外围基团诱导β-异靛蓝骨架氮杂-氟硼二吡咯(BODIPY)类似物的手性研究

doi:10.6023/cjoc202503026

有机化学 ›› 2025, Vol. 45 ›› Issue (11): 4163-4170.DOI: 10.6023/cjoc202503026 上一篇下一篇

研究论文

外围基团诱导β-异靛蓝骨架氮杂-氟硼二吡咯(BODIPY)类似物的手性研究

陈紫薇, 段思康, 汪乙慧, 范华丹, 杨梦婕, 王思斯^*(), 卢华^*()

杭州师范大学材料与化学化工学院有机硅化学及材料技术教育部重点实验室全省有机硅材料技术重点实验室杭州 311121

收稿日期:2025-03-25 修回日期:2025-06-18 发布日期:2025-08-11
基金资助:
国家自然科学基金(22571064); 国家自然科学基金(22401067); 杭州师范大学交叉学科研究(2024JCXK01)

Peripheral-Group Induced Chirality of β-Isoindigo Based Aza Dipyrrometheneboron Difluoride (BODIPY) Analogs

Ziwei Chen, Sikang Duan, Yihui Wang, Huadan Fan, Mengjie Yang, Sisi Wang^*(), Hua Lu^*()

Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121

Received:2025-03-25 Revised:2025-06-18 Published:2025-08-11
Contact: *E-mail: sisiwang@hznu.edu.cn; hualu@hznu.edu.cn
Supported by:
National Natural Science Foundation of China(22571064); National Natural Science Foundation of China(22401067); Interdisciplinary Research Project of Hangzhou Normal University(2024JCXK01)

文章分享

1. 250815-1.pdf(2351KB)

摘要/Abstract

螺烯型化合物因具有独特的手性特性而备受关注, 但获得其单一对映体通常需要耗时且昂贵的手性拆分. 此外, 这类化合物的手性光学响应通常局限于紫外光区. 针对这些问题, 提出了一种简便的策略: 通过在β-异靛蓝骨架氮杂-氟硼二吡咯(BODIPY)类似物(BIABs)母核结构的外围引入光学纯的联萘酚基团, 制备了6个具有光学活性的化合物. 所得的(R)/(S)-联萘酚-BIABs不仅表现出优异的光稳定性, 还展现出深红光发射、显著的科顿效应(Δε)以及高吸收不对称因子(g_abs)等特点. 同时, 这些化合物在深红区域实现了可调控的圆偏振发光(CPL), 并具有较高的CPL发光亮度. 该策略为光学活性化合物的合成提供了一种通用性强、操作简便的新途径.

关键词: 螺手性, 圆偏振发光, β-异靛蓝, (R)/(S)-联萘酚, 氟硼二吡咯(BODIPY)类似物

Helicene-type compounds are renowned for their unique chiral properties, however, obtaining their enantiomers usually requires laborious and costly chiral separations. Moreover, their chiroptical activity is typically limited to the ultraviolet spectral range, which restricts their broader applicability. To overcome these limitations, a novel and efficient strategy for synthesizing optically active compounds through the incorporation of an optically pure binaphthol (BINOL) group onto the periphery of β-isoindigo based aza dipyrrometheneboron difluoride (aza-BODIPY) analogues (BIABs) was presented. The resulting (R)/(S)-BINOL-BIABs demonstrate exceptional photostability, deep-red emission, strong Cotton effect (Δε) and high absorbance dissymmetry factor (g_abs). Moreover, tunable circularly polarized luminescence (CPL) with high brightness in the deep-red region was achieved. This strategy offers straightforward procedures for synthesizing optically active compounds.

Key words: helically chirality, circularly polarized luminescence (CPL), β-isoindigo, (R)/(S)-binaphthol, dipyrromethene- boron difluoride (BODIPY) analogue

引用此文

陈紫薇, 段思康, 汪乙慧, 范华丹, 杨梦婕, 王思斯, 卢华. 外围基团诱导β-异靛蓝骨架氮杂-氟硼二吡咯(BODIPY)类似物的手性研究[J]. 有机化学, 2025, 45(11): 4163-4170.

Ziwei Chen, Sikang Duan, Yihui Wang, Huadan Fan, Mengjie Yang, Sisi Wang, Hua Lu. Peripheral-Group Induced Chirality of β-Isoindigo Based Aza Dipyrrometheneboron Difluoride (BODIPY) Analogs[J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4163-4170.

