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  

Synthesis and Properties of Visible-light-driven Fluorescence Turn-on Diarylethenes Based on Benzo[b]naphtho[1,2-d]thiophene

作　　者：赵杰 王治文 李华清 艾琦 蔡培庆 司俊杰 姚鑫 胡晓光 刘祖刚 Zhao Jie;Wang Zhiwen;Li Huaqing;Ai Qi;Cai Peiqing;Si Junjie;Yao Xin;Hu Xiaoguang;Liu Zugang(College of Optical and Electronic Technology,China Jiliang University,Hangzhou 310000;School of Material Science&Engineering,Zhengzhou University,Zhengzhou 450001)

机构地区：[1]中国计量大学光学与电子科技学院,杭州310000 [2]郑州大学材料科学与工程学院,郑州450001

出　　处：《化学学报》2022年第9期1223-1230,共8页Acta Chimica Sinica

摘　　要：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.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 sign

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 

分 类 号：O626.12[理学—有机化学] O641.1[理学—化学]