Simple substituents make big differences in photophysical performances of 2,1,3-benzothiadizole-conjugated spiropyrans

doi:10.1016/j.cjche.2024.04.016

中国化学工程学报 ›› 2024, Vol. 72 ›› Issue (8): 53-59.DOI: 10.1016/j.cjche.2024.04.016

Simple substituents make big differences in photophysical performances of 2,1,3-benzothiadizole-conjugated spiropyrans

Xiaoming Zhu¹, Yunting Liu¹, Mingyue Cao¹, Guangle Niu²

1 State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China;
2 School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China

收稿日期:2024-02-08 修回日期:2024-04-17 出版日期:2024-08-28 发布日期:2024-10-17
通讯作者: Guangle Niu,E-mail:niugl@bit.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (62105184); the Natural Science Foundation of Shandong Province, China (2022HWYQ-007 and ZR2021QB043); and the Special Fund of Taishan Scholars Project of Shandong Province, China (tsqn201909012).

Simple substituents make big differences in photophysical performances of 2,1,3-benzothiadizole-conjugated spiropyrans

Xiaoming Zhu¹, Yunting Liu¹, Mingyue Cao¹, Guangle Niu²

1 State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China;
2 School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China

Received:2024-02-08 Revised:2024-04-17 Online:2024-08-28 Published:2024-10-17
Contact: Guangle Niu,E-mail:niugl@bit.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (62105184); the Natural Science Foundation of Shandong Province, China (2022HWYQ-007 and ZR2021QB043); and the Special Fund of Taishan Scholars Project of Shandong Province, China (tsqn201909012).

摘要/Abstract

摘要： Developing multifunctional spiropyran dyes is of particular importance in diverse applications. In the present study, we synthesized two 2,1,3-benzothiadiazole-conjugated spiropyrans (BT-SP-NO₂ and BT-SP-NMe₂) with distinct substituents. These donor-acceptor-structured spiropyrans exhibited typical twisted intramolecular charge transfer features and strong emissions in low-polarity solvents with fluorescence quantum yields (QYs) of up to 90.7%. Like traditional spiropyrans, the electron-acceptor-substituted BT-SP-NO₂ exhibited excellent photochromic behavior under multiple alternating UV-Vis irradiation, while the electron-donor-substituted BT-SP-NMe₂ was an acidochromic dye. In addition, the substituent groups distinctly affected the packing modes of these spiropyrans in the solid state. BT-SP-NMe₂ showed a much stronger solid-state emission (QY of 59.0%) than BT-SP-NO₂. Moreover, these two dyes were utilized as biocompatible probes for the specific light-up imaging of lipid droplets.

关键词: Spiropyran, 2,1,3-Benzothiadiazole, Photochromism, Fluorescent dye, Fluorescence imaging

Abstract: Developing multifunctional spiropyran dyes is of particular importance in diverse applications. In the present study, we synthesized two 2,1,3-benzothiadiazole-conjugated spiropyrans (BT-SP-NO₂ and BT-SP-NMe₂) with distinct substituents. These donor-acceptor-structured spiropyrans exhibited typical twisted intramolecular charge transfer features and strong emissions in low-polarity solvents with fluorescence quantum yields (QYs) of up to 90.7%. Like traditional spiropyrans, the electron-acceptor-substituted BT-SP-NO₂ exhibited excellent photochromic behavior under multiple alternating UV-Vis irradiation, while the electron-donor-substituted BT-SP-NMe₂ was an acidochromic dye. In addition, the substituent groups distinctly affected the packing modes of these spiropyrans in the solid state. BT-SP-NMe₂ showed a much stronger solid-state emission (QY of 59.0%) than BT-SP-NO₂. Moreover, these two dyes were utilized as biocompatible probes for the specific light-up imaging of lipid droplets.

Key words: Spiropyran, 2,1,3-Benzothiadiazole, Photochromism, Fluorescent dye, Fluorescence imaging

Xiaoming Zhu, Yunting Liu, Mingyue Cao, Guangle Niu. Simple substituents make big differences in photophysical performances of 2,1,3-benzothiadizole-conjugated spiropyrans[J]. 中国化学工程学报, 2024, 72(8): 53-59.