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

分享此文

图/表 5

Scheme 1. Synthetic routes of β-isoindigo-based aza-BODIPY analogues (BIABs) (R)/(S)-4a, (R)-4b, (R)/(S)-5a and (R)-5b

Figure 1. Photophysical properties of (R)-BINOL-BIABs (R)-4a/4b/5a/5b (10 μmol/L) in dichloromethane at room temperature (a) Absorption spectra and (b) fluorescence spectra; (c) Photographs in daylight (up) and under UV light (down, λex=365 nm); (d) Photostability studies: (R)-4a, (R)-4b, and Rho 6G (525 nm, 850 mW/cm2); (R)-5a, (R)-5b, and MB (635 nm, 450 mW/cm2)

Compd.	λ_abs/nm	ε_max^a/10⁴	λ_em/nm	SS^b/cm^－1	Φ_F^c	τ^d/ns	k_r^e/(10⁸ s^－1)	k_nr^f/(10⁸ s^－1)
(R)-4a	579	3.59	616	1037	0.46	5.5	0.84	0.98
(R)-4b	611	3.07	635	618	0.28	4.1	0.68	1.76
(R)-5a	638	2.48	672	793	0.27	5.0	0.54	1.46
(R)-5b	668	2.72	695	581	0.22	3.4	0.65	2.29

Table 1. Photophysical properties of (R)-BINOL-BIABs

Figure 2. Chiral optical activity of (R)/(S)-BINOL-BIABs 4a~5b (10 μmol/L in dichloromethane, measured at room temperature) (a, b) Circular dichroism (CD) spectra of (R)/(S)-BINOL-BIABs; (c~f) CD and CPL spectra of optically resolved (R,M,M)-5a and (R,P,P)-5a, (R,M,M)-5b and (R,P,P)-5b (λex=638 nm for 5a, 688 nm for 5b)

Compd.	λ_abs/nm	Δε^a (S₀-S₁)	Δε^b S₀-S_n	\|g_abs\|^c/10^－3	\|g_lum\|^d/10^－3	B_cpl^e/(L•mol^－1•cm^－1)	\|μ\|^f/10^－18	\|m\|^f/10^－20	cosθ^f	\|g_cal,abs\|^g[10^－3
(R)-4a	579	16.8	－77.0	0.47	0.76	6.28	8.55	0.55	－0.162	0.42
(R)-5a	638	103.2	－236.9	4.16	2.90	9.71	7.29	2.31	－0.418	5.30
(R)-5b	668	69.2	－109.7	2.54	2.96	8.86	—	—	—	—

