Anti-solvatochromic fluorescence enhancement via the suppression of S1-T2 intersystem crossing by polarity
Attenuated fluorescence of organic fluorescent probes is typically observed in hydrophilic environments due to solvatochromic fluorescence quenching, where the brightness decreases along with increasing solvent polarity. However, strategies to overcome this challenge remains elusive. Herein, we repo...
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Elsevier
2025-07-01
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| Series: | Next Materials |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S294982282500228X |
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| author | Hao Li Juanjuan Zhang Yue-Tong Fang Yu-Min Wang Gui-Yuan Wu Zhenggang Lan Zhou Lu |
| author_facet | Hao Li Juanjuan Zhang Yue-Tong Fang Yu-Min Wang Gui-Yuan Wu Zhenggang Lan Zhou Lu |
| author_sort | Hao Li |
| collection | DOAJ |
| description | Attenuated fluorescence of organic fluorescent probes is typically observed in hydrophilic environments due to solvatochromic fluorescence quenching, where the brightness decreases along with increasing solvent polarity. However, strategies to overcome this challenge remains elusive. Herein, we report polarity-facilitated anti-solvatochromic fluorescence enhancement, i.e., the emission becoming stronger in solvents with higher polarity, of two novel donor-acceptor type fluorescent probes. Using the femtosecond (nanosecond) UV/vis pump-broadband probe spectroscopy combined with density function theory calculations, we investigate the excited-state dynamics of these fluorescent probes as a function of solvent polarity. The femtosecond transient absorption spectra reveal an initial hypsochromic shift of the excited-state absorption signature, immediately after excitation, indicating rapid stabilization of the lowest excited state through dipole-dipole interactions. The gradual ground-state recovery is accompanied by the formation of a new persistive excited-state absorption signature suggesting the competition between fluorescent recombination and intersystem crossing (ISC). Our TDDFT calculations suggest that a rare S1-T2 intersystem crossing is inhibited by solvent polarity, prolonging the S1 lifetime and thereby preventing the solvatochromic fluorescence quenching. This study provides new insights into the ISC-mediated fluorescence enhancement, offering potentials for investigating polarity-sensitive chemical and biological processes. |
| format | Article |
| id | doaj-art-6d4f4f4a21824aefa4e2f877e3492f02 |
| institution | OA Journals |
| issn | 2949-8228 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Next Materials |
| spelling | doaj-art-6d4f4f4a21824aefa4e2f877e3492f022025-08-20T02:25:11ZengElsevierNext Materials2949-82282025-07-01810071010.1016/j.nxmate.2025.100710Anti-solvatochromic fluorescence enhancement via the suppression of S1-T2 intersystem crossing by polarityHao Li0Juanjuan Zhang1Yue-Tong Fang2Yu-Min Wang3Gui-Yuan Wu4Zhenggang Lan5Zhou Lu6Anhui Province Key Laboratory for Control and Applications of Optoelectronic Information Materials, School of Physics and Electronic Information, Anhui Normal University, Wuhu, Anhui 241002, China; Anhui Sanan Optoelectronics Corporation, Wuhu, Anhui 241008, China; Corresponding author at: Anhui Province Key Laboratory for Control and Applications of Optoelectronic Information Materials, School of Physics and Electronic Information, Anhui Normal University, Wuhu, Anhui 241002, China.School of Environment, South China Normal University, Guangzhou 510006, China; SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Environmental Theoretical Chemistry, South China Normal University, Guangzhou 510006, ChinaAnhui Province Key Laboratory for Control and Applications of Optoelectronic Information Materials, School of Physics and Electronic Information, Anhui Normal University, Wuhu, Anhui 241002, ChinaAnhui Province Key Laboratory for Control and Applications of Optoelectronic Information Materials, School of Physics and Electronic Information, Anhui Normal University, Wuhu, Anhui 241002, ChinaAnhui Province Key Laboratory for Control and Applications of Optoelectronic Information Materials, School of Physics and Electronic Information, Anhui Normal University, Wuhu, Anhui 241002, ChinaSchool of Environment, South China Normal University, Guangzhou 510006, China; SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Environmental Theoretical Chemistry, South China Normal University, Guangzhou 510006, ChinaAnhui Province Key Laboratory for Control and Applications of Optoelectronic Information Materials, School of Physics and Electronic Information, Anhui Normal University, Wuhu, Anhui 241002, ChinaAttenuated fluorescence of organic fluorescent probes is typically observed in hydrophilic environments due to solvatochromic fluorescence quenching, where the brightness decreases along with increasing solvent polarity. However, strategies to overcome this challenge remains elusive. Herein, we report polarity-facilitated anti-solvatochromic fluorescence enhancement, i.e., the emission becoming stronger in solvents with higher polarity, of two novel donor-acceptor type fluorescent probes. Using the femtosecond (nanosecond) UV/vis pump-broadband probe spectroscopy combined with density function theory calculations, we investigate the excited-state dynamics of these fluorescent probes as a function of solvent polarity. The femtosecond transient absorption spectra reveal an initial hypsochromic shift of the excited-state absorption signature, immediately after excitation, indicating rapid stabilization of the lowest excited state through dipole-dipole interactions. The gradual ground-state recovery is accompanied by the formation of a new persistive excited-state absorption signature suggesting the competition between fluorescent recombination and intersystem crossing (ISC). Our TDDFT calculations suggest that a rare S1-T2 intersystem crossing is inhibited by solvent polarity, prolonging the S1 lifetime and thereby preventing the solvatochromic fluorescence quenching. This study provides new insights into the ISC-mediated fluorescence enhancement, offering potentials for investigating polarity-sensitive chemical and biological processes.http://www.sciencedirect.com/science/article/pii/S294982282500228XAnti-solvatochromicFluorescence enhancementPolarityIntersystem crossing |
| spellingShingle | Hao Li Juanjuan Zhang Yue-Tong Fang Yu-Min Wang Gui-Yuan Wu Zhenggang Lan Zhou Lu Anti-solvatochromic fluorescence enhancement via the suppression of S1-T2 intersystem crossing by polarity Next Materials Anti-solvatochromic Fluorescence enhancement Polarity Intersystem crossing |
| title | Anti-solvatochromic fluorescence enhancement via the suppression of S1-T2 intersystem crossing by polarity |
| title_full | Anti-solvatochromic fluorescence enhancement via the suppression of S1-T2 intersystem crossing by polarity |
| title_fullStr | Anti-solvatochromic fluorescence enhancement via the suppression of S1-T2 intersystem crossing by polarity |
| title_full_unstemmed | Anti-solvatochromic fluorescence enhancement via the suppression of S1-T2 intersystem crossing by polarity |
| title_short | Anti-solvatochromic fluorescence enhancement via the suppression of S1-T2 intersystem crossing by polarity |
| title_sort | anti solvatochromic fluorescence enhancement via the suppression of s1 t2 intersystem crossing by polarity |
| topic | Anti-solvatochromic Fluorescence enhancement Polarity Intersystem crossing |
| url | http://www.sciencedirect.com/science/article/pii/S294982282500228X |
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