齐聚噻吩及其衍生物有机光伏材料

齐聚噻吩及其衍生物具有良好的环境稳定性和优异的光电性能,是一类具有良好发展前景的有机功能材料。本文综述了近年来齐聚噻吩及其衍生物的发展状况,简述了其主要合成方法;根据结构将其分为两大类:一类是不含极性基团或仅含弱极性基团的齐聚噻吩衍生物,另一类是给体-受体型齐聚噻吩衍生物,并讨论了它们作为有机光伏材料的应用。给体-受体型齐聚噻吩衍生物由于分子内的电荷传输作用,其光物理和电化学性能均优于不含极性基团的齐聚噻吩,该类材料在小分子光伏器件中具有最高的光电转换效率(>10%)。文章最后简要分析了影响光伏器件性能的主要因素。     

基于一种新型聚噻吩衍生物为给体的非富勒烯聚合物太阳能电池（英文）

在各种共轭聚合物给体材料中,以聚3-己基噻吩为代表的聚噻吩衍生物因其结构简单、易制备以及良好的空穴传输性能,在富勒烯衍生物为受体材料的聚合物太阳能电池体系中一直是研究重点之一。但是在近年来发展迅速的稠环小分子非富勒烯体系中的相关研究较少。在本工作中,我们通过在噻吩侧链引入烷硫基和氟取代基,设计合成了一种新型的聚噻吩衍生物给体PBSBT-2F;并对其吸收光谱、分子能级、传输性能以及光伏性能进行研究。基于PBSBT-2F:ITIC的聚合物太阳能电池取得6.7%的能量转换效率,其中开路电压为0.75 V,短路电流为13.5 mA·cm~(-2),填充因子为66.6%。结果表明:PBSBT-2F在非富勒烯体系中有很大的应用潜力。     

带有噻吩侧基的有机硼小分子电子受体光伏材料

有机小分子电子受体材料的侧基能够影响异质结有机太阳能电池的给体/受体匹配和器件性能。我们设计并合成了一个硼原子带有噻吩侧基的有机硼小分子(MBN-Th)。该分子的LUMO离域在整个骨架上,HOMO定域在中心核上,其独特的电子结构使该分子具有两个强的吸收峰(波长分别为490和726nm),因此分子具有宽的吸收光谱和强的太阳光吸收能力。与苯基侧基相比,噻吩侧基使分子的HOMO能级下移0.1 eV,LUMO能级保持不变,进而引起分子带隙减小和吸收光谱蓝移20nm。基于该有机硼小分子受体材料的异质结有机太阳能电池,实现了4.21%的能量转化效率和300–850nm的宽响应光谱。实验结果表明,硼原子上的噻吩侧基是调控有机硼小分子光电性质的有效方法,可以用于有机硼小分子受体材料的设计。     

基于碳纳米管的光伏电池

碳纳米管具有独特的一维结构和优异的光电特性,是构建光伏电池的理想材料。本文主要综述了近年来碳纳米管基光伏电池的结构设计、制备方法以及碳纳米管在器件中的不同功能应用。首先概述了碳纳米管的结构和光电特性,重点讨论了碳纳米管作为光电转换材料、导电电极和载流子传输层等功能层时器件的原理、制作方法及优缺点,介绍了碳纳米管在微型光伏电池、碳纳米管/硅异质结光伏电池、染料敏化光伏电池、钙钛矿光伏电池、有机光伏电池以及柔性光伏电池中的应用,最后总结了碳纳米管基光伏电池的优势和挑战,以期为新型碳基光伏电池的设计和制作提供思路和参考。     

有机光伏器件激活层的微结构有序性与电荷输运

本文在对有机光伏电池载流子产生机理分析的基础上,从有机光伏电池激活层的微观结构对光电转换效率影响的角度,系统介绍了目前该领域的一些重要研究成果,详细分析了影响光电转换效率的主要因素,并提出了一系列改善光伏电池效率的方法,对未来该领域的研究作了展望。     

有机光伏器件激活层的微结构有序性与电荷输运

本文在对有机光伏电池载流子产生机理分析的基础上,从有机光伏电池激活层的微观结构对光电转换效率影响的角度,系统介绍了目前该领域的一些重要研究成果,详细分析了影响光电转换效率的主要因素,并提出了一系列改善光伏电池效率的方法,对未来该领域的研究作了展望。     

有机光伏器件激活层的微结构有序性与电荷输运

本文在对有机光伏电池载流子产生机理分析的基础上,从有机光伏电池激活层的微观结构对光电转换效率影响的角度,系统介绍了目前该领域的一些重要研究成果,详细分析了影响光电转换效率的主要因素,并提出了一系列改善光伏电池效率的方法,对未来该领域的研究作了展望.     