Table 2. Chiroptical properties of (R)-BINOL-BIABs

参考文献 36

[1]	Shen, Y.; Chen, C.-F. Chem. Rev. 2012, 112, 1463. doi: 10.1021/cr200087r pmid: 22017405
[2]	Gingras, M. Chem. Soc. Rev. 2013, 42, 968. doi: 10.1039/c2cs35154d pmid: 23151799
[3]	Zhao, W.-L.; Li, M.; Lu, H.-Y.; Chen, C.-F. Chem. Commun. 2019, 55, 13793. doi: 10.1039/C9CC06861A
[4]	Nakai, Y.; Mori, T.; Inoue, Y. J. Phys. Chem. A 2012, 116, 7372. doi: 10.1021/jp304576g
[5]	Mori, T. Chem. Rev. 2021, 121, 2373. doi: 10.1021/acs.chemrev.0c01017
[6]	Bouz, G.; Žádný, J.; Storch, J.; Vacek, J. Biotechnol. Adv. 2025, 79, 108513. doi: 10.1016/j.biotechadv.2024.108513
[7]	Fang, L.; Lin, W.-B.; Shen, Y.; Chen, C.-F. Chin. J. Org. Chem. 2018, 38, 541 (in Chinese). doi: 10.6023/cjoc201710028
	(房蕾, 林伟彬, 沈赟, 陈传峰, 有机化学, 2018, 38, 541.) doi: 10.6023/cjoc201710028
[8]	Huang, T.; Yuan, L.; Lu, X.; Qu, Y.; Qu, C.; Xu, Y.; Zheng, Y.-X.; Wang, Y. Chem. Sci. 2024, 15, 15170. doi: 10.1039/D4SC03854A
[9]	Yuan, L.; Ding, Q.-J.; Tu, Z.-L.; Liao, X.-J.; Luo, X.-F.; Yan, Z.-P.; Wu, Z.-G.; Zheng, Y.-X. Chin. Chem. Lett. 2022, 33, 1459. doi: 10.1016/j.cclet.2021.08.104
[10]	Zhang, L.; Song, I.; Ahn, J.; Han, M.; Linares, M.; Surin, M.; Zhang, H.-J.; Oh, J. H.; Lin, J. Nat. Commun. 2021, 12, 142. doi: 10.1038/s41467-020-20390-y pmid: 33420007
[11]	Yang, Y.; da Costa, R. C.; Fuchter, M. J.; Campbell, A. J. Nat. Photonics 2013, 7, 634. doi: 10.1038/nphoton.2013.176
[12]	Crassous, J.; Fuchter, M. J.; Freedman, D. E.; Kotov, N. A.; Moon, J.; Beard, M. C.; Feldmann, S. Nat. Rev. Mater. 2023, 8, 365. doi: 10.1038/s41578-023-00543-3
[13]	Domínguez, Z.; López-Rodríguez, R.; Álvarez, E.; Abbate, S.; Longhi, G.; Pischel, U.; Ros, A. Chem.-Eur. J. 2018, 24, 12660. doi: 10.1002/chem.201801908 pmid: 29901866
[14]	Cei, M.; Di Bari, L.; Zinna, F. Chirality 2023, 35, 192. doi: 10.1002/chir.v35.4
[15]	Zhang, F.; Michail, E.; Saal, F.; Krause, A.-M.; Ravat, P. Chem. Eur. J. 2019, 25, 16241. doi: 10.1002/chem.v25.71
[16]	Chen, K.; Liu, Y.-J.; Wang, Z.-L.; Hu, S.-L.; Zhao, Y.-L.; Wang, W.; Liu, G.-G.; Wang, Z.-H.; Jiang, W. J. Am. Chem. Soc. 2024, 146, 13499. doi: 10.1021/jacs.4c02914 pmid: 38696816
[17]	Ju, Y.-Y.; Xie, L.-E.; Xing, J.-F.; Deng, Q.-S.; Chen, X.-W.; Huang, L.-X.; Nie, G.-H.; Tan, Y.-Z.; Zhang, B. Angew. Chem., Int. Ed. 2025, 64, e202414383.
[18]	Liu, B.-K.; Zhang, Y.-L.; Chen, Y.; Liu, X.-G.; Zhang, L. Chin. J. Org. Chem. 2020, 40, 2879 (in Chinese). doi: 10.6023/cjoc202005005
	(刘秉康, 张艳丽, 陈瑜, 刘旭光, 张磊, 有机化学, 2020, 40, 2879.) doi: 10.6023/cjoc202005005
[19]	Liu, Y.-J.; Wang, Z.-H. Chin. J. Org. Chem. 2021, 41, 4844 (in Chinese). doi: 10.6023/cjoc202100096
	(刘豫健, 王朝晖, 有机化学, 2021, 41, 4844.) doi: 10.6023/cjoc202100096
[20]	Ito, H.; Segawa, Y.; Murakami, K.; Itami, K. J. Am. Chem. Soc. 2019, 141, 3. doi: 10.1021/jacs.8b09232
[21]	Xia, Y.-F.; Jiang, L.; Yang, Q.; Yu, X.; Chen, F.-K. Chin. J. Org. Chem. 2024, 44, 2841 (in Chinese). doi: 10.6023/cjoc202405006
	(夏羽菲, 江丽, 杨巧, 于琇, 陈丰坤, 有机化学, 2024, 44, 2841.) doi: 10.6023/cjoc202405006
[22]	Liang, J.-C.; Gan, F.-W.; Zhang, G.-L.; Shen, C.-S.; Qiu, H.-B. Nat. Commun. 2025, 16, 3788. doi: 10.1038/s41467-025-59222-2
[23]	Luo, L.-C.; Li, L.; Mu, Y.-B.; Li, B.-W.; Wan, X.-B. Chin. J. Org. Chem. 2022, 42, 1960 (in Chinese).
	(罗力铖, 李亮, 穆有炳, 李博文, 万晓波, 有机化学, 2022, 42, 1960.) doi: 10.6023/cjoc202202031
[24]	Du, J.-P.; Qin, P.-J.; Xu, L.-C.; Feng, S.-S.; Xu, Y.-X.; Huang, J. Chin. J. Org. Chem. 2020, 40, 194 (in Chinese). doi: 10.6023/cjoc201907001
	(杜俊平, 秦鹏举, 绪连彩, 封珊珊, 徐云祥, 黄江, 有机化学, 2020, 40, 194.) doi: 10.6023/cjoc201907001
[25]	Gu, H.; Ming, S.-L; Lin, K.-W.; Chen, S.; Liu, X.-M.; Lu, B.-Y.; Xu, J.-K. Electrochim. Acta 2018, 260, 772. doi: 10.1016/j.electacta.2017.12.033
[26]	Lei, T.; Wang, J.-Y.; Pei, J. Acc. Chem. Res. 2014, 47, 1117. doi: 10.1021/ar400254j
[27]	Stalder, R.; Mei, J.; Graham, K. R.; Estrada, L. A.; Reynolds, J. R. Chem Mater. 2014, 26, 664. doi: 10.1021/cm402219v
[28]	Mack, J.; Kobayashi, N. Chem. Rev. 2011, 111, 281. doi: 10.1021/cr9003049
[29]	Zatsikha, Y. V.; Shamova, L. I.; Nemykin, V. N. J. Org. Chem. 2021, 86, 4733. doi: 10.1021/acs.joc.1c00110 pmid: 33688739
[30]	Xu, Y.-Q.; Ni, Z.-G.; Xiao, Y.; Chen, Z.-W.; Wang, S.-S.; Gai, L.-Z.; Zheng, Y.-X.; Shen, Z.; Lu, H.; Guo, Z.-J. Angew. Chem., Int. Ed. 2023, 62, e202218023.
[31]	Chen, Z.-W.; Ni, Z.-G.; Chen, X.-Y.; Xu, Y.-Q.; Yu, C.-Y.; Wang, S.-S.; Wang, X.-Y.; Lu, H. Aggregate 2024, 5, e498.
[32]	Yu, C.-Y.; Xu, Y.; Bi, X.; Ni, Z.; Xiao, H.; Hu, X.; Lu, H. Tetrahedron Lett. 2023, 133, 154833. doi: 10.1016/j.tetlet.2023.154833
[33]	Bi, X.; Wang, S.; Zhang, J.; Peng, Y.; Shen, Z.; Lu, H. Chin. J. Inorg. Chem. 2025, 41, 1049 (in Chinese).
	(毕羡, 王思斯, 张金月, 彭雨佳, 沈珍, 卢华, 无机化学, 2025, 41, 1049.)
[34]	Wang, K.; Wang, H.-L.; Mack, J.; Li, W.-J.; Kobayashi, N.; Jiang, J.-Z. Acta Chim. Sinica 2012, 70, 1791 (in Chinese). doi: 10.6023/A12050262
	(王康, 王海龙, 约翰·马克, 李文军, 小林长夫, 姜建壮, 化学学报, 2012, 70, 1791.) doi: 10.6023/A12050262
[35]	Tay, A. C. Y.; Frogley, B. J.; Ware, D. C.; Conradie, J.; Ghosh, A.; Brothers, P. J. Angew. Chem., Int. Ed. 2019, 58, 3057. doi: 10.1002/anie.v58.10
[36]	Wang, S.-S.; Wang, Z.-L.; Song, W.-T.; Gao, H.; Wu, F.; Zhao, Y.; Chan, K.-S.; Shen, Z. Dalton Trans. 2022, 51, 2708. doi: 10.1039/D1DT04203C

