新型茚并芴-6,12-二酮衍生物的合成与性能研究

doi:10.6023/cjoc202206038

摘要/Abstract

以2,5-二溴对二甲苯和苯硼酸衍生物为原料, 经氧化、酯化、Suzuki偶联、皂化和合环反应, 高产率地得到不同烷基链修饰的茚并芴-6,12-二酮衍生物5. 在分子中灵活地引入不同长度的烷基链, 既提高了分子的溶解性, 又可以研究取代基对化合物性质的影响. 研究发现新化合物的溶解性和热学、光学稳定性均优于并五苯. 化合物5的最低的未占分子轨道(LUMO)能级都低于–3.4 eV, 因此具有较高的电子亲和能. 2,8-二异丙基茚并芴-6,12-二酮(5b)和2,8-二正丁基茚并芴-6,12-二酮(5c)具有刚性分子骨架并形成倾斜的面对面层状堆积, 层间距分别为0.3457和0.3423 nm, 分子层之间较强的π-π相互作用有利于载流子的传输. 为有机功能分子的设计提供一定的指导, 同时为有机场效应晶体管提供新的材料来源.

关键词: 茚并芴, 有机半导体材料, Suzuki偶联反应, 单晶结构, 刚性骨架

Indeno fluorene-6,12-dione derivatives 5 modified by different alkyl substitutions were designed and synthesized from 2,5-dibromo-p-xylene and phenylboronic acid derivatives through oxidation, esterification, Suzuki coupling, saponi- fication and cyclization reactions. Alkyl chains of different lengths were introduced into molecules to improve the solubility of the compounds and investigate the effects of systematic substitution variation on their properties. It was found that the solubility, thermal and optical stability of the new compounds were better than those of pentacene. Compounds 5 have increased electronegativities because of the low lowest unoccupied molecular orbital (LUMO) energies (≤–3.4 eV). 2,8- Diisopropylindeno[1,2-b]fluorene-6,12-dione (5b) and 2,8-dibutylindeno[1,2-b]fluorene-6,12-dione (5c) have rigid molecular frameworks and pack into slipped face-to-face π-stacks, the layer spacings are 0.3457 and 0.3423 nm, respectively. The molecular packing could facilitate carrier transport. The properties of these new materials indicate that they are good candidates for applications in organic optoelectronics.

Key words: indeno[1,2-b]fluorene, organic semiconductor, Suzuki coupling reaction, crystal structure, rigid framework

引用此文

王静, 吴琳琳, 王倩. 新型茚并芴-6,12-二酮衍生物的合成与性能研究[J]. 有机化学, 2023, 43(1): 223-228.

Jing Wang, Linlin Wu, Qian Wang. Synthesis and Characterization of New Indeno[1,2-b]fluorene-6,12-dione Derivatives[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 223-228.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

图式1. 化合物5a~5d的合成路线

Scheme 1. Synthetic route to compounds 5a~5d

图1. 化合物5a~5d (10 μmol/L)在二氯甲烷(DCM)溶剂中的紫外-可见吸收光谱

Figure 1. Normalized UV-Vis absorption spectra in dichloromethane (DCM) of 5a~5d (10 μmol /L)

Compound	λ_abs/nm	E_g^a/eV	λ_em/nm	T_dec/℃	E_ox/V	Eonset ox/V	E1 red/V	E2 red/V	Eonset red/V	E_HOMO^b/eV	E_LUMO^c/eV	Eel g/eV
5a	495, 315, 293	2.25	590	390
5b	508, 335, 295	2.12	610	345	1.69	1.51	–1.13	–1.54	–0.98	–5.91	–3.42	2.49
5c	509, 335, 295	2.13	625	385	1.70	1.53	–1.12	–1.53	–0.95	–5.93	–3.45	2.48
5d	505, 335, 295	2.14	617	400	1.69	1.52	–1.13	–1.54	–0.98	–5.92	–3.42	2.50

表1. 化合物5a~5d的光学、热分解温度和电化学数据

Table 1. Optical data, decomposition temperatures and electrochemical properties for compounds 5a~5d