参考文献

[1] G. Das, T. Prakasam, N. Alkhatib, R.G. AbdulHalim, F. Chandra, S.K. Sharma, B. Garai, S. Varghese, M.A. Addicoat, F. Ravaux, R. Pasricha, R. Jagannathan, N. Saleh, S. Kirmizialtin, M.A. Olson, A. Trabolsi, Light-driven self-assembly of spiropyran-functionalized covalent organic framework, Nat. Commun. 14 (1) (2023) 3765.
[2] A.S. Kozlenko, I.V. Ozhogin, A.D. Pugachev, M.B. Lukyanova, I.M. El-Sewify, B.S. Lukyanov, A modern look at spiropyrans: from single molecules to smart materials, Top. Curr. Chem. 381 (1) (2023) 8.
[3] X.H. Wang, B. Xu, W.J. Tian, A new function of photochromic spiropyran: an efficient photoinitiator for two-photon polymerization, Light Sci. Appl. 12 (1) (2023) 140.
[4] Y. Xiong, P. Rivera-Fuentes, E. Sezgin, A. Vargas Jentzsch, C. Eggeling, H.L. Anderson, Photoswitchable spiropyran dyads for biological imaging, Org. Lett. 18 (15) (2016) 3666-3669.
[5] H.Q. Zheng, Y. Yang, Z.Y. Wang, D.R. Yang, G.D. Qian, Y.J. Cui, Photo-stimuli-responsive dual-emitting luminescence of a spiropyran-encapsulating metal-organic framework for dynamic information encryption, Adv. Mater. 35 (26) (2023) e2300177.
[6] W.C. Zhong, K.Q. Liang, W.F. Liu, L. Shang, Ligand-protected nanocluster-mediated photoswitchable fluorescent nanoprobes towards dual-color cellular imaging, Chem. Sci. 14 (33) (2023) 8823-8830.
[7] S. Zhang, Y. An, X.-m. Chen, Q. Li, Artificial molecular machines: design and observation, Smart Mol. 1 (2023) e20230015.
[8] S. Chatterjee, B. Liu, H.S. Peng, Chelation strategies in spiropyran-based chemosensors for colorimetric and fluorescent sensing of metal ions and anions, Coord. Chem. Rev. 508 (2024) 215779.
[9] R. Klajn, Spiropyran-based dynamic materials, Chem. Soc. Rev. 43 (1) (2014) 148-184.
[10] G.W. Ding, F.Q. Gai, Z.M. Gou, Y.J. Zuo, Multistimuli-responsive fluorescent probes based on spiropyrans for the visualization of lysosomal autophagy and anticounterfeiting, J. Mater. Chem. B 10 (26) (2022) 4999-5007.
[11] X. Xiao, W. Zheng, Y. Zhao, C.H. Li, Visible light responsive spiropyran derivatives based on dynamic coordination bonds, Chin. Chem. Lett. 34 (2) (2023) 107457.
[12] L. Kortekaas, W.R. Browne, The evolution of spiropyran: fundamentals and progress of an extraordinarily versatile photochrome, Chem. Soc. Rev. 48 (12) (2019) 3406-3424.
[13] L. Kortekaas, J. Chen, D. Jacquemin, W.R. Browne, Proton-stabilized photochemically reversible E/Z isomerization of spiropyrans, J. Phys. Chem. B 122 (24) (2018) 6423-6430.
[14] Y.N. Xue, J.T. Tian, W.G. Tian, K. Zhang, J.J. Xuan, X.H. Zhang, Spiropyran based recognitions of amines: UV-Vis spectra and mechanisms, Spectrochim. Acta Mol. Biomol. Spectrosc. 250 (2021) 119385.
[15] M. Piantek, G. Schulze, M. Koch, K.J. Franke, F. Leyssner, A. Kruger, C. Navio, J. Miguel, M. Bernien, M. Wolf, W. Kuch, P. Tegeder, J.I. Pascual, Reversing the thermal stability of a molecular switch on a gold surface: ring-opening reaction of nitrospiropyran, J. Am. Chem. Soc. 131 (35) (2009) 12729-12735.
[16] J. Mei, H. Tian, Most recent advances on enzyme-activatable optical probes for bioimaging, Aggregate 2 (2) (2021) e32.
