苯并䓛盘状液晶: 合成、柱状相和光物理性质

doi:10.6023/A21080397

摘要/Abstract

盘状液晶分子由稠环芳核和围绕的多条柔性链构成, 具有独特的自组装有序超分子结构、半导体性质和光学性质. 其可通过溶液或喷墨打印技术加工成为光电子薄膜器件, 具有低成本优势. 通过Suzuki-Miyaura交叉偶联和Scholl氧化环化策略, 合成了一系列新的具有苯并䓛结构的非对称酸酐、羧酸酯、酰亚胺和苯并咪唑稠环衍生物, 并对其液晶性和光物理性质进行了详细研究. 通过偏振光学显微镜(POM), 差示扫描量热法(DSC)和小角度X射线散射(SAXS)测试表明, 这些极性盘状化合物自组装堆积呈六方柱状(Col_hex)液晶相, 其中, 最宽的液晶温度范围达206 ℃. 官能团和共轭体系大小决定了相变温度和液晶范围. 荧光测试结果表明, 化合物溶液中绝对量子产率高达34%, 根据官能团不同, 这些化合物发蓝、绿和红光. 借助密度泛函理论(DFT)计算, 解释了该系列极性盘状液晶分子发光性质的差异. 基于本工作的合成方法, 从萘酸酐原料出发为构建结构多变、性质丰富的π-共轭(杂环)芳烃盘状液晶化合物提供了新途径.

关键词: 苯并䓛, 苯并菲, 酰亚胺, 盘状液晶, 荧光, Suzuki-Miyaura偶联反应, Scholl反应

Discotic liquid crystal consisting of polycyclic aromatic hydrocarbon (PAH) core and peripheral alkyl chains is a kind of soft organic materials showing semiconductivity and fluorescence, and it can be fabricated into opto-electronic devices by solution process or printing technique, with low-cost advantage. We report benzo[g]chrysene unsymmetrical functional discotic liquid crystals, which were synthesized by Suzuki-Miyaura cross-coupling reaction and Scholl oxidative annulation. Five new π-extended compounds containing ester, anhydride, imide and benzoimidazole unit were synthesized and characterized. Their liquid crystalline property was fully characterized by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS), these compounds showed ordered columnar hexagonal (Col_hex) mesophase with broad mesophase range as wide as 206 ℃. The functional groups have essential impact on the phase transition temperatures. The ultraviolet-visible (UV-Vis) absorption and photoluminescent property were studied, they displayed fluorescent quantum yield as high as 34% in solution, and the emission spectra can be tuned from blue, green to red by functional group and π-conjugation extension. Density functional theory (DFT) computation results explained these physical properties. We anticipate that more π-extended functional molecules can be developed from naphthalic anhydride by our method.

Key words: benzo[g]chrysene, triphenylene, imide, discotic liquid crystal, fluorescence, Suzuki-Miyaura cross-coupling, Scholl reaction

引用此文

朱雪敏, 白小燕, 王海峰, 胡平, 汪必琴, 赵可清. 苯并䓛盘状液晶: 合成、柱状相和光物理性质[J]. 化学学报, 2021, 79(12): 1486-1493.

Xue-Min Zhu, Xiao-Yan Bai, Hai-Feng Wang, Ping Hu, Bi-Qin Wang, Ke-Qing Zhao. Benzo[g]chrysene Discotic Liquid Crystals: Synthesis, Columnar Mesophase and Photophysical Properties[J]. Acta Chimica Sinica, 2021, 79(12): 1486-1493.