图2. 化合物5a~5d (10 μmol /L)在DCM溶剂中的荧光发射光谱

Figure 2. Normalized fluorescence spectra of 5a~5d (10 μmol/ L) recorded in DCM Excitation wavelength of 5a: 400 nm, excitation wavelength of 5b~5d: 450 nm, slit width 5 nm

图3. 化合物5b~5d (0.001mol /L)的循环伏安曲线图

Figure 3. Cyclic voltammograms of 5b~5d(0.001 mol /L)

图4. 化合物5a~5d在氮气保护下升温速度为10 ℃?min–1时的热重分析(TGA)曲线

Figure 4. Thermogravimetric analysis (TGA) plots of 5a~5d with a heating rate of 10 ℃?min–1 under N2

图5. 化合物(a) 5b和(b) 5c的单晶结构

Figure 5. X-ray crystal structures of compounds (a) 5b and (b) 5c Red spheres depict O atoms and gray spheres C. Alkyl groups and hydrogen atoms have been omitted for clarity in packing.

参考文献 32

[1]	Jiang, H.; Zhu, S. L.; Cui, Z. D.; Li, Z. Y.; Liang, Y. Q.; Zhu, J. M.; Hu, Peng.; Zhang, H. L.; Hu, W. P. Chem. Soc. Rev. 2022, 51, 3071. doi: 10.1039/D1CS01136G
[2]	Jiang, H.; Hu, W. P. Angew. Chem., Int. Ed. 2020, 59, 1408. doi: 10.1002/anie.201814439 pmid: 30927312
[3]	Dong, H. L.; Zhu, H. F.; Meng, Q.; Gong, X.; Hu, W. P. Chem. Soc. Rev. 2012, 41, 1754. doi: 10.1039/C1CS15205J
[4]	Baeg, K. J.; Caironi, M.; Noh, Y. Y. Adv. Mater. 2013, 25, 4210. doi: 10.1002/adma.201205361
[5]	Koo, J. H.; Kim, D. C.; Shim, H. J.; Kim, T. H.; Kim, D. H. Adv. Funct. Mater. 2018, 28, 1801834.
[6]	Zschieschang, U.; Yamamoto, T.; Takimiya, K.; Kuwabara, H.; Ikeda, M.; Sekitani, T.; Someya, T.; Klauk, H. Adv. Mater. 2011, 23, 654. doi: 10.1002/adma.201003374
[7]	Zhan, Y. Q.; Mei, Y. F.; Zheng, L. R. J. Mater. Chem. C 2014, 2, 1220. doi: 10.1039/C3TC31765J
[8]	Zhang, C. C.; Chen, P. L.; Hu, W. P. Chem. Soc. Rev. 2015, 44, 2087. doi: 10.1039/C4CS00326H
[9]	Chen, D.; Pei, Q. B. Chem. Rev. 2017, 117, 11239. doi: 10.1021/acs.chemrev.7b00019
[10]	Han, S. T.; Zhou, Y.; Roy, V. A. L. Adv. Mater. 2013, 25, 5425. doi: 10.1002/adma.201301361
[11]	McNellis, E. R.; Schott, S.; Sirringhaus, H.; Sinova, J. Phys. Rev. Mater. 2018, 2, 074405.
[12]	Kuehne, A. J. C.; Gather, M. C. Chem. Rev. 2016, 116, 12823. doi: 10.1021/acs.chemrev.6b00172
[13]	Liu, Y.; Yu, G.; Liu, Y. Q. Sci. China: Chem. 2010, 53, 779. doi: 10.1007/s11425-010-0040-8
[14]	Cai, Z. X.; Awais, M. A.; Zhang, N.; Yu, L. P. Chem, 2018, 4, 2538. doi: 10.1016/j.chempr.2018.08.017
[15]	Cinar, M. E.; Ozturk, T. Chem. Rev. 2015, 115, 3036. doi: 10.1021/cr500271a
