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

doi:10.6023/A22040169

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

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

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

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)

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

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

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

References 43

[1]	Jeong Y. C.; Yang S. I.; Ahn K. H.; Kim E. Chem. Commun. 2005, 19, 2503.
[2]	Jeong Y. C.; Yang S. I.; Kim E.; Ahn K. H. Tetrahedron 2006, 62, 5855. doi: 10.1016/j.tet.2006.04.029
[3]	Jeong Y. C.; Han J. P.; Kim Y.; Kim E.; Yang S. I.; Ahn K. H. Tetrahedron 2007, 63, 3173. doi: 10.1016/j.tet.2007.02.007
[4]	Uno K.; Niikura H.; Morimoto M.; Ishibashi Y.; Miyasaka H.; Irie M. J. Am. Chem. Soc. 2011, 133, 13558. doi: 10.1021/ja204583e
[5]	Pang S. C.; Hyun H.; Lee S.; Jang D.; Lee M. J.; Kang S. H.; Ahn K. H. Chem. Commun. 2012, 48, 3745. doi: 10.1039/c2cc30738c
[6]	Roubinet B.; Bossi M. L.; Alt P.; Leutenegger M.; Shojaei H.; Schnorrenberg S.; Nizamov S.; Irie M.; Belov V. N.; Hell S. W. Angew. Chem., Int. Ed. 2016, 55, 15429. doi: 10.1002/anie.201607940 pmid: 27767250
[7]	Yang H.; Li M. Q.; Li C.; Luo Q. F.; Zhu M. Q.; Tian H. Angew. Chem., Int. Ed. 2020, 59, 8560. doi: 10.1002/anie.201909830
[8]	Li C.; Xiong K.; Chen Y.; Fan C.; Wang Y. L.; Ye H.; Zhu M. Q. ACS Appl. Mater. Inter. 2020, 12, 27651. doi: 10.1021/acsami.0c03122
[9]	Roubinet B.; Weber M.; Shojaei H.; Bates M.; Bossi M. L.; Belov V. N.; Irie M.; Hell S. W. J. Am. Chem. Soc. 2017, 139, 6611. doi: 10.1021/jacs.7b00274 pmid: 28437075
[10]	Uno K.; Bossi M. L.; Konen T.; Belov V. N.; Irie M.; Hell S. W. Adv. Opt. Mater. 2019, 7, 1801746.
[11]	Qiang Z.; Shebek K. M.; Irie M.; Wang M. ACS Macro. Lett. 2018, 7, 1432. doi: 10.1021/acsmacrolett.8b00686
[12]	Irie M. Chem. Rev. 2000, 100, 1685. doi: 10.1021/cr980069d
[13]	Irie M.; Fukaminato T.; Matsuda K.; Kobatake S. Chem. Rev. 2014, 114, 12174. doi: 10.1021/cr500249p
[14]	Zhang J. J.; Zou Q.; Tian H. Adv. Mater. 2013, 25, 378. doi: 10.1002/adma.201201521
[15]	Zhu S.; Li W.; Zhu W. Prog. Chem. 2016, 28, 975.
[16]	Xu C.; Zhang J.; Xu W.; Tian H. Mater. Chem. Front. 2021, 5, 1060. doi: 10.1039/D0QM00567C
[17]	Singh R.; Xiao C.-C.; Wei C.-L.; Ho F.-C.; Khang T. M.; Gouda C.; Wu T.-K.; Li Y.-K.; Wei K.-H.; Lin H.-C. Mater. Chem. Front. 2021, 5, 438. doi: 10.1039/D0QM00605J
[44]	Maegawa R.; Kitagawa D.; Hamatani S.; Kobatake S. New J. Chem. 2021, 45, 18969. doi: 10.1039/D1NJ04047B
[45]	Frisch M. J.; Trucks G. W.; Schlegel H. B.; Scuseria G. E.; Robb M. A.; Cheeseman J. R.; Scalmani G.; Barone V.; Mennucci B.; Petersson G. A.; Nakatsuji H.; Caricato M.; Li X.; Hratchian H. P.; Izmaylov A. F.; Bloino J.; Zheng G.; Sonnenberg J. L.; Hada M.; Ehara M.; Toyota K.; Fukuda R.; Hasegawa J.; Ishida M.; Nakajima T.; Honda Y.; Kitao O.; Nakai H.; Vreven T.; Montgomery J. A.; Peralta J. E.; Ogliaro F.; Bearpark M.; Heyd J. J.; Brothers E.; Kudin K. N.; Staroverov V. N.; Keith T.; Kobayashi R.; Normand J.; Raghavachari K.; Rendell A.; Burant J. C., Iyengar S. S.; Tomasi J.; Cossi M.; Rega N.; Millam J. M.; Klene M.; Knox J. E.; Cross J. B.; Bakken V.; Adamo C.; Jaramillo J.; Gomperts R.; Stratmann R. E.; Yazyev O.; Austin A. J.; Cammi R.; Pomelli C.; Ochterski J. W.; Martin R. L.; Morokuma K.; Zakrzewski V. G.; Voth G. A.; Salvador P.; Dannenberg J. J.; Dapprich S.; Daniels A. D.; Farkas Ö.; Foresman J. B.; Ortiz J. V.; Cioslowski J.; Fox D. J. Gaussian 09, Gaussian Inc., Wallingford CT, 2009.