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

分享此文

图/表 12

图式1. 苯并?衍生物的分子结构、命名、合成及收率

Scheme 1. Molecular structure, nomenclature, synthesis and yield of benzo[g]chrysene derivatives

图式2. 苯并?酯衍生物BCe的合成

Scheme 2. Synthesis of benzo[g]chrysene ester BCe

图1. 苯并?衍生物从液态缓慢降温至液晶态的POM织构图

Figure 1. POM textures of liquid crystal phase of benzo[g]chrysene derivatives slowly cooled from isotropic liquid state

图2. 苯并?衍生物的DSC曲线图(升温/降温速率: 10 ℃/min)

Figure 2. DSC curves of benzo[g]chrysene derivatives with heating and cooling rate of 10 ℃/min

Compound	Mesophases, transition temperature and enthalpy changes
Compound	2nd heating/℃ (ΔH/(kJ•mol^-1))	1st cooling/℃ (ΔH/(kJ•mol^-1))
BCd	Cr 104 (38.0) Col_hex 181 (2.7) I	I 178 (–2.8) Col_hex 77 (–43.6) Cr
BCo	Cr 97 (50.8) Col_hex 179 (3.6) I	I 175 (–4.1) Col_hex 12 (–38.1) Cr
BCe	Cr 1 (23.7) Col_hex 48 (3.4) I	I 44 (–3.1) Col_hex –6 (–23.3) Cr
BCbb	Cr 1 (21.3) Col_hex 207 (4.0) I	I 200 (–4.6) Col_hex –6 (–20.9) Cr
BCb	Cr 102 (68.8) Col_hex 215 (3.2) I	I 212 (–4.7) Col_hex 70 (–52.2) Cr

表1. 苯并?衍生物的相变温度和焓变

Table 1. Phase transition temperature and enthalpy change of benzo[g]chrysene derivatives

图3. 苯并?衍生物柱状相小角X-射线散射图(从各向同性液体冷却至柱状相)

Figure 3. SAXS of the benzo[g]chrysene derivatives at columnar mesophase (cooling from isotropic liquid to Colhex phase)

Compound	2θ_exp/(°)	d_exp/nm	d_calc/nm	I/%	hk	Lattice parameter/nm
BCd (120 ℃)	3.92	2.252	2.252	100	10	a=2.600 A=5.85 nm²
	6.90	1.280	1.300	3	11
	19.16	0.463	—	0.4	h_ch
	24.98	0.356	—	3.8	h_π
BCo (160 ℃)	3.76	2.348	2.348	100	10	a=2.711 A=6.37 nm²
	6.61	1.337	1.356	2.3	11
	19.12	0.464	—	0.7	h_ch
	24.04	0.370	—	6.7	h_π
BCe (35 ℃)	4.10	2.153	2.153	100	10	a=2.486 A=5.35 nm²
	7.01	1.261	1.243	1.3	11
	19.48	0.455	—	1.0	h_ch
	24.96	0.356	—	3.3	h_π
BCbb (180 ℃)	3.70	2.385	2.385	100	10	a=2.754 A=6.56 nm²
	7.56	1.168	1.193	0.8	20
	19.05	0.466	—	0.1	h_ch
	24.20	0.367	—	0.4	h_π
BCb (200 ℃)	4.07	2.169	2.169	100	10	a=2.505 A=5.43 nm²
	6.96	1.269	1.252	1.3	11
	19.21	0.462	—	0.2	h_ch
	24.87	0.358	—	2.0	h_π

表2. 苯并?衍生物液晶相X射线散射数据

Table 2. X-ray diffraction parameters of columnar mesophase of benzo[g]chrysene derivatives

图4. 苯并?衍生物BCb在CDCl3中随浓度变化的核磁氢谱

Figure 4. Concentration-dependent 1H NMR of BCb in CDCl3

图5. 苯并?衍生物的紫外/可见吸收光谱和荧光发射光谱. (a)紫外-可见吸收光谱(THF, 10-5 mol•L-1), (b)溶液荧光光谱(THF, 10-5 mol•L-1), (c)薄膜荧光光谱

Figure 5. The UV-Vis absorption spectra in solution and fluorescent spectra in solution and thin film of the benzo[g]chrysene derivatives. (a) the UV-Vis absorption spectra of sample in THF (10-5 mol•L-1), (b) fluorescent emission of sample in THF (10-5 mol•L-1), (c) fluorescent emission of sample as thin film