外围基团诱导β-异靛蓝骨架氮杂-氟硼二吡咯(BODIPY)类似物的手性研究

Peripheral-Group Induced Chirality of β-Isoindigo Based Aza Dipyrrometheneboron Difluoride (BODIPY) Analogs

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 5

参考文献 36

相关文章 6

编辑推荐

相关统计

本文评价

[1]	李艳秋, 贾亚薇, 陈磅宽. 手性共轭有机三芳基硼(Ar₃B)发光材料研究进展[J]. 有机化学, 2025, 45(4): 1119-1136.
[2]	赵晨阳, 任静晓, 欧阳光辉, 刘鸣华. 手性双芘-谷氨酸两亲分子的超分子组装及圆偏振发光调控[J]. 有机化学, 2025, 45(11): 4171-4177.
[3]	孙翠萍, 薛雨婷, 陈磅宽. 杂螺烯圆偏振发光材料的研究进展[J]. 有机化学, 2025, 45(11): 4048-4069.
[4]	宋青岳, 杨桂懿, 张樾, 丘子杰. 螺烯衍生物的合成及其光电性质研究进展[J]. 有机化学, 2025, 45(11): 3953-3973.
[5]	夏羽菲, 江丽, 杨巧, 于琇, 陈丰坤. 圆偏振发光三重氮杂[6]螺烯: N-烷基化调控其手性光学性质[J]. 有机化学, 2024, 44(9): 2841-2846.
[6]	刘金果, 殷凤, 胡君, 巨勇. 超分子手性组装体的构建与应用[J]. 有机化学, 2021, 41(3): 1031-1052.