空穴传输材料三芳胺衍生物的合成及性质研究

以二芳胺和芳碘体系为原料,经乌尔曼反应制备了一系列三芳胺衍生物,经NMR,IR,MS等表征了其结构,通过示差扫描量热法(DSC)测定了其玻璃化转变温度,并利用循环伏安法结合紫外可见光谱测定了其HOMO能级和LUMO能级.     

含三芳胺聚西夫碱的合成与表征

在有机电致发光器件中 ,为了提高器件性能 ,普遍使用空穴输送材料 (ＨＴＭ)以提高空穴注入密度[1～ 3 ] .三芳胺类化合物就是普遍使用的小分子ＨＴＭ .尽管三芳胺类小分子化合物空穴传输性能好 ,但却受到小分子ＨＴＭ普遍的结晶现象和靠真空蒸镀方式成膜的局限[4,5] ,目前 ,许多学者将注意力转向聚合物ＨＴＭ的研究[6～ 8] .聚合物ＨＴＭ可以避免小分子ＨＴＭ的结晶现象 ,具有较高的玻璃化温度并且用旋涂法即可成膜 ,大大简化了成膜工艺 .本文以三芳胺和双羰基化合物进行缩聚反应并制备出未见报道的含三芳胺聚西夫碱空穴输送材料 .这种材料…     

星状四芳胺类空穴传输材料的合成

有机电致发光器件 (ＯＥＬＤ)是继阴极射线管平板显示器 (ＣＲＴ)和液晶显示器 (ＬＣＤ)之后的第三代平板显示器。它具有主动发光、驱动电压低(2伏左右 )、发光亮度高 (1 3 0 0 0ｃｄ ｍ2 以上 ) ,无软Ｘ 射线污染 ,响应速度快 (1 0 -6 ～ 1 0 -8秒 )等优点。从 1 987年美藉华人邓清云等提出多层结构的ＯＥＬＤ的器件结构以来的十多年间 ,ＯＥＬＤ以及其材料的研究已成为显示技术以及显示材料等方面的研究热点 ,发展很快[1～ 3] 。在 1 999年日本先锋公司已开发出了单色的汽车用ＯＥＬ平板显示器商品 ,今年东芝公司又开发出了 2 .7英寸的彩…     

含三芳胺聚西夫碱空穴输送材料结晶性、热稳定性和传输性研究

采用缩聚反应合成了两种未见报道的含三芳胺聚西夫碱空穴输送材料（PC－1，PC－2），该材料具有非晶态结构、良好的热稳定性和空穴传输性，用IR，UV－Vis，^1H NMR对所合成的聚合物进行了表征；用XRD技术对在不同溶剂中得到的聚合物的结晶现象进行了研究；用热重分析（TG）和差热分析（DTA）技术对材料在氮气中的热稳定性进行了研究，并进一步用量子化学从头算方法，对电离热（Ip）和前线轨道能进行了计算，结果表明，用二甲苯为溶剂得到的聚合物无结晶现象，PC－1，PC－2均具有良好的热稳定性和空穴传输性。     

结构不对称三芳胺类化合物的合成、表征及性质研究

以二芳胺和3,5-二甲基碘苯为原料,利用乌尔曼(Ullmann)反应,合成出了4个结构不对称三芳胺衍生物1～4,除了化合物1之外均为新化合物.利用IR,1H NMR,13C NMR,HRMS和元素分析对其结构进行了表征.考察了它们的光学、电化学和热稳定性质.实验结果表明,所合成的4个目标化合物在氯仿稀溶液中发出绿色荧光,具有良好的电化学和热稳定性.所合成的目标化合物是潜在的空穴传输材料及发绿光的材料.     

三芳胺合成的研究进展

三芳胺化合物的合成方法主要有3种:(1)非金属催化的胺化反应;(2)铜催化的Ullnann反应,包括使用过量铜粉为催化剂的传统的Ullmann反应、使用相转移催化剂的Ullmann反应以及使用配体的post-Ullmann反应;(3)钯催化的Buchwald-Hartwig反应.该类反应活性的关键是配体的选择,根据配体结构的不同可分为双膦螯合型配体、单膦配体和非膦配体.对该类化合物的这几种合成方法的研究进展进行了总结.     

苯乙烯相连的卟啉-三芳胺共轭体的合成及表征

以三芳胺甲醛和4-二乙氧基甲基苄基亚磷酸二乙酯为原料经Wittig-Horner反应制得化合物4-[4-(N,N-二苯胺基)苯乙烯基]苯甲醛, 4-[4-(N,N-二对甲苯胺基)苯乙烯基]苯甲醛和4-[4-(N,N-二对甲氧基苯胺基)苯乙烯基]苯甲醛, 这些化合物与吡咯在丙酸中回流得到一类通过苯乙烯相连的卟啉-三芳胺共轭体, 并采用¹H NMR, ¹³C NMR, MS及UV-vis对卟啉化合物的结构进行了表征.     

