基于苯并[b]萘并[1,2-d]噻吩的可见光驱动光环化荧光turn-on型二芳基乙烯的合成与性能研究

doi:10.6023/A22040169

摘要/Abstract

可见光驱动光环化的荧光turn-on型二芳基乙烯分子开关是超分辨显微成像的理想材料, 但目前关于该类型分子的报道仍较少. 本工作合成了一种基于苯并[b]萘并[1,2-d]噻吩(BNTP)的405 nm可见光驱动光环化的荧光turn-on型二芳基乙烯分子BNTP-BTTO4, 同时系统研究了该分子的光物理性能与稳定性, 并借助密度泛函理论(DFT)计算厘清了分子实现可见光驱动光环化及荧光turn-on原因. 另外, 本研究发现BNTP引入后分子表现出比参比分子Ph-BTTO4更优异的抗疲劳性、热稳定性和光稳定性, 尤其是在历经200 min 405 nm可见光照射后, BNTP-BTTO4(c)吸收强度只下降4%, 光稳定性大幅提升. 本研究为设计开发性能优异的可见光驱动光环化的荧光turn-on型二芳基乙烯提供了新的思路.

关键词: 光致变色, 二芳基乙烯, 可见光驱动, 荧光turn-on, 苯并[b]萘并[1,2-d]噻吩

Diarylethenes (DAEs) fluorescent photoswitches have attracted much attention because of their promising applications in super-resolution bioimaging such as PALM (photoactivatable localization microscopy) and STORM (stochastic optical reconstruction microscopy). Up to now, the developed materials mainly relied on the combination of diarylethene photoswitches and fluorescent dye moiety, in which the fluorescence intensities are modulated by fluorescence resonance energy transfer or intramolecular electron transfer. However, these fluorescence turn-off mode photoswitches are not suitable for PALM and STORM. Thus, the construct of fluorescence turn-on diarylethenes is highly desirable, especially all visible-light-driven photoswitchable DAEs that rule out the use of high energy UV light. Herein, we report a 405 nm visible-light-triggered fluorescence turn-on DAE BNTP-BTTO4 based on benzo[b]naphtho[1,2-d]thiophene (BNTP) group, and the photophysical and stability properties of BNTP-BTTO4 was systematically investigated. Moreover, with the assistance of density functional theory (DFT) calculations, the reasons for the visible-light-driven photocyclization and fluorescent turn-on were clarified. The introduction of electron-donating BNTP redshifts the absorption edge of the BNTP-BTTO4 open-isomer (ca. 430 nm) compared with the control molecule Ph-BTTO4 open-isomer (ca. 390 nm). In addition, it was found that the introduction of BNTP resulted in the molecule exhibiting good fatigue resistance, thermal stability, and photostability than the control molecule. There was no obvious changes in the absorption spectra of BNTP-BTTO4 upon alternative irradiation with 365 or 405 nm light and visible light longer than 450 nm for 20 cycles. Furthermore, almost no change was observed in the absorption spectra of photostationary state BNTP-BTTO4(c) after storing in the dark for 24 h at either room temperature or 60 ℃. Particularly, the absorption intensity of BNTP-BTTO4(c) only decreased by 4% after 200 min of 405 nm visible light irradiation, and the photostability was significantly improved compared with the control molecule. This study provides a new idea for the design and development of visible-light-driven fluorescence turn-on DAEs with excellent performance.

Key words: photochromic, diarylethenes, visible-light-driven, fluorescence turn-on, benzo[b]naphtho[1,2-d]thiophene

引用此文

赵杰, 王治文, 李华清, 艾琦, 蔡培庆, 司俊杰, 姚鑫, 胡晓光, 刘祖刚. 基于苯并[b]萘并[1,2-d]噻吩的可见光驱动光环化荧光turn-on型二芳基乙烯的合成与性能研究[J]. 化学学报, 2022, 80(9): 1223-1230.

Jie Zhao, Zhiwen Wang, Huaqing Li, Qi Ai, Peiqing Cai, Junjie Si, Xin Yao, Xiaoguang Hu, Zugang Liu. Synthesis and Properties of Visible-light-driven Fluorescence Turn-on Diarylethenes Based on Benzo[b]naphtho[1,2-d]thiophene[J]. Acta Chimica Sinica, 2022, 80(9): 1223-1230.

