Bingqing Sun, Hui Wang, Jing Cheng, Hongbao Wu, Lei Liu
{"title":"Roles of ESIPT and TICT in the Photophysical Process of a Ratiometric Fluorescence Sensor for Al<sup>3</sup>.","authors":"Bingqing Sun, Hui Wang, Jing Cheng, Hongbao Wu, Lