Theoretical Investigation on the “ON-OFF” Mechanism of a Fluorescent Probe for Thiophenols: Photoinduced Electron Transfer and Intramolecular Charge Transfer

Author:

Wang Yuxi12ORCID,Zhang Meng1,Li Wenzhi12,Wang Yi1,Zhou Panwang2ORCID

Affiliation:

1. School of Biological Engineering, Dalian Polytechnic University, Dalian 116034, China

2. Institute of Molecular Sciences and Engineering, Institute of Frontier and Interdisciplinary Science, Shandong University, Qingdao 266237, China

Abstract

In this study, the sensing mechanism of (2E,4E)-5-(4-(dimethylamino)phenyl)-1-(2-(2,4dinitrophenoxy)phenyl)penta-2,4-dien-1-one (DAPH-DNP) towards thiophenols was investigated by density functional theory (DFT) and time-dependent DFT (TD-DFT). The DNP group plays an important role in charge transfer excitation. Due to the typical donor-excited photo-induced electron transfer (d-PET) process, DAPH-DNP has fluorescence quenching behavior. After the thiolysis reaction between DAPH-DNP and thiophenol, the hydroxyl group is released, and DAPH is generated with the reaction showing strong fluorescence. The fluorescence enhancement of DAPH is not caused by an excited-state intramolecular proton transfer (ESIPT) process. The potential energy curves (PECs) show that DAPH-keto is less stable than DAPH-enol. The frontier molecular orbitals (FMOs) of DAPH show that the excitation process is accompanied by intramolecular charger transfer (ICT), and the corresponding character of DAPH was further confirmed by hole-electron and interfragment charge transfer (IFCT) analysis methods. Above all, the sensing mechanism of the turn-on type probe DAPH-DNP towards thiophenol is based on the PET mechanism.

Funder

Natural Science Foundation of Shandong Province, China

Publisher

MDPI AG

Subject

Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science

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