Citation: Fengzhi Wang, Ke Hu, Jinquan Chen, Zhubin Hu, Haitao Sun, Tony D. James, Yufang Xu, Xuhong Qian. Meta-amino substituted naphthalimides exhibit large charge transfer and strong N-H vibrations enabling use as ratiometric fluorescent probe[J]. Chinese Chemical Letters, ;2026, 37(1): 110971. doi: 10.1016/j.cclet.2025.110971 shu

Meta-amino substituted naphthalimides exhibit large charge transfer and strong N-H vibrations enabling use as ratiometric fluorescent probe

Fengzhi Wang ^a ,
Ke Hu ^b ,
Jinquan Chen ^{b, c} ,
Zhubin Hu ^b ,
Haitao Sun ^{b, c, *,} ,
Tony D. James ^{d, e, *,} ,
Yufang Xu ^{a, *,} ,
Xuhong Qian ^{a, b}

a.
Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China
b.
State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University, Shanghai 200241, China
c.
Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan 030006, China
d.
Department of Chemistry, University of Bath, BA2 7AY, Bath, United Kingdom
e.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China

htsun@phy.ecnu.edu.cn

T.D.James@bath.ac.uk

yfxu@ecust.edu.cn

Received Date: 29 November 2024
Revised Date: 13 February 2025
Accepted Date: 18 February 2025
Available Online: 19 February 2025

Figures(6)

Fluorescent probes based on intramolecular charge transfer (ICT) have obvious advantages for accurate quantitative analysis. To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process, which is closely related to their ICT characteristics. 1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore. Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied, its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated. Herein, combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer (CT) is exhibited by the meta-amino substituted 1,8-naphthalimide (m-NH₂) compared to the para-amino substituted one (p-NH₂). The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation (m-NAc and p-NAc) can be attributed to the larger ICT and stronger -NH₂ vibrations. This observation is further demonstrated by deuterium oxide experiments, viscosity experiments and quantum chemical calculations. The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed. This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics, and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
- Meta-substituted,
- Naphthalimide,
- Theoretical insights,
- Charge transfer,
- Vibration
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