含苯乙腈母体的酰替芳胺类衍生物的合成

合成了１１种未见文献报道的含苯乙腈母体的新型酰替芳胺类化合物，其结构经ＩＲ、＾１ＨＭＲ、元素等证实，并进行了室内平板杀菌活性试验。     

芳胺转化为酰芳胺的方法

按照形成酰胺键所用原料分类,可将芳胺酰基化分为羧酸衍生物法、羧酸法和其他方法。羧酸衍生物法主要有酰氯法和酸酐法;羧酸法主要有偶联法、TAPC研磨法、P(OMe)3/I2催化法、纳米MgO催化法;其他方法主要是乙腈法、N,N-二甲基乙酰胺法、Au/HAP催化下的羟基合成法。     

含三芳胺基的吡啶甲酸衍生物及其环金属铱配合物的合成与性能

通过Ullmann反应和Negishi偶联反应, 合成了一种含三芳胺功能基的吡啶-2-甲酸衍生物; 并以此为辅助配体、1-苯基异喹啉为环金属配体, 设计合成了一种新型环金属铱配合物. 该配合物的二氯甲烷溶液, 在391～461 nm范围呈现了强烈的金属-配体电荷转移(MLCT)电子跃迁吸收带; 其最大发光波长为609 nm. 与传统的二(1-苯基异喹啉)(吡啶-2-甲酸)合铱配合物相比, 设计的环金属铱配合物具有增强的MLCT电子跃迁吸收和低的氧化电位, 是一种有发展潜力的红色磷光材料.     

一种非线性结构空穴传输材料的合成及其光伏性能研究

以三苯胺为电子给体单元,4-叔丁基-甲氧基苯环为母核,设计合成了1种非线性“Y型”结构的空穴传输材料（2TPA-ph-tbyl）。光电化学测试结果表明该材料与钙钛矿材料能级匹配。单晶X射线衍射结果表明,该分子通过端位基团三苯胺形成分子间C-H/π相互作用。这种较强的侧链堆积作用使2TPA-ph-tbyl获得了3.13× 10-5 cm2 V-1 s-1的空穴迁移率,是商用空穴传输材料PEDOT：PSS的1.5倍。将其制备成倒置结构钙钛矿太阳能电池,开路电压达到1000 mV、短路电流密度为21.53 mA?cm-2,填充因子为0.71,其光电转换效率达到15.2%,高于PEDOT：PSS（13.7%）。稳态光致发光和阻抗测试表明,2TPA-ph-tbyl可以促进钙钛矿-空穴传输材料界面电荷传输,降低界面电荷复合,从而提高电池的开路电压和短路电流。上述结果表明,具有非线性结构的空穴传输材料可以通过增强分子间的侧链堆积效应,提高材料的空穴迁移率,进而提高电池的光电转换效率。     

Butterfly-Like Triarylamines with High Hole Mobility and On/Off Ratio in Bottom-Gated OFETs

Highly π-extended butterfly-shaped triarylamine dyads with aryleneethynylene spacer were constructed using an efficient synthetic route. These aryleneethynylene-bridged dyads are highly fluorescent and exhibited high HOMO levels, and low bandgaps, which are suitable for high-performance p-type OFETs. The field-effect transistors were fabricated through a solution-processable method and exhibited promising p-type performance with field-effect mobility up to 4.3 cm²/Vs and high I_on/off of 10⁸ under ambient conditions.     

Modular Synthesis of Triarylamines and Poly(triarylamine)s through a Radical Mechanism

A modular protocol for the triarylamine synthesis has been developed using diarylamines and electron-rich arenes, such as phenols, as the building blocks. The KI/KIO₄ system proves to be highly efficient for the cross-dehydrogenative coupling of phenothiazines/phenoxazines with phenols/anilines. A wide range of functional groups attached to both coupling partners were well tolerated. Through the manipulation of reaction temperatures, the sequential assembly of bis-triarylamines could be achieved to provide the unsymmetrically bis-aminated phenols efficiently. Furthermore, the multiple aminated polyphenols were rapidly constructed in good to high yields by a single operation.     

芳香族腙类空穴传输材料的合成及其光电性能研究

芳香族腙类空穴传输材料的合成及其光电性能研究;腙;合成;芳醛;空穴传输材料     

Nafion基氧化还原聚合物在空气中的电荷传输性能

利用三明治电池和伏安法测试了不同制备条件的Nafion基氧化还原聚合物膜在空气中的电荷传输性能. 研究结果表明, 混合适量聚乙二醇(PEG)的Nafion基金属联吡啶配合物{Nafion[M(bpy)2+3, PEG](M=Ru, Fe)}膜的表观电荷传递扩散系数(Dct)达到10-6-10-7 cm2·s-1 , 电子或空穴迁移率(μ)达到10-4-10-5 cm2·V-1·s-1. 在导电玻璃(ITO)电极与Nafion基氧化还原聚合物膜界面引入一层导电聚苯胺(PANI)后, 降低了其接触电阻, 使氧化还原聚合物膜的Dct提高至10-5-10-6 cm2·s-1, μ提高至10-3-10-4 cm2·V-1·s-1, 且工作电流提高了近两个数量级. 该固态氧化还原聚合物膜的性能比较稳定, 在空气中放置30天后其Dct和μ降低得很少.     