基于侧链不对称喹喔啉聚合物的高效非富勒烯太阳电池

喹喔啉衍生物由于合成简单,易功能化,成本较低等特点在众多领域都有广泛应用。其自身具有平面刚性结构,也是构建光电聚合物的重要单体。基于喹喔啉单元的有机分子化学结构和电子结构可修饰性强,通过骨架、侧链和取代基等修饰,易于调控分子的能级和吸光光谱,因此,当使用喹喔啉体系的共轭给体与球形富勒烯受体(如PCBM)及弱结晶性非富勒烯受体(如ITIC)均可表现出优异的光伏性能。在本工作中,基于结晶性较强的非富勒烯受体(o-IDTBR),我们首次制备出侧链不对称喹喔啉(简称：不对称喹喔啉)基聚合物(TPQ-1)与之匹配。相比于侧链对称性喹喔啉(简称：对称喹喔啉)(HFQx-T)与o-IDTBR组合,“弱结晶给体-强结晶受体”组合能表现出更佳均匀的相分离尺度,从而获得更高的短路电流及能量转换效率。TPQ-1与o-IDTBR共混后器件效率为8.6%,加入15%的TB7-Th后,器件效率达到9.6%。     

三种双功能光折变模型分子的合成及光谱性质研究

20世纪 90年代 ,出现了一种新型的有机光电功能材料——有机光折变材料 .由于其在高密度数据存储、全息图象加工、光放大等许多领域具有潜在的应用前景 ,因此 ,在短短的 1 0年中 ,取得了巨大进展 [1～ 3] .在众多的有机光折变材料中 ,咔唑类材料由于其优异的性能而越来越受到重视 ,成为人们研究的重点之一[4 ] .由于咔唑类材料是一类具有等电子结构的二苯胺分子 ,当在其 3-和 6 -位引入吸电子基团后 ,不仅能保持较好的电荷转移能力 ,而且还具有电光效应 .这样 ,在有机光折变材料中 ,带有吸电子基团的乙基咔唑分子既可以作为电荷载流子的传输…     

聚合物/富勒烯共混体系双分子穿插对有机体相异质结太阳能电池性能的影响

有机体相异质结太阳能电池有源层形貌直接影响器件能量转换效率.在聚合物/小分子共混体系中,当小分子尺寸小于聚合物侧链间距时,且与聚合物相互作用能形成基态-电荷转移态复合物时能够形成双分子穿插结构.双分子穿插结构改变了共混体系的薄膜形貌,不利于器件的光电转换过程.本文从双分子穿插结构形成过程入手,论述了双分子穿插行为对共混体系结晶行为及相分离行为的影响,以及对器件光电转换过程中激子扩散与分离及载流子传输等物理过程的影响;详细阐述了现阶段抑制双分子穿插行为的化学、物理方面的主要方法及相关原理.同时,我们进一步提出了该领域尚待解决的问题并对其发展前景进行了展望.     

Fabrication and morphology control of the electrostatic self-assembled system containing porphyrin electrolytes and sulfonated fullerene derivatives

A series of water-soluble porphyrin electrolytes with quaternary ammonium ions side chains (TEMZnPN and THMZnPN) and sulfonated fullerene derivatives were synthesised and characterised. The self-assembled system was fabricated through the electrostatic interaction between the quaternary ammonium ions on the porphyrin derivatives and the sulfonic ions on the fullerene derivatives. The optical properties of the self-assembled system in aqueous solution were recorded by ultraviolet–visible and fluorescence spectroscopy. Scanning electron microscopy indicated that the morphology of the self-assembled films was highly relative to the distance between the quaternary ammonium ions and the porphyrin core, which could be easily adjusted by changing the length of the alkyl chain in the porphyrin derivatives.     

Research on pyrazoles. XLVII. Synthesis of pyrazoles with long-chain alkyl substituents

A number of alkylpyrazoles with long alkyl side chains are synthesized.In investigating the pharmacological activity of a number of pyrazole derivatives [2, 3], it was found that alkylpyrazoles have an appreciable effect on the central nervous system. To investigate this effect in greater detail, a number of alkylpyrazoles with long alkyl side chains at positions 1 and 3 were synthesized.For part XLVI see [1].     

Synthesis of derivatives of imidazo[4,5-b]pyridine： Novel sulfur contained side chains for macrolide antibiotics

Two series of novel derivatives of imidazo[4,5-b]pyridine were synthesized. These compounds could be used as side chains of semisynthesised ketolide antibiotics. The side chains have free amine group which can attached to ketolide core. Macrolides with this kind of side chains will show obvious activities against erythromycin-resistant strains. The structure of the side chains was confirmed by ^1H, ^13C NMR, MS, HMBC spectra. 2007 Ping Sheng Lei. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

The Effect of the Side Chain on Gelation Properties of Bile Acid Alkyl Amides

Six bile acid alkyl amide derivatives were studied with respect to their gelation properties. The derivatives were composed of three different bile acids with hexyl or cyclohexyl side chains. The gelation behaviour of all six compounds were studied for 36 solvents with varying polarities. Gelation was observed mainly in aromatic solvents, which is characteristic for bile-acid-based low molecular weight gelators. Out of 108 bile acid-solvent combinations, a total of 44 gel systems were formed, 28 of which from lithocholic acid derivatives, only two from deoxycholic acid derivatives, and 14 from cholic acid derivatives. The majority of the gel systems were formed from bile acids with hexyl side chains, contrary to the cyclohexyl group, which seems to be a poor gelation moiety. These results indicate that the spatial demand of the side chain is the key feature for the gelation properties of the bile acid amides.     

