Benzodithiophene Hole‐Transporting Materials for Efficient Tin‐Based Perovskite Solar Cells

Developing efficient interfacial hole transporting materials (HTMs) is crucial for achieving high‐performance Pb‐free Sn‐based halide perovskite solar cells (PSCs). Here, a new series of benzodithiophene (BDT)‐based organic small molecules containing tetra‐ and di‐triphenyl amine donors prepared via a straightforward and scalable synthetic route is reported. The thermal, optical, and electrochemical properties of two BDT‐based molecules are shown to be structurally and energetically suitable to serve as HTMs for Sn‐based PSCs. It is reported here that ethylenediammonium/formamidinium tin iodide solar cells using BDT‐based HTMs deliver a champion power conversion efficiency up to 7.59%, outperforming analogous reference solar cells using traditional and expensive HTMs. Thus, these BDT‐based molecules are promising candidates as HTMs for the fabrication of high‐performance Sn‐based PSCs.     

电荷传输材料1-(4-甲氧基)苯基-2-[4′-(4″-甲氧基)三苯胺基]-乙烯的合成

在氮气保护下,以二苯胺、对碘苯甲醚和对甲氧基氯苄为原料,经过改良的Ullmann反应、Vilsmeier-Haack反应和Wittig反应,最终合成了电荷传输材料1-(4-甲氧基)苯基-2-[4′-(4″-甲氧基)三苯胺基]-乙烯,并优化了反应条件。该合成工艺具有反应温度低、反应时间短、操作简单的优点。     

微波辐射合成4-溴-4＇,4″-二甲基三苯胺

以氢氧化钾（4）为缚酸剂,CuCl、1,10-菲啰啉（3）为催化剂,在微波辐射条件下,对碘甲苯（1）和对溴苯胺（2）在甲苯（5）中反应合成了4-溴-4＇,4″-二甲基三苯胺,其结构经1HNMR和IR表征。由正交实验确定最佳工艺条件为：1用量为24 mmol,n（1）∶n（2）∶n（3）=2.4∶1.0∶4.0,微波功率为250 W,于105℃反应120 min,收率77.1%。     

新型三苯胺衍生物的合成及光谱和电化学性能

以三苯胺、芴酮等为原料,通过亲核加成反应合成了3个新型三苯胺衍生物:4-亚芴基肼撑亚甲基苯基二苯胺、双(4-亚芴基肼撑亚甲基苯基)苯胺和三(4-亚芴基肼撑亚甲基苯基)胺(a～c)。用FTIR、1HNMR、元素分析对3种化合物的结构进行了表征,并考察了其紫外吸收光谱、荧光光谱、电化学行为和热稳定性。结果表明,3个化合物(a～c)的薄膜均显示较强的红色荧光;且均具有明显的聚集诱导发光(Aggregation-induced emission,AIE)性能;其电离势(5.62～5.65 eV)与正电极(ITO)的功函数(4.8 eV)相匹配,可有效降低空穴注入的能垒,有利于空穴的传输;化合物(a～c)的热分解温度分别是317、292和303℃,均具有良好的热稳定性。     

一种新型三苯胺类空穴传输材料的合成与性能研究

以2,7-二碘-9,9-二甲基芴为原料分别经过Buchwald-Hartwig交叉偶联反应、Ullmann反应,对目标化合物9,9-二甲基N2,N7二苯基N2,N7二-对甲苯基-9H-芴-2,7-二胺（d-TPA）进行合成研究。通过¹H NMR、¹³C NMR以及HRMS-ESI等表征方法确定结构的正确性。研究表明：以铜粉为催化剂的Ullmann反应收率为85%,是最高效的合成方法。通过X射线衍射（XRD）测试和循环伏安法（CV）测试,结果表明：该材料为非晶材料,成膜性较好,且目标化合物的HOMO轨道能级值为-5.23 eV,与常用阳极材料ITO功函相近且化学稳定性较好,有利于空穴由阳极向空穴传输层的注入。将目标化合物用作空穴传输材料制备了有机发光二级管（OLED）并进行性能测试表征,结果显示：所得器件的启亮电压为3.8 V,最大发光亮度为21 412 cd/m²,最大电流效率为4.78 cd/A,表明该化合物有望成为一种性能优异的新型空穴传输材料。     

Synthesis and Analysis of Triphenylamine: A Review

In this paper, synthesis and characteristic of arylamine‐type molecules, particularly triphenylamine are discussed. An overview of the physical properties and chemical characteristics of these types of molecules is provided. Different synthesis methods and mechanisms involved for the production of these molecules and their analysis by HPLC are presented. Finally, a brief note about their purification is presented.     