Designing Hole Transport Materials with High Hole Mobility and Outstanding Interface Properties for Perovskite Solar Cells

Organic–inorganic halide perovskite solar cells (PSCs) have attracted much attention due to their rapid increase in power conversion efficiencies (PCEs), and many efforts are devoted to further improving the PCEs. Designing highly efficient hole transport materials (HTMs) for PSCs may be one of the effective ways. Herein we theoretically designed three new HTMs (FDT−N, FDT−O, and FDT−S) by introducing a nitrogen-phenyl group, an oxygen atom, and a sulfur atom into the spiro core of an experimentally synthesized HTM (FDT), respectively. And then we performed quantum chemical calculation to study their application potential. The results show that the devices with FDT−O and FDT−S instead of FDT may have higher open circuit voltages owing to their lower highest occupied molecular orbital (HOMO) energy levels. Moreover, FDT−S exhibits the best hole transport performance among the studied HTMs, which may be due to the significant HOMO-HOMO overlap in the hole hopping path with the largest transfer integral. Furthermore, the results on interface properties indicate that introducing oxygen and sulfur atoms can enhance the MAPbI₃/HTM interface interaction. The present work not only offers two promising HTMs (FDT−O and FDT−S) for PSCs but also provides theoretical help for subsequent research on HTMs.     

Lithium Polystyrene Sulfonate as a Hole Transport Material in Inverted Perovskite Solar Cells

Despite the exceptional efficiency of perovskite solar cells (PSCs), further improvements can be made to bring their power conversion efficiencies (PCE) closer to the Shockley-Queisser limit, while the development of cost-effective strategies to produce high-performance devices are needed for them to reach their potential as a widespread energy source. In this context, there is a need to improve existing charge transport layers (CTLs) or introduce new CTLs. In this contribution, we introduced a new polyelectrolyte (lithium poly(styrene sulfonate (PSS))) (Li:PSS) polyelectrolyte as an HTL in inverted PSCs, where Li⁺ can act as a counter ion for the PSS backbone. The negative charge on the PSS backbone can stabilize the presence of p-type carriers and p-doping at the anode. Simple Li:PSS performed poorly due to poor surface coverage and voids existence in perovskite film as well as low conductivity. PEDOT:PSS was added to increase the conductivity to the simple Li:PSS solution before its use which also resulted in lower performance. Furthermore, a bilayer of PEDOT:PSS and Li:PSS was employed, which outperformed simple PEDOT:PSS due to high quality of perovskite film with large grain size also the large electron injection barrier (ϕ_e) impeded back diffusion of electrons towards anode. As a consequence, devices employing PEDOT:PSS / Li:PSS bilayers gave the highest PCE of 18.64%.     

Enhanced Hole Transport in Ternary Blend Polymer Solar Cells

Recently, ternary blend polymer solar cells have attracted great attention to improve a short-circuit current density (J_SC) effectively, because complementary absorption bands can harvest the solar light over a wide wavelength range from visible to near-IR region. Interestingly, some ternary blend solar cells have shown improvements not only in J_SC but also in fill factor (FF). Previously, we also reported that a ternary blend solar cell based on a low-bandgap polymer (PTB7-Th), a wide-bandgap polymer (PDCBT), and a fullerene derivative (PCBM) exhibited a higher FF than their binary analogues. Herein, we study charge transport in PTB7-Th/PDCBT/PCBM ternary blend films to address the origin of the improvement in FF. We found that hole polarons are located in PTB7-Th domains and their mobility is enhanced in the ternary blend film.     

Efficient Synthesis of Triarylamines Catalyzed by Copper(I) Diazabutadiene Complexes

Cuprous chloride was coordinated by diazabutadiene (DAB‐R) ligands to form Cu(I)‐(DAB‐R) complexes, most of which have a 1:1 ratio of Cu to DAB‐R as reported. In the case of a special DAB‐ⁱPP, N,N′‐bis(2,6‐diisopropylphenyl)‐1,4‐diaza‐1,3‐butadiene, an unexpected composition of complex was found with the formula Cu(I)Cl(DAB)₂. When employed as catalyst for triarylamine synthesis from the coupling of aryl halides with primary and secondary arylamines, the new Cu(I)‐(DAB‐ⁱPP) complex displayed high efficiency.