Compd.	λ_abs/ nm	ε/(×10⁴, L•mol^-1• cm^-1)	λ_em/nm solution	λ_em/nm film	Solution quantum yield/%
BCd	284 307 422	5.08	551	576	21.98
BCo	280 305 419	5.45	529	540	23.67
BCe	302 336 371	5.66	466	498	34.33
BCbb	282 306 418	5.53	532	552	22.23
BCb	284 444	6.43	551	573	26.74

表3. 苯并?衍生物的紫外-可见光吸收和荧光发射数据汇总

Table 3. Summary of UV-Vis absorption and photoluminescent emission parameters of the benzo[g]chrysene derivatives

图6. 苯并?衍生物在THF溶液中的前线轨道HOMO-LUMO及能隙差

Figure 6. Benzo[g]chrysene derivatives HOMO-LUMO and energy gap in THF

图7. 苯并?衍生物在真空中的前线轨道HOMO-LUMO及能隙差

Figure 7. Benzo[g]chrysene derivatives HOMO-LUMO and energy gap in vacuum

参考文献 21

[1]	Wöhrle, T.; Wurzbach, I.; Kirres, J.; Kostidou, A.; Kapernaum, N.; Litterscheidt, J.; Haenle, J. C.; Staffeld, P.; Baro, A.; Giesselmann, F.; Laschat, S. Chem. Rev. 2016, 116, 1139. doi: 10.1021/acs.chemrev.5b00190
[2]	Sergey Sergeyev, S.; Pisula, W.; Geerts, Y. H. Chem. Soc. Rev. 2007, 36, 1902. pmid: 17982517
[3]	Bushby, R.; Kawata, K. Liq. Cryst. 2011, 38, 1415. doi: 10.1080/02678292.2011.603262
[4]	Kumar, S. Liq. Cryst. 2004, 31, 1037. doi: 10.1080/02678290410001724746
[5]	Schmidt-Mende, L.; Fechtenkotter, A.; Mullen, K.; Moons, E.; Friend, R. H.; MacKenzie, J. O. Science 2001, 293, 1119. pmid: 11498585
[6]	Ghosh, T.; Gerbig, L.; Lambov, M.; Dechant, M.; Lehmann, M. J. Mater. Chem. C 2020, 8, 5562. doi: 10.1039/C9TC07086A
[7]	Dechant, M.; Lehmann, M.; Uzurano, G.; Fujii, A.; Ozaki, M. J. Mater. Chem. C 2021, 9, 5689. doi: 10.1039/D1TC00710F
[8]	(a) Kwon, O.; Cai, X.; Qu, W.; Liu, F.; Szydłowska, J.; Gorecka, E.; Han, M. J.; Yoon, D. K.; Poppe, S.; Tschierske, C. Adv. Funct. Mater. 2021, 31, 2102271. doi: 10.1002/adfm.v31.28
	(b) Li, Y.; Concellón, A.; Lin, C.; Romero, N. A.; Lina, S.; Swager, T. M. Chem. Sci. 2020, 11, 4695. doi: 10.1039/D0SC00714E
[9]	(a) Zhao, K. C.; Du, J. Q.; Wang, H. F.; Zhao, K. Q.; Hu, P.; Wang, B. Q.; Monobe, H.; Heinrich, B.; Donnio, B. Chem. Asian. J. 2019, 14, 462. doi: 10.1002/asia.v14.3
	(b) Liu, C. X.; Wang, H.; Du, J. Q.; Zhao, K. Q.; Hu, P.; Wang, B. Q.; Monobe, H.; Heinrich, B.; Donnio, B. J. Mater. Chem. C 2018, 6, 4471. doi: 10.1039/C7TC05315K
	(c) Ma, T.; Wang, H. F.; Zhao, K. Q.; Wang, B. Q.; Hu, P.; Monobe, H.; Heinrich, B.; Donnio, B. ChemPlusChem 2019, 84, 1439. doi: 10.1002/cplu.v84.9