[16]	Dai, X. X.; Cheng, X. D.; Kan, Z. P.; Xiao, Z. Y.; Duan, T. N.; Hu, C.; Lu, S. R. Chin. J. Org. Chem. 2020, 40, 4031. (in Chinese) doi: 10.6023/cjoc202005023
	(戴学新, 成晓东, 阚志鹏, 肖泽云, 段泰男, 胡超, 陆仕荣, 有机化学, 2020, 40, 4031.)
[17]	Li, H. Y.; Tee, B. C. K.; Cha, J. J.; Cui, Y.; Chung, J. W.; Lee, S. Y.; Bao, Z. N. J. Am. Chem. Soc. 2012, 134, 2760. doi: 10.1021/ja210430b
[18]	Dong, H. L.; Hu, W. P. Acc. Chem. Res. 2016, 49, 2435. doi: 10.1021/acs.accounts.6b00368
[19]	Kitamura, M.; Arakawa, Y. J. Phys.: Condens. Matter 2008, 20, 184011. doi: 10.1088/0953-8984/20/18/184011
[20]	Jurchescu, O. D.; Popinciuc, M.; van Wees, B. J.; Palstra, T. T. M. Adv. Mater. 2007, 19, 688. doi: 10.1002/adma.200600929
[21]	Maliakal, A.; Raghavachari, K.; Katz, H.; Chandross, E.; Siegrist, T. Chem. Mater. 2004, 16, 4980. doi: 10.1021/cm049060k
[22]	Ebata, H.; Izawa, T.; Miyazaki, E.; Takimiya, K.; Ikeda, M.; Kuwabara, H.; Yui, T. J. Am. Chem. Soc. 2007, 129, 15732. doi: 10.1021/ja074841i
[23]	Usta, H.; Risko, C.; Wang, Z.; Huang, H.; Deliomeroglu, M. K.; Zhukhovitskiy, A.; Facchetti, A.; Marks, T. J. J. Am. Chem. Soc. 2009, 131, 5586. doi: 10.1021/ja809555c
[24]	Fan, Z. P.; Li, X. Y.; Luo, X. E.; Fei, X.; Sun, B.; Chen, L. C.; Shi, Z. F.; Sun, C. L.; Shao, X. F.; Zhang, H. L. Adv. Funct. Mater. 2017, 27, 1702318. doi: 10.1002/adfm.201702318
[25]	Sung, H.; Lin, H. Macromolecules 2004, 37, 7945. doi: 10.1021/ma0489927
[26]	Hou, J. H.; Tan, Z. A.; Yan, Y.; He, Y. J.; Yang, C. H.; Li, Y. F. J. Am. Chem. Soc. 2006, 128, 4911. doi: 10.1021/ja060141m
[27]	Zhao, C. C.; Zhang, Y.; Ng, M. K. J. Org. Chem. 2007, 72, 6364. doi: 10.1021/jo0704311
[28]	Rose, B. D.; Santa Maria, P. J., Fix, A. G.; Vonnegut, C. L.; Zakharov, L. N.; Parkin, S. R. Michael M. H. Beilstein J. Org. Chem. 2014, 10, 2122. doi: 10.3762/bjoc.10.219
[29]	Wang, J.; Zeng, W. L.; Xu, H.; Li, B.; Cao, X. P.; Zhang, H. L. Chin. J. Chem. 2012, 30, 681. doi: 10.1002/cjoc.201100141
[30]	Gao, X. K.; Wu, W. P.; Liu, Y. Q.; Jiao, S. B.; Qiu, W. F.; Yu, G.; Wang, L. P.; Zhu, D. B. J. Mater. Chem. 2007, 17, 736 doi: 10.1039/B613093C
[31]	Romain, M.; Chevrier, M.; Bebiche, S.; Mohammed-Brahim, T.; Rault-Berthelot, J.; Jacques, E.; Poriel, C. J. Mater. Chem. C 2015, 3, 5742. doi: 10.1039/C5TC00355E
[32]	Kobayashi, N.; Sasaki, M.; Nomoto, K. Chem. Mater. 2009, 21, 552. doi: 10.1021/cm802826m