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图/表 6

图1. BNTP-BTTO4与Ph-BTTO4的合成路线

Figure 1. Synthetic routes for BNTP-BTTO4 and Ph-BTTO4

图2. (a)甲苯溶液中, Ph-BTTO4和BNTP-BTTO4开环体的吸收光谱(5.0×10–5 mol•L–1). (b)甲苯溶液中, 405 nm可见光与λ>450 nm可见光交替照射下BNTP-BTTO4吸收光谱变化(5.0×10–5 mol•L–1), 内插附图: 光照前后颜色与荧光变化

Figure 2. (a) Absorption spectra of Ph-BTTO4(o) and BNTP-BTTO4(o) in toluene (5.0×10–5 mol•L–1). (b) Absorption spectra changes of BNTP-BTTO4 in toluene (5.0×10–5 mol•L–1) upon alternative 405 nm and visible light (>450 nm) irradiation, inset: Corresponding color changes of BNTP-BTTO4 under UV and daylight

图3. (a)甲苯溶液中, Ph-BTTO4(c)和BNTP-BTTO4(c)的稳态荧光光谱(5.0×10–5 mol•L–1). (b)甲苯溶液中, Ph-BTTO4(c)和BNTP-BTTO4(c)的瞬态荧光光谱(5.0×10–5 mol•L–1); (c)不同极性溶剂中Ph-BTTO4(c)和BNTP-BTTO4(c)的归一化稳态荧光光谱; (d) Ph-BTTO4(c)和BNTP-BTTO4(c)的Mataga-Lippert散点图

Figure 3. (a) Fluorescence spectra of Ph-BTTO4(c) and BNTP-BTTO4(c) in toluene (5.0×10–5 mol•L–1). (b) Transient decay spectra of Ph-BTTO4(c) and BNTP-BTTO4(c) in toluene (5.0×10–5 mol•L–1). (c) Normalized fluorescence spectra of Ph-BTTO4(c) and BNTP-BTTO4(c) in various solvents. (d) Mataga-Lippert plot for Ph-BTTO4(c) and BNTP-BTTO4(c)

图4. 基态下Ph-BTTO4与BNTP-BTTO4的HOMO和LUMO分布图

Figure 4. The HOMO and LUMO of Ph-BTTO4 and BNTP-BTTO4 in their ground state

	Ph-BTTO4		BNTP-BTTO4
	Open	Closed	Open	Closed
Theoretical data
E_VA(S₁)^a/eV	3.42	2.48	3.21	2.52
E_HOMO^b/eV	6.20	5.50	5.92	5.54
E_LUMO^b/eV	2.29	2.78	2.30	2.76
E_gap/eV	3.91	2.72	3.62	2.78
Experimental data
ε/(L•mmol^–1•cm^–1)	5.3		15.8
$\lambda_{max}^{EM}$/nm		592		593
ϕ_F		0.26		0.05
τ/ns		3.22		0.19

表1. Ph-BTTO4与BNTP-BTTO4的理论和光物理数据

Table 1. Theoretical and photophysical data for Ph-BTTO4 and BNTP-BTTO4

图5. (a)甲苯溶液中, Ph-BTTO4与BNTP-BTTO4在405 nm可见光与λ>450 nm可见光交替照射下最大吸收处吸收强度变化(5.0×10–5 mol•L–1); (b)甲苯溶液中, PSS状态时Ph-BTTO4与BNTP-BTTO4的吸收与暗黑环境放置24 h后的吸收(5.0×10–5 mol•L–1); (c)甲苯溶液中, 365 nm紫外光与405 nm可见光持续照射下Ph-BTTO4(c)与BNTP-BTTO4(c)最大吸收处吸收强度变化(5.0×10–5 mol•L–1)

Figure 5. (a) Absorbance switching of Ph-BTTO4 and BNTP-BTTO4 in toluene (5.0×10–5 mol/L) monitored at λmax upon alternative irradiation with 405 nm and visible light (>450 nm). (b) Absorbance spectra of Ph-BTTO4 and BNTP-BTTO4 in toluene (5.0×10–5 mol/L) at PSS before and after storing in the dark for 24 h. (c) Photostability of Ph-BTTO4(c) and BNTP-BTTO4(c) in toluene (5.0×10–5 mol/L) under continued 365 and 405 nm light illumination The intensity of 365 and 405 nm light (5 W) is approximately 48 mW/cm2 via optical power meter detection, the distance between light and optical power meter is 10 cm

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