[17] J.D. Wang, F.J. Huo, Y.B. Zhang, C.X. Yin, Spiropyran isomerization triggering ESIPT for visualization of pH fluctuations during oxidative stress in living cells, Chin. Chem. Lett. 34 (5) (2023) 107818.
[18] J. Li, X.C. Yin, B. Li, X.K. Li, Y.J. Pan, J. Li, Y. Guo, Spiropyran in situ switching: a real-time fluorescence strategy for tracking DNA G-quadruplexes in live cells, Anal. Chem. 91 (8) (2019) 5354-5361.
[19] S. Barman, J. Das, S. Biswas, T.K. Maiti, N.D. Pradeep Singh, A spiropyran-coumarin platform: an environment sensitive photoresponsive drug delivery system for efficient cancer therapy, J. Mater. Chem. B 5 (21) (2017) 3940-3944.
[20] X.R. Tian, J. Li, Y.H. Zhang, Y. Gao, M.W. Afzal, A.L. Wang, T.D. James, Y.J. Bai, Y. Guo, A spiropyran with low pK_a for tracking DNA G-quadruplexes and revealing the dissipation of △Ψm with senescence using an in situ switching strategy, Sensor. Actuator. B Chem. 359 (2022) 131618.
[21] R.Q. Yang, Y. Jiao, B.Y. Wang, B. Xu, W.J. Tian, Solid-state reversible dual fluorescent switches for multimodality optical memory, J. Phys. Chem. Lett. 12 (4) (2021) 1290-1294.
[22] J. Li, X.K. Li, J.B. Jia, X. Chen, Y.J. Lv, Y. Guo, J. Li, A ratiometric near-infrared fluorescence strategy based on spiropyran in situ switching for tracking dynamic changes of live-cell lysosomal pH, Dyes Pigments. 166 (2019) 433-442.
[23] J.Z. He, Y.H. Yang, Y.Q. Li, Z. He, Y.L. Chen, Z.H. Wang, H.M. Zhao, G.H. Jiang, Multiple anti-counterfeiting guarantees from simple spiropyran derivatives with solid photochromism and mechanochromism, Cell Rep. Phys. Sci. 2 (11) (2021) 100643.
[24] Q.K. Qi, C. Li, X.G. Liu, S. Jiang, Z.C. Xu, R. Lee, M.Q. Zhu, B. Xu, W.J. Tian, Solid-state photoinduced luminescence switch for advanced anticounterfeiting and super-resolution imaging applications, J. Am. Chem. Soc. 139 (45) (2017) 16036-16039.
[25] J. Ochi, K. Tanaka, Y. Chujo, Recent progress in the development of solid-state luminescent o-carboranes with stimuli responsivity, Angew. Chem., Int. Ed. Engl. 59 (25) (2020) 9841-9855.
[26] J. Zhang, B. He, Y. Hu, P. Alam, H. Zhang, J.W.Y. Lam, B.Z. Tang, Stimuli-responsive AIEgens, Adv. Mater. 33 (32) (2021) e2008071.
[27] Z. Zhang, M. Kang, H. Tan, N. Song, M. Li, P. Xiao, D. Yan, L. Zhang, D. Wang, B.Z. Tang, The fast-growing field of photo-driven theranostics based on aggregation-induced emission, Chem. Soc. Rev. 51 (6) (2022) 1983-2030.
[28] S.J. Zou, Y. Shen, F.M. Xie, J.D. Chen, Y.Q. Li, J.X. Tang, Recent advances in organic light-emitting diodes: toward smart lighting and displays, Mater. Chem. Front. 4 (3) (2020) 788-820.
[29] J. Mei, N.L. Leung, R.T. Kwok, J.W. Lam, B.Z. Tang, Aggregation-induced emission: together we shine, united we soar!, Chem. Rev. 115 (21) (2015) 11718-11940.
[30] K.X. Teng, W.K. Chen, L.Y. Niu, W.H. Fang, G.L. Cui, Q.Z. Yang, BODIPY-based photodynamic agents for exclusively generating superoxide radical over singlet oxygen, Angew. Chem., Int. Ed. Engl. 60 (36) (2021) 19912-19920.