Effect of oxadiazole side chains based on alternating fluorene-thiophene copolymers for photovoltaic cells

Three soluble alternating conjugated copolymers, comprised of 9,9-dihexylfluorene and thiophene derivatives with/without oxadiazole side chains, were synthesized via the palladium-catalyzed Suzuki coupling reaction. The structures of the polymers were confirmed with ¹H NMR and ¹³C NMR, and the effect of oxadiazole side chains on the thermal, optical, electrochemical and photovoltaic properties were investigated. The introduction of rigid oxadiazole side chains could benefit to improve thermal stabilities of the conjugated polymers. Cyclic voltammograms revealed that the LUMO energy levels of P2 and P3 were reduced in comparison with P1 due to the introduction of electron-deficient oxadiazole side chains, indicating that electron-injection and transporting properties have been improved. Photovoltaic cells (PVCs) were fabricated based on the blend of the as-synthesized copolymers and the fullerene acceptor [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) in a 1:1 weight ratio. The maximum power conversion efficiency (PCE = 1.49%) was obtained for P3 as the electron donor under the illumination of AM 1.5, 100 mW/cm².     

The synthesis and fluorescent properties of analogues of the zinc(II) specific fluorophore zinquin ester

The synthesis and fluorescent properties in the absence and presence of zinc(II) of a range of 2-substituted derivatives of N-(6-methoxy-2-methyl-8-quinolyl)-4-methylbenzenesulfonamide are described. These analogues formed complexes with zinc(II) as indicated by a bathochromic shift in their UV/vis spectra. Analogues with isobutenyl and isobutyl side chains at the 2-position formed fluorescent complexes whose fluorescence was stronger than that of the 2-methyl-containing parent. These derivatives were converted, via conversion to the phenol with boron tribromide and reaction with ethyl bromoacetate, to systems with ester-containing side chains analogous to zinquin ester, a specific cellular fluorophore for zinc(II). All of these ester derivatives formed complexes with zinc(II) resulting in a bathochomic shift in their UV/vis spectra. Compounds with isobutyl, isobutenyl, and styryl side chains exhibited increased fluorescence compared to that of zinquin ester in the presence of zinc(II). The compound with the 2-isobutyl side chain was more selective in its fluorescence for zinc(II) over cadmium(II) compared to zinquin ester.     

Synthesis of derivatives of imidazo[4,5-b]pyridine:Novel sulfur contained side chains for macrolide antibiotics

Two series of novel derivatives of imidazo[4,5-b]pyridine were synthesized.These compounds could be used as side chains of semisynthesised ketolide antibiotics.The side chains have free amine group which can attached to ketolide core.Macrolides with this kind of side chains will show obvious activities against erythromycin-resistant strains.The structure of the side chains was confirmed by ~1H,~(13)C NMR,MS,HMBC spectra.     

FLASH PHOTOLYSIS STUDIES OF PROTEINS AND INDOLE DERIVATIVES IN SOLUTION

Abstract— Transients obtained upon flash photolysis of a number of proteins in aqueous solution appear to derive from electron ejection from tryptophyl residue side chains. These decay by a second order process. Oxygen is an effective quencher for the protein transients but is less so for the flash-induced signals obtained from simple indole derivatives. Experiments using other quenchers indicate that the signals are not due to an indole triplet state, but that the triplet state may be a precursor of the flash-induced metastabie species. Compounds which bind to the active site of chymotrypsin were found to exert only non-specific effects on the flash-induced signals.     

新型含短氟碳链侧基的氧杂环丁烷单体的合成与表征

应用含短氟碳链的功能性聚合物可以避免因使用含长氟碳链化合物给环境带来的潜在危害. 以全氟丁基磺酰氟为原料, 通过磺酰化和N-烷基化合成带有端羟基的中间体4, 再通过2,2-二溴甲基氧杂环丁烷(2)与4的Williamson醚化反应合成了含全氟丁基磺酰胺侧基的新型氧杂环丁烷衍生物1a和1b. 以5,5-二甲基海因为原料, 采用类似的合成路线, 合成了带海因侧基的新型氧杂环丁烷单体6.     

Computer Simulation of Long Side‐Chain Substituted Poly(phenylene vinylene) Polymers

A molecular dynamics (MD) simulation was employed to investigate structure features and segment orientation of four poly(phenylene vinylene) (PPV) derivatives with long, flexible side chains at room temperature. In the simulations, the main chains of the polymers were found to be semirigid and exhibit a tendency to coil into ellipsoidal helices or form zigzag conformations of limited regularity. The simulations show that continuous quasi‐coplanar segments along the backbone are in a range of ≈2–4 repeat units. The ordered orientation and coupling distance of interchain aromatic rings can be correlated with optical properties of materials. A simplified quantum‐mechanical method was developed to investigate optical properties based on MD trajectories. The method was tested to simulate the absorption spectra of four PPV derivatives. The absorption maxima of the calculated spectra are in reasonable agreement with experimental data. This work implies that long‐range electron transfer along the backbones of these polymers may not occur, but may be mediated by interchain interactions.