甲氧基修饰平面化三苯胺电子给体的合成与性能研究

摘要以2-氨基苯甲酸甲酯为原料,经过Ullmann 反应、亲核加成等反应,合成了一种甲氧基修饰的平面化三苯胺电子给体CMo,通过¹H NMR确定结构的正确性。与常见电子给体三苯胺TPA、吲哚啉YD作对比,紫外吸收光谱显示,CMo的最大吸收波长为304 nm,相比YD(298 nm)和TPA(297 nm)发生了红移,且最大吸收峰随极性的增强变化率大,表明CMo可离域化程度很大,给电子能力更好;循环伏安测试表明,CMo的HOMO能级(-5.21 eV)和LUMO能级(-1.48 eV)都高于YD(-5.38 eV、-1.70 eV)和TPA(-5.53 eV、-1.79 eV),可以作为新的电子给体材料应用于有机光电器件中。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	张叶
	周雪琴
	刘东志
	李巍

关键词：平面化电子给体三苯胺衍生物有机光电功能材料

Abstract： Using methyl 2-aminobenzoate as starting material, the Ullmann reaction and nucleophilic addition reaction were used to obtain a methoxy-modified planarized triphenylamine electron donor CMo. The elucidation of chemical structure were proved by ¹H NMR, compared with common electron donor triphenylamine TPA and indoline YD, the ultraviolet absorption spectrum shows that the maximum absorption wavelength of CMo is 304 nm, which is red-shifted compared to YD (298 nm) and TPA (297 nm), and the maximum absorption peak has a large change rate with the enhancement of polarity, indicating that CMo can be delocalized to a large extent and has better electron donating ability. Cyclic voltammetry test shows that HOMO energy level (-5.21 eV) and LUMO energy level (-1.48 eV) of CMo are higher than that of YD (-5.38 eV, -1.70 eV) and TPA (-5.53 eV, -1.79 eV), and can be used as a new electron donor material in organic optoelectronic devices.

Keywords： planarization electron donors triphenylamine derivatives organic photoelectric functional materials

Received 2021-04-20;

Fund:国家自然科学基金资助(21776207)。

Corresponding Authors: 李巍,副研究员,E-mail:liwei2008@tju.edu.cn。 Email: liwei2008@tju.edu.cn

About author: 张叶(1995-),女,硕士研究生,主要研究方向为有机光电功能材料。

引用本文:

张叶, 周雪琴, 刘东志, 李巍.甲氧基修饰平面化三苯胺电子给体的合成与性能研究[J]. 化学工业与工程, 2023,40(4): 15-22

ZHANG Ye, ZHOU Xueqin, LIU Dongzhi, LI Wei.Synthesis and properties of methoxy-modified planarized triphenylamine electron donor[J]. Chemcial Industry and Engineering, 2023,40(4): 15-22