Solution‐processable and electroactive aromatic polyamides with 3,5‐bis(trifluoromethyl)triphenylamine moiety

New fluorine‐containing, triphenylamine‐based diamine and dicarboxylic acid monomers, namely 3,5‐bis(trifluoromethyl)‐4′,4″‐diaminotriphenylamine and 3,5‐bis(trifluoromethyl)‐4′,4″‐dicarboxytriphenylamine, were synthesized and polymerized with commercially available aromatic dicarboxylic acids and diamines, respectively, leading to two series of aromatic polyamides, 5a–h and 7a–e . Most of the polyamides were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, flexible and strong films with good mechanical properties. The polyamides had useful levels of thermal stability associated with high glass transition temperatures of 273–305 °C and 10% weight‐loss temperatures in excess of 500 °C. Cyclic voltammograms of films of polymers 5a–h on indium–tin oxide‐coated glass substrates exhibited reversible oxidation redox couples with E_1/2 around 1.15 V versus Ag/AgCl in tetrabutylammonium perchlorate/acetonitrile solution, accompanied by a color change from colorless neutral state to reddish brown oxidized state. The 7 series polymers displayed a higher oxidation potential and less electrochemical stability as compared to the 5 series analogues. © 2017 Society of Chemical Industry     

Synthesis and Properties of Fully Triphenylamine-based Polyamides Bearing 3,5-bis(Trifluoromethyl) and/or 3,5-dimethyl Substituents on the Pendent Phenyl Units

Four new fully triphenylamine-based polyamides coded as polyamide (CF₃,CF₃), polyamide (CF₃,CH₃), polyamide (CH₃,CF₃), and polyamide (CH₃,CH₃) were synthesized by the phosphorylation polyamidation reaction from various combinations of 3,5-bis(trifluoromethyl)-4′,4″-dicarboxytriphenylamine, 3,5-dimethyl-4′,4″-dicarboxytriphenylamine, 3,5-bis(trifluoromethyl)-4′,4″-diaminotriphenylamine, and 3,5-dimethyl-4′,4″-diaminotriphenylamine. All the polyamides were amorphous and readily soluble in many common organic solvents and could be solution-cast into transparent, flexible, and strong films with good mechanical properties. They had useful levels of thermal stability associated with high glass-transition temperatures of 268–287°C and 10?wt%-loss temperatures in excess of 500°C. Cyclic voltammograms of the film of polyamide (CH₃,CH₃) on the indium-tin oxide-coated glass substrates exhibited two oxidation redox couples with E_1/2 around 0.82 and 1.29?V vs. Ag/AgCl in tetrabutylammonium perchlorate/acetonitrile solution, accompanied by a color change from pale yellow neutral state to dark green oxidized state. The CF₃-substituted polyamides displayed a higher oxidation potential and less electrochemical stability as compared to the CH₃-substituted analogues.     

基于1,8-萘酰亚胺延迟荧光材料的合成及性能研究

通过Suzuki交叉偶联反应得到三苯胺和N-苯基咔唑分别取代的1,8-萘酰亚胺衍生物,化合物结构经1HNMR、质谱和元素分析表征。两种材料都是双极分子,存在分子内电荷转移,单线态-三线态能级差分别为0.40和0.32 eV。荧光量子效率和荧光寿命的测试结果表明,两种材料均能发射延迟荧光。     

取代联噻吩染料敏化剂的合成与光伏性能研究

合成了以三苯胺为电子给体,氰基乙酸为电子受体,乙烯基单噻吩、乙烯基联噻吩和乙烯基烷基取代联噻吩作为共轭桥链的4个有机染料TD1、TD2、TD3和TD4。用核磁共振、质谱和傅里叶变换红外光谱对其结构进行了表征。通过电池性能、吸收和发射光谱分析及电化学测试,研究了增加共轭桥链、引入烷基链及烷基链的长短对染料光物理、电化学和光伏等性能的影响。结果表明,引入烷基链可以显著地提高短路电流和开路电压,并获得了较高的光电转化效率。其中以己基取代联噻吩作为共轭桥链的TD3,表现出最大的光电转化效率6.78%,达到了相同条件下测得的N719(7.64%)光电转化效率的88.7%。