基于三苯胺的D-A- π -A-D型化合物的合成及光物理性能  

Synthesis and Photophysical Properties of D-A-π-A-D Compound Based on Triphenylamine

作　　者：窦立薇 高亚楠 高宏[1,3] 翟兆兰 DOU Li-wei;GAO Ya-nan;GAO Hong;ZHAI Zhao-lan(Key Lab.of Biomass Energy and Material,Key Lab.of Chemical Engineering of Forest Products,National Forestry and Grassland Administration,National Engineering Lab.for Biomass Chemical Utilization,Institute of Chemical Industry of Forest Products,Chinese Academy of Forestry,Nanjing 210042,China;Jiangsu Co-innovation Center of Efficient Processing and Utilization of Forest Resources,Nanjing Forestry University,Nanjing 210037,China;Research Institute of Forestry New Technology,Chinese Academy of Forestry,Beijing 100091,China)

机构地区：[1]中国林业科学研究院林产化学工业研究所生物质化学利用国家工程实验室国家林业和草原局林产化学工程重点实验室江苏省生物质能源与材料重点实验室,江苏南京210042 [2]南京林业大学江苏省林业资源高效加工利用协同创新中心,江苏南京210037 [3]中国林业科学研究院林业新技术研究所,北京100091

出　　处：《化学试剂》2022年第3期415-421,共7页Chemical Reagents

基　　金：国家自然科学基金资助项目(31670576)。

摘　　要：以甲氧基三苯胺为电子供体,苯并噻二唑为电子受体,咔唑为共轭π桥,通过三步Suzuki偶联反应合成了D-A-π-A-D型荧光化合物4,4′-[(7,7′-9 H-咔唑-2,7-)-二(苯并噻二唑-7,4-)]-二(N,N-二(4-甲氧基苯基))苯胺(DTB-CZ),并用^(1)HNMR、^(13)CNMR、MALDI-TOF等手段对其结构进行表征。研究了它的光谱性能、电化学性能、轨道能级和热性能,并与D-π-D型化合物2TPA-CZ1的性能进行了比较。初步探索了DTB-CZ作为空穴传输材料在PSC中的应用。研究结果表明,DTB-CZ在甲苯溶液中的最大吸收波长为479 nm,最大发射波长为608 nm,在薄膜状态下最大吸收波长为495 nm,HOMO/LUMO能级为-4.91/-2.82 eV,带隙值为2.09 eV,热分解温度(T_(5d))为449.6℃,玻璃化转变温度(T_(g))为143.1℃。相比2TPA-CZ1,在甲苯溶液中吸收和发射波长分别红移了104、182 nm,在薄膜状态下吸收波长红移109 nm;带隙值降低0.84 eV;T_(5d)和T_(g)分别提高了9.6、24.7℃。结果表明,苯并噻二唑的引入,使化合物的共轭程度增大,带隙值降低,使得吸收和发射波长红移,使其具有更好的热稳定性和形态稳定性。D-A-π-A-D type compound DTB-CZ was synthesized by three-step Suzuki cross coupling reaction,in which methoxytriphenylamine,benzothiadiazole and carbazole acted as donor(D),acceptor(A)and the middleπ-bridge,respectively.The title DTB-CZ was structurally characterized by ^(1)HNMR,^(13)CNMR and MALDI-TOF,and studied for spectral performance,electrochemical performance,orbital energy level and thermal performance,and then compared with that of 2TPA-CZ1 with D-π-D structure.The performance of DTB-CZ was preliminarily investigated for application as a hole transport material in PSC.The results showed that DTB-CZ has the maximum absorption and emission at the wavelengths of 479 nm,and 608 nm,repectively,in toluene solution,and the maximum absorption at the wavelength of 495 nm in the film state.The HOMO/LUMO energy level and the band gap of DTB-CZ are-4.91/-2.82 eV,and 2.09 eV,respectively.The thermal decomposition temperature and the glass transition temperature of DTB-CZ are at 449.6℃and 143.1℃,respectively.Compared with that of 2TPA-CZ1,the absorption and emission wavelengths in toluene solution were red-shifted by 104 nm and 182 nm,respectively,and the absorption wavelength by 109 nm in the film state;the band gap value decreased by 0.84 eV;the thermal decomposition temperature and glass transition temperature increased by 9.6℃and 24.7℃,respectively.It showed that the introduction of benzothiadiazole enhanced the conjugation degree and narrowed the band gap,which made the absorption and emission red shift,leading to better thermal and morphological stability.

关 键 词：甲氧基三苯胺 苯并噻二唑 咔唑 D-A-π-A-D 光物理性能 

分 类 号：O621.3[理学—有机化学]