[31] X.Z. Zhao, Q.C. Yao, S.R. Long, W.J. Chi, Y.X. Yang, D. Tan, X.G. Liu, H.Q. Huang, W. Sun, J.J. Du, J.L. Fan, X.J. Peng, An approach to developing cyanines with simultaneous intersystem crossing enhancement and excited-state lifetime elongation for photodynamic antitumor metastasis, J. Am. Chem. Soc. 143 (31) (2021) 12345-12354.
[32] Y. Tian, Z.H. Zhou, J.K. Gong, J.W. Li, C. He, J. Chen, S. Chen, R.J. Zeng, Z.Q. Mao, P.S. Zhang, Dual-locking fluorescent nanoprobes for HAase-triggered carbon monoxide imaging in living cells, Sensor. Actuator. B Chem. 394 (2023) 134421.
[33] R. Zou, Y. Yu, H.R. Pan, P.S. Zhang, F.M. Cheng, C.H. Zhang, S. Chen, J. Chen, R.J. Zeng, Cross-linking induced emission of polymer micelles for high-contrast visualization level 3 details of latent fingerprints, ACS Appl. Mater. Interfaces 14 (14) (2022) 16746-16754.
[34] J.R. Liu, Y. Wu, J. Tang, T. Wang, F. Ni, Q.M. Wu, X.J. Yang, Ayyaz Ahmad, N. Ramzan, Y.S. Xu, Polymeric assembled nanoparticles through kinetic stabilization by confined impingement jets dilution mixer for fluorescence switching imaging, Chin. J. Chem. Eng. 56 (2023) 89-96.
[35] H. Gu, W.J. Liu, H.D. Li, W. Sun, J.J. Du, J.L. Fan, X.J. Peng, 2, 1, 3-Benzothiadiazole derivative AIEgens for smart phototheranostics, Coord. Chem. Rev. 473 (2022) 214803.
[36] B.A.D. Neto, P.H.P.R. Carvalho, J.R. Correa, Benzothiadiazole derivatives as fluorescence imaging probes: beyond classical scaffolds, Acc. Chem. Res. 48 (6) (2015) 1560-1569.
[37] B.A.D. Neto, J.R. Correa, J. Spencer, Fluorescent benzothiadiazole derivatives as fluorescence imaging dyes: a decade of new generation probes, Chemistry 28 (4) (2022) e202103262.
[38] J. Qi, L. Feng, X. Zhang, H. Zhang, L. Huang, Y. Zhou, Z. Zhao, X. Duan, F. Xu, R.T.K. Kwok, J.W.Y. Lam, D. Ding, X. Xue, B.Z. Tang, Facilitation of molecular motion to develop turn-on photoacoustic bioprobe for detecting nitric oxide in encephalitis, Nat. Commun. 12 (1) (2021) 960.
[39] Z.R. Xu, Z.J. Zhang, X.Q. Deng, J.G. Li, Y.H. Jiang, W.C. Law, C.B. Yang, W.J. Zhang, X.L. Chen, K. Wang, D. Wang, G.X. Xu, Deep-brain three-photon imaging enabled by aggregation-induced emission luminogens with near-infrared-III excitation, ACS Nano 16 (4) (2022) 6712-6724.
[40] X.M. Zhu, L. Feng, S.X. Cao, J.G. Wang, G.L. Niu, Donor-acceptor-acceptor-conjugated dual-state emissive acrylonitriles: investigating the effect of acceptor unit order and biological imaging, Org. Lett. 24 (45) (2022) 8305-8309.
[41] L.J.W.Y. Hong Y., Tang B. Z., Aggregation-induced emission, Chem. Soc. Rev. 40 (2011) 5361–5388.
[42] M. Gao, B.Z. Tang, Fluorescent sensors based on aggregation-induced emission: recent advances and perspectives, ACS Sens. 2 (10) (2017) 1382-1399.
[43] G.L. Niu, R.Y. Zhang, X.J. Shi, H. Park, S. Xie, R.T.K. Kwok, J.W.Y. Lam, B.Z. Tang, AIE luminogens as fluorescent bioprobes, Trac. Trends Anal. Chem. 123 (2020) 115769.
[44] M. Ahn, M.J. Kim, K.R. Wee, Electron push-pull effects in 3, 9-Bis(p-(R)-diphenylamino)perylene and constraint on emission color tuning, J. Org. Chem. 84 (18) (2019) 12050-12057.
[45] S. Watanabe, A. Tahara, T. Isozaki, S. Kinoshita, R. Takeuchi, W. Kashihara, T. Suzuki, Effects of two electron-donating and/or-withdrawing substituents on two-photon absorption for diphenylacetylene derivatives, J. Phys. Chem. A 127 (30) (2023) 6204-6212.