	(d) Zhong, Y. J.; Zhao, K. Q.; Wang, B. Q.; Hu, P.; Monobe, H.; Heinrich, B.; Donnio, B. Dyes Pigm. 2020, 173, 107964. doi: 10.1016/j.dyepig.2019.107964
	(e) Ma, T.; Zhong, Y. J.; Wang, H. F.; Zhao, K. Q.; Wang, B. Q.; Hu, P.; Monobe, H.; Donnio, B. Chem. Asian J. 2021, 16, 1106. doi: 10.1002/asia.v16.9
[10]	(a) Hang, J. F.; Lin, H.; Zhao, K. Q.; Hu, P.; Wang, B. Q.; Monobe, H.; Zhu, C.; Donnio, D. Eur. J. Org. Chem. 2021, 13, 1989.
	(b) Yang, Y.; Wang, H.; Wang, H. F.; Liu, C. X.; Zhao, K. Q.; Wang, B. Q.; Hu, P.; Monobe, H.; Heinrich, B.; Donnio, B. Cryst. Growth Des. 2018, 18, 4296. doi: 10.1021/acs.cgd.8b00083
[11]	(a) Foster, E. J.; Jones, R. B.; Lavigueur, C.; Williams, V. E. J. Am. Chem. Soc. 2006, 128, 8569. pmid: 16802823
	(b) Voisin, E.; Foster, E. J.; Rakotomalala, M.; Williams, V. E. Chem. Mater. 2009, 21, 3251. pmid: 16802823
[12]	Adam, D.; Schuhmacher, P.; Simmerer, J.; Haussling, L.; Siemensmeyer, K.; Etzbachi, K. H.; Ringsdorf, H.; Haarer, D. Nature 1994, 371, 141. doi: 10.1038/371141a0
[13]	Zhao, K. Q.; An, L. L.; Zhang, X. B.; Yu, W. H.; Hu, P.; Wang, B. Q.; Xu, J.; Zeng, Q. D.; Monobe, H.; Shimizu, Y.; Heinrich, B.; Donnio, B. Chem. Eur. J. 2015, 21, 10379. doi: 10.1002/chem.201500889
[14]	Wurthner, F.; Saha-Moller, C. R.; Fimmel, B.; Ogi, S.; Leowanawat, P.; Schmidt, D. Chem. Rev. 2016, 116, 962. doi: 10.1021/acs.chemrev.5b00188
[15]	Gao, X.; Hu, Y. J. Mater. Chem. C 2014, 2, 3099. doi: 10.1039/C3TC32046D
[16]	Pu, J.; Yang, T.; Wang, Y.; Zhu, Q.; Yang, M.; Liu, C.; Wang, W. Liq. Cryst. 2020, 47, 291. doi: 10.1080/02678292.2019.1645899
[17]	(a) Psutka, K. M.; Bozek, K. J. A.; Maly, K. E. Org. Lett. 2014, 16, 5442. doi: 10.1021/ol502678m pmid: 31362501
	(b) Psutka, K. M.; LeDrew, J.; Taing, H.; Eichhorn, S. H.; Maly, K. E. J. Org. Chem. 2019, 84, 10796. doi: 10.1021/acs.joc.9b01330 pmid: 31362501
	(c) Fan, S. Y.; Xu, H. T.; Li, Q. G.; Fang, D. M.; Yu, W. H.; Xiang, S. K.; Hu, P.; Zhao, K. Q.; Feng, C.; Wang, B. Q. Liq. Cryst. 2020, 47, 1041. doi: 10.1080/02678292.2019.1704898 pmid: 31362501
	(d) Feng, C.; Ding, Y. H.; Han, X. D.; Yu, W. H.; Xiang, S. K.; Wang, B. Q.; Hu, P.; Li, L. C.; Chen, X. Z.; Zhao, K. Q. Dyes Pigm. 2017, 139, 87. doi: 10.1016/j.dyepig.2016.12.001 pmid: 31362501
