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

doi:10.6023/cjoc202503026

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (11): 4163-4170.DOI: 10.6023/cjoc202503026 Previous Articles Next Articles

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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)

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Abstract

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

Cite this article

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.

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Fig. & Tab. 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

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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

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Fig. & Tab. 5

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