acetylene, benzene, furan, pyrrole, thiophene and phenylvinylene, are examined at the B3LYP/6-311++G(2d,2p) level. The topography of MESP is employed for mapping the strength of electronic conjugation between these building blocks. When electron-rich molecular regions are connected to each other, the MESP value of the corresponding conjugation critical point (CCP) is able to provide a quantitative measure of the strength of the conjugation. The systems with stronger conjugation are generally seen to possess a larger negative value of CCP and a smaller difference (ΔV(CM-CCP)) between the MESP values of respective conjugated minimum (CM) and the CCP, in agreement with the experimental as well as other theoretical results. The present MESP topography-based approach thus offers a measure of the quantitative strength of π-conjugation in molecules.     

Design of a Quinoidal Thieno[3,4‐b]thiophene‐Diketopyrrolopyrrole‐Based Small Molecule as n‐Type Semiconductor

A quinoidal small‐molecule semiconductor QDPPBTT was synthesized. Organic thin‐film transistor (OTFT) devices based on QDPPBTT showed an electron mobility as high as 0.13 cm² V^?1 s^?1 and I_on/I_off ratio of 10⁶ under ambient conditions. We suggested that 2D extended π‐conjugation and quinoid‐enhancing effect had an important role in electron mobility and stability of n‐type FET devices, which might be a good strategy in designing new material systems.     

The Prospect of Dimensionality in Porous Semiconductors

With the advent of silicon-based semiconductors, a plethora of previously unknown technologies became possible. The development of lightweight low-dimensional organic semiconductors followed soon after. However, the efficient charge/electron transfers enabled by the non-porous 3D structure of silicon is rather challenging to be realized by their (metal-)organic counterparts. Nevertheless, the demand for lighter, more efficient semiconductors is steadily increasing resulting in a growing interest in (metal-)organic semiconductors. These novel materials are faced with a variety of challenges originating from their chemical design, their packing and crystallinity. Although the effect of molecular design is quite well understood, the influence of dimensionality and the associated change in properties (porosity, packing, conjugation) is still an uncharted area in (metal-)organic semiconductors, yet highly important for their practical utilization. In this Minireview, an overview on the design and synthesis of porous semiconductors, with a particular emphasis on organic semiconductors, is presented and the influence of dimensionality is discussed.     

Mechanism of high thermal stability of commercial polyesters and polyethers conjugated with bio‐based caffeic acid

In previous report, we discovered that a novel improvement technique to enhance the thermal properties of poly(L ‐lactide)s (PLLAs) by terminal conjugation with 3,4‐diacetoxycinnamic acid (DACA). In this study, we clarified the mechanism of the enhancement of thermal stability by using commercial polyesters and polyethers. The effect of thermal improvement by the terminal conjugation of DACA on poly(DL ‐lactide), poly(ε‐caprolactone), and poly(ethylene glycol) was almost the same as about 100 °C increase. The amount of residual tin catalyst, which enhances the thermal degradation of polyesters, was reduced at undetected level after the terminal conjugation of DACA probably due to the removal of tin during DACA conjugation process. Furthermore, the π‐π stacking interactions of DACA units and the chemical protection of terminal hydroxyl groups, which enhances intramolecular scission, were also important for the high thermal stability. We clarified that the extreme high thermal stability by DACA conjugation was induced by these above mechanisms. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and Crystal Structure of （SiCl3）2Fe（CO）4

The compound （SiCl3）2Fe（CO）4 was synthesized and structurally characterized by X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P2 1/n with α = 8.287（2）, b = 9.829（2）, c = 9.042（2） A, β = 96.19（3）°, V= 732.2（3） A^3, C4Cl6FeO4Si2, Mr = 436.77, Z = 2, Dc = 1.981 g/cm^3, F（000） = 424, μ（MoKα） = 2.282 mm^-1, the final R = 0.048 and wR = 0.164 for 1109 observed reflections （I 〉 2σ（I））. The crystal structure of （SiCl3）2Fe（CO）4 reveals that the Si（l）- Fe-Si（l）^a sequence is linear and perpendicular to the Fe（CO）4 cross-shaped plane.     

Alternative Functionalization of Hydrogen-Bonded Diketopyrrolopyrrole Derivatives**

Diketopyrrolopyrrole (DPP) derivatives with thiophene capping rings are widely used as semiconductors in organic electronics. Their optoelectronic properties can be adjusted by adding different electroactive groups or by extending the conjugation of the central core, as well as by regulating their self-assembly through noncovalent interactions. One effective strategy demonstrated to improve the performance and morphology of organic solar cells is incorporating hydrogen-bonding units into DPPs. While the functionalization of the DPP lactams and the coupling of aromatic units to the thiophene rings are the most common procedures to tune the properties of such derivatives, modifying the thiophene capping units with hydrogen-bonding groups is a challenging synthetic task. Despite this difficulty, incorporating amide-containing substituents into the thiophene rings of single core thiophene-capped DPP derivatives could yield exciting results, as the advantages of having hydrogen-bonded π-conjugated systems based on these modified DPPs have not been explored thoroughly. This work reports on an efficient method for synthesizing such derivatives.     

基于Cz-DPP不对称D-A结构新型有机小分子光伏材料的合成与性质

本文设计合成了一系列以咔唑(CZ)和吡咯并吡咯二酮(DPP)为基本结构单元的D-A结构的新型小分子材料,并对其进行了一系列的性能表征.合成的材料以咔唑作为给电子单元,吡咯并吡咯二酮作为吸电子单元,采用三键作为π桥,并引入4-氟苯基、4-氰基苯基和4-甲氧基苯基作为末端取代基团对材料进行修饰.其中材料CZBTDPPF和CZBTDPPO因分别具有1.85和1.79 eV的较窄带隙而分别获得了相对较高的的光电转化效率(1.97%和1.91%).由此可见,引入4-氟苯基和4-甲氧基苯基作为末端取代基团对于延长材料共轭结构、拓宽材料吸收从而实现材料光伏性能的提升具有重要的作用.