[18]	(a) Camerel, F.; Donnio, B.; Ziessel, R. Soft Matter 2011, 7, 412. doi: 10.1039/C0SM00547A
	(b) Ye, Q.; hang, J. J.; Huang, K. W.; Chi, C. Org. Lett. 2011, 13, 5960. doi: 10.1021/ol202357f
[19]	(a) Liu, H.; Zhu, L.; Lou, X.; Yuan, L.; Zhang, X. Acta Chim. Sinica 2020, 78, 1240 (in Chinese). doi: 10.6023/A20070323
	( 刘红文, 朱隆民, 娄霄峰, 袁林, 张晓兵, 化学学报, 2020, 78, 1240.) doi: 10.6023/A20070323
	(b) Ren, J.; Wang, L.; Guo, R.; Tang, Y.; Zhou, H.; Lin, W. Acta Chim. Sinica 2021, 79, 87 (in Chinese). doi: 10.6023/A20080399
	( 任江波, 王蕾, 郭锐, 唐永和, 周红梅, 林伟英, 化学学报, 2021, 79, 87.) doi: 10.6023/A20080399
	(c) Xie, Z.; Fu, M.; Yin, B.; Zhu, Q. Chin. J. Org. Chem. 2018, 38, 1364 (in Chinese). doi: 10.6023/cjoc201712031
	( 谢振达, 付曼琳, 尹彪, 朱勍, 有机化学, 2018, 38, 1364.) doi: 10.6023/cjoc201712031
	(d) Yang, S.; Yan, S.; Yang, J.; Zhang, C.; Han, G. Chin. J. Org. Chem. 2018, 38, 425 (in Chinese).
	( 杨素华, 闫素君, 杨静, 张策, 韩国英, 有机化学, 2018, 38, 425.) doi: 10.6023/cjoc201708062
	(e) Wang, X.; Qi, S.; Du, J.; Li, Q.; Zhu, L.; Xue, L.; Zhao, Q.; Yang, Q.; Li, Y.; Cong, X. Chin. J. Org. Chem. 2021, 41, 719 (in Chinese). doi: 10.6023/cjoc202008005
	( 王欣宇, 戚少龙, 杜建时, 李强, 祝录宝, 薛龙启, 赵晴, 杨清彪, 李耀先, 丛宪玲, 有机化学, 2021, 41, 719.) doi: 10.6023/cjoc202008005
	(f) Chen, E.; Tang, Y.; Wang, L.; Ren, J.; Lin, W. Chin. J. Org. Chem. 2021, 41, 1200 (in Chinese). doi: 10.6023/cjoc202009016
	( 陈恩庆, 唐永和, 王蕾, 任江波, 林伟英, 有机化学, 2021, 41, 1200.) doi: 10.6023/cjoc202009016
[20]	(a) Bai, Y. F.; Chen, L. Q.; Xiang, S. K.; Zhang, K.; Li, Q. G.; Feng, C.; Hu, P.; Wang, B. Q.; Zhao, K. Q. RSC Adv. 2016, 6, 90494. doi: 10.1039/C6RA17701H
	(b) Lu, B.; Xiao, Y. Q.; Li, T. F.; Liu, K.; Lu, X. H.; Lian, J. R.; Zeng, P. J.; Qu, J. L.; Zhan, X. W. ACS Appl. Mater. Interfaces 2019, 11, 33006. doi: 10.1021/acsami.9b10834
	(c) Zhao, X. Q.; Ge, C. W.; Xu, X. P.; Huang, J. T.; Yang, X. D.; Peng, Q.; Li, W. S.; Gao, X. K. Chem. Commun. 2019, 55, 10234. doi: 10.1039/C9CC03682B
	(d) Zhao, X. Q.; Ge, C. W.; Yang, X. D.; Gao, X. K. Mater. Chem. Front. 2017, 1, 1635. doi: 10.1039/C7QM00030H
[21]	Godbert, N.; Crispini, A.; Ghedini, M.; Carini, M.; Chiaravalloti, F.; Ferrise, A. J. Appl. Cryst. 2014, 47, 668. doi: 10.1107/S1600576714003240