[18]	Herder M.; Schmidt B. M.; Grubert L.; PätzeL M.; Schwarz J.; Hecht S. J. Am. Chem. Soc. 2015, 137, 2738. doi: 10.1021/ja513027s
[19]	Yin J.; Kwon Y.; Kim D.; Lee D.; Kim G.; Hu Y.; Ryu J. H.; Yoon J. J. Am. Chem. Soc. 2014, 136, 5351. doi: 10.1021/ja412628z
[20]	Carling C. J.; Boyer, J. C.; Branda, N. R. J. Am. Chem. Soc. 2009, 131, 10838. doi: 10.1021/ja904746s pmid: 19722663
[21]	Boyer J. C.; Carling C. J.; Gates B. D.; Branda N. R. J. Am. Chem. Soc. 2010, 132, 15766. doi: 10.1021/ja107184z
[22]	Kashihara R.; Morimoto M.; Ito S.; Miyasaka H.; Irie M. J. Am. Chem. Soc. 2017, 139, 16498 doi: 10.1021/jacs.7b10697 pmid: 29112401
[23]	Mori K.; Ishibashi Y.; Matsuda H.; Ito S.; Nagasawa Y.; Nakagawa H.; Uchida K.; Yokojima S.; Nakamura S.; Irie M.; Miyasaka H. J. Am. Chem. Soc. 2011, 133, 2621. doi: 10.1021/ja108992t
[24]	Zhang Z. W.; Zhang J. J.; Wu B.; Li X.; Chen Y.; Huang J. H.; Zhu L. L.; Tian H. Adv. Opt. Mater. 2018, 6, 1700847.
[25]	Zhang Z. W.; Wang W. H.; Jin P. P.; Xue J. D.; Sun L.; Huang J. H.; Zhang J. J.; Tian H. Nat. Commun. 2019, 10, 1. doi: 10.1038/s41467-018-07882-8
[26]	Yam V. W. W.; Ko C. C.; Zhu N. Y. J. Am. Chem. Soc. 2004, 126, 12734. doi: 10.1021/ja047446q
[27]	Poon C. T.; Lam W. H.; Wong H. L.; Yam V. W. W. J. Am. Chem. Soc. 2010, 132, 13992. doi: 10.1021/ja105537j
[28]	Poon C. T.; Lam W. H.; Yam V. W. W. Chem. Eur. J. 2013, 19, 3467. doi: 10.1002/chem.201203105
[29]	Iwai R.; Morimoto M.; Irie M. Photochem. Photobiol. Sci. 2020, 19, 783. doi: 10.1039/D0PP00064G
[30]	Chen S. J.; Li W. L.; Li X.; Zhu W. H. J. Mater. Chem. C 2017, 5, 2717. doi: 10.1039/C7TC00023E
[31]	Li Z. Y.; He C. J.; Lu Z. Q.; Li P. S.; Zhu Y. P. Dyes Pigm. 2020, 182, 108623. doi: 10.1016/j.dyepig.2020.108623
[32]	Ai Q.; Hong S. J.; Khan M. A.; Ahn K. H. Bull. Korean Chem. Soc. 2018, 39, 1308. doi: 10.1002/bkcs.11597
[33]	Wang L. P.; Wang L. M.; Zhang L. Mater. Chem. Phys. 2018, 212, 155. doi: 10.1016/j.matchemphys.2018.03.026
[34]	Zhang Q. S.; Kuwabara H.; Potscavage W. J.; Huang S. P.; Hatae Y.; Shibata T.; Adachi C. J. Am. Chem. Soc. 2014, 136, 18070. doi: 10.1021/ja510144h
[35]	Lakowicz J. R. Principles of Fluorescence Spectroscopy, Springer, New York, 2006, p. 208.
[36]	Ai Q.; Pang S. C.; Ahn K. H. Chem. Eur. J. 2016, 22, 656. doi: 10.1002/chem.201504131
[37]	Wu Y.; Chen S. J.; Yang Y. H.; Zhang Q.; Xie Y. S.; Tian H.; Zhu W. H. Chem. Commun. 2012, 48, 528. doi: 10.1039/C1CC15824D
[38]	Zhang D. D.; Song X. Z.; Cai M. H.; Kaji H.; Duan L. Adv. Mater. 2018, 30, 1705406.
[39]	Jia X.; Shao C.; Bai X.; Zhou Q.; Wu B.; Wang L.; Yue B.; Zhu H.; Zhu L. Proc. Natl. Acad. Sci. U. S. A. 2019, 116, 4816. doi: 10.1073/pnas.1821991116
[40]	Wu H.; Chi W.; Baryshinkov G.; Wu B.; Gong Y.; Zheng D.; Li X.; Zhao Y.; Liu X.; Agren H.; Zhu L. Angew. Chem., Int. Ed. 2019, 58, 4328. doi: 10.1002/anie.201900703
[41]	Jia X.; Yue B.; Zhou L.; Niu X.; Wu W.; Zhu L. Chem. Commun. 2020, 56, 4336. doi: 10.1039/D0CC00371A
[42]	Liu J. Y.; Zhou K. R.; Wang D.; Deng C.; Duan K.; Ai Q.; Zhang Q. S. Front. Chem. 2019, 7, 312. doi: 10.3389/fchem.2019.00312
[43]	Kitagawa D.; Nakahama T.; Nakai Y.; Kobatake S. J. Mater. Chem. C 2019, 7, 2865. doi: 10.1039/C8TC05357J

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