[46] L. Xu, X. Shen, Z. Zhou, T. He, J. Zhang, H. Qiu, M.L. Saha, S. Yin, P.J. Stang, Metallacycle-cored supramolecular polymers: fluorescence tuning by variation of substituents, J. Am. Chem. Soc. 140 (49) (2018) 16920-16924.
[47] V. Punitharasu, M.F.M. Kavungathodi, J. Nithyanandhan, Interplay between π-bridges and positions of branched alkyl groups of unsymmetrical D-A-D-π-a squaraines in dye-sensitized solar cells: mode of dye anchoring and the charge transfer process at the TiO₂/dye/electrolyte interface, ACS Appl. Mater. Interfaces 9 (38) (2017) 32698-32712.
[48] M. Schulz-Senft, P.J. Gates, F.D. Sonnichsen, A. Staubitz, Diversely halogenated spiropyrans - useful synthetic building blocks for a versatile class of molecular switches, Dyes Pigments. 136 (2017) 292-301.
[49] C.L. Li, Y.F. Shi, P.F. Li, N. Zhang, N. Wang, X.D. Yin, P.K. Chen, Access to highly luminescent N-doped diazaborepins with penta-, hexa-, and heptagon substructures, Org. Lett. 23 (18) (2021) 7123-7128.
[50] T. Zhang, F.J. Huo, W.J. Zhang, J.B. Chao, C.X. Yin, Ultra-pH-sensitive sensor for visualization of lysosomal autophagy, drug-induced pH alteration and malignant tumors microenvironment, Sensor. Actuator. B Chem. 345 (2021) 130393.
[51] M. Jiang, X. Gu, J.W.Y. Lam, Y. Zhang, R.T.K. Kwok, K.S. Wong, B.Z. Tang, Two-photon AIE bio-probe with large Stokes shift for specific imaging of lipid droplets, Chem. Sci. 8 (8) (2017) 5440-5446.
[52] R.W. Horobin, F. Rashid-Doubell, J.D. Pediani, G. Milligan, Predicting small molecule fluorescent probe localization in living cells using QSAR modeling. 1. Overview and models for probes of structure, properties and function in single cells, Biotech. Histochem. 88 (8) (2013) 440-460.
[53] M.Y. Cao, T. Zhu, M.Y. Zhao, F.D. Meng, Z.Q. Liu, J.G. Wang, G.L. Niu, X.Q. Yu, Structure rigidification promoted ultrabright solvatochromic fluorescent probes for super-resolution imaging of cytosolic and nuclear lipid droplets, Anal. Chem. 94 (30) (2022) 10676-10684.
[54] J. Chen, C. Wang, W.J. Liu, Q.L. Qiao, H. Qi, W. Zhou, N. Xu, J. Li, H.L. Piao, D. Tan, X.G. Liu, Z.C. Xu, Stable super-resolution imaging of lipid droplet dynamics through a buffer strategy with a hydrogen-bond sensitive fluorogenic probe, Angew. Chem., Int. Ed. Engl. 60 (47) (2021) 25104-25113.
[55] G.S. Peng, J.N. Dai, R. Zhou, G.N. Liu, X.M. Liu, X. Yan, F.M. Liu, P. Sun, C.G. Wang, G.Y. Lu, Highly efficient red/NIR-emissive fluorescent probe with polarity-sensitive character for visualizing cellular lipid droplets and determining their polarity, Anal. Chem. 94 (35) (2022) 12095-12102.
[56] M. Taki, K. Kajiwara, E. Yamaguchi, Y. Sato, S. Yamaguchi, Fused thiophene-S, S-dioxide-based super-photostable fluorescent marker for lipid droplets, ACS Mater. Lett. 3 (1) (2021) 42-49.

Simple substituents make big differences in photophysical performances of 2,1,3-benzothiadizole-conjugated spiropyrans

Simple substituents make big differences in photophysical performances of 2,1,3-benzothiadizole-conjugated spiropyrans

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 0

编辑推荐

Metrics

本文评价