[1] EARMME T. Solution-processed efficient blue phosphorescent organic light-emitting diodes (PHOLEDs) enabled by hole-transport material incorporated single emission layer[J]. Materials (Basel, Switzerland), 2021, doi:10.3390/ma14030554
[2] ZHOU Z, QIAO H, HOU Y, et al. Epitaxial halide perovskite-based materials for photoelectric energy conversion[J]. Energy & Environmental Science, 2021, 14(1):127-157
[3] ZHANG J, ZHANG W, WU Y, et al. Wafer-scale Si-GaN monolithic integrated E-mode cascode FET realized by transfer printing and self-aligned etching technology[J]. IEEE Transactions on Electron Devices, 2020, 67(8):3304-3308
[4] SUN H, LIU D, WANG T, et al. Enhanced internal quantum efficiency in dye-sensitized solar cells:Effect of long-lived charge-separated state of sensitizers[J]. ACS Applied Materials & Interfaces, 2017, 9(11):9880-9891
[5] SUN H, LIU D, WANG T, et al. Charge-separated sensitizers with enhanced intramolecular charge transfer for dye-sensitized solar cells:Insight from structure-performance relationship[J]. Organic Electronics, 2018, 61:35-45
[6] DEVADIGA D, SELVAKUMAR M, SHETTY P, et al. Recent developments in metal-free organic sensitizers derived from carbazole, triphenylamine, and phenothiazine for dye-sensitized solar cells[J]. International Journal of Energy Research, 2021, 45 (5):6584-6643
[7] 于奕峰, 胡智超, 吕海军, 等. 三苯胺类太阳能电池染料敏化剂的研究进展[J]. 河北科技大学学报, 2015, 36(2):210-218 YU Yifeng, HU Zhichao, LYU Haijun, et al. Research progress of triphenylamine dye sensitizers of solar cells[J]. Journal of Hebei University of Science and Technology, 2015, 36(2):210-218(in Chinese)
[8] HORIUCHI T, YASHIRO T, KAWAMURA R, et al. Indoline dyes with benzothiazole unit for dye-sensitized solar cells[J]. Chemistry Letters, 2016, 45(5):517-519
[9] KOTTESWARAN S, RAMASAMY P. The influence of triphenylamine as a donor group on Zn-porphyrin for dye sensitized solar cell applications[J]. New Journal of Chemistry, 2021, 45(5):2453-2462
[10] KURUMISAWA Y, HIGASHINO T, NIMURA S, et al. Renaissance of fused porphyrins:Substituted methylene-bridged thiophene-fused strategy for high-performance dye-sensitized solar cells[J]. Journal of the American Chemical Society, 2019, 141(25):9910-9919
[11] EZHOV A V, VYAL'BA F Y, ZHDANOVA K A, et al. Synthesis of donor-π-acceptor porphyrins for DSSC:DFT-study, comparison of anchoring mode and effectiveness[J]. Journal of Porphyrins and Phthalocyanines, 2020, 24(4):538-547
[12] SUN H, LI P, LIU D, et al. Tuning photophysical properties via alkoxyl groups in charge-separated triphenylamine sensitizers for dye-sensitized solar cells[J]. Journal of Photochemistry and Photobiology A:Chemistry, 2019, 368:233-241
[13] DO K, KIM D, CHO N, et al. New type of organic sensitizers with a planar amine unit for efficient dye-sensitized solar cells[J]. Organic Letters, 2012, 14(1):222-225
[14] TIAN L, WANG Y, ZHANG Y, et al. Molecular engineering of indoline dyes and their application in dye-sensitized solar cells:Effect of planarity and side chain on interfacial charge-transfer processes[J]. ACS Applied Energy Materials, 2021, 4(1):242-248
[15] LIU Y, ZHANG X, LI C, et al. Energy-level control via molecular planarization and its effect on interfacial charge-transfer processes in dye-sensitized solar cells[J]. The Journal of Physical Chemistry C, 2019, 123(22):13531-13537
[16] LIANG M, CHEN J. Arylamine organic dyes for dye-sensitized solar cells[J]. Chemical Society Reviews, 2013, 42(8):3453-3488
[17] FANG Z, CHELLAPPAN V, WEBSTER R D, et al. Bridged-triarylamine starburst oligomers as hole transporting materials for electroluminescent devices[J]. Journal of Materials Chemistry, 2012, doi:10.1039/c2jm32840b
[18] CAI L P, TSAO H N, ZHANG W, et al. Organic sensitizers with bridged triphenylamine donor units for efficient dye-sensitized solar cells[J]. Advanced Energy Materials, 2013, 3(2):200-205
[19] XU M, ZHOU D, CAI N, et al. Electrical and photophysical analyses on the impacts of arylamine electron donors in cyclopentadithiophene dye-sensitized solar cells[J]. Energy & Environmental Science, 2011, 4(11):4735-4742
[20] WANG S, GUO J, HE L, et al. Influence of thiophene and benzene unit in triphenylamine dyes on the performance of dye-sensitized solar cells[J]. Synthetic Metals, 2013, 168:1-8
[21] LU X, FENG Q, LAN T, et al. Molecular engineering of quinoxaline-based organic sensitizers for highly efficient and stable dye-sensitized solar cells[J]. Chemistry of Materials, 2012, 24(16):3179-3187
[22] 徐清, 陈红征, 施敏敏, 等. 甲氧基取代三苯胺的合成及其性能研究[J]. 材料科学与工程学报, 2007, 25(2):190-192, 217 XU Qing, CHEN Hongzheng, SHI Minmin, et al. Synthesis and properties of methoxy-substituted triphenylamines[J]. Journal of Materials Science and Engineering, 2007, 25(2):190-192, 217(in Chinese)
[23] ZENG W, CAO Y, BAI Y, et al. Efficient dye-sensitized solar cells with an organic photosensitizer featuring orderly conjugated ethylenedioxythiophene and dithienosilole blocks[J]. Chemistry of Materials, 2010, 22(5):1915-1925
[24] SANKAR M, BHYRAPPA P. Effect of solvent on the electronic absorption spectral properties of Ni(Ⅱ) and Cu(Ⅱ)-complexes of some mixed β-octasubstituted-meso-tetraphenylporphyrins[J]. Chemical Physics Letters, 2019, 730:643-648