Issue 4, 2022, Issue in Progress

The sensing mechanism of a flavone-based ESIPT fluorescent chemodosimeter for selective recognition towards fluoride: a theoretical

Abstract

The sensing mechanism of 3-hydroxyflavone-based (3-HF) fluorescent chemodosimeter 3-triisopropylsilylflavone (3-TPSF) for detecting fluoride (F) has been theoretically investigated. The calculated Laplacian bond order confirms that the Si–O bond of 3-TPSF is the reaction site of F. The free energy barrier of 18.33 kcal mol−1 indicates that F-triggered desilylation reaction can occur and then form the anionic state of 3-HF (3-HF) with a fluorescence peak at 545 nm. 3-HF captures H+ of the mixed aqueous medium to be transformed into 3-HF with an intramolecular hydrogen bond (O1–H⋯O2). The energy barrier of 1.86 kcal mol−1 in the S1 state obtained from the constructed potential energy curves confirms that the excited state intramolecular proton transfer (ESIPT) in 3-HF occurs to form a tautomer structure, which produces a long-wavelength emission of 549 nm. The fluorescence emitted from both 3-HF and 3-HF agrees with the experimental value of 530 nm appearing after adding F. Charge transfer analyses indicate that the extent of intramolecular charge transfer in 3-HF is more intense than that of 3-TPSF, which induces a large Stokes shift of 180 nm. Therefore, the sensing mechanism is attributed to the combination of a large charge transfer feature and ESIPT that are caused by desilylation reaction. The significant fluorescence change makes 3-TPSF a chemodosimeter for detecting F.

Graphical abstract: The sensing mechanism of a flavone-based ESIPT fluorescent chemodosimeter for selective recognition towards fluoride: a theoretical

Supplementary files

Article information

Article type
Paper
Submitted
25 Aug 2021
Accepted
22 Dec 2021
First published
14 Jan 2022
This article is Open Access
Creative Commons BY-NC license

RSC Adv., 2022,12, 2262-2269

The sensing mechanism of a flavone-based ESIPT fluorescent chemodosimeter for selective recognition towards fluoride: a theoretical

R. Wei, L. Jia, X. Jia and H. Zhai, RSC Adv., 2022, 12, 2262 DOI: 10.1039/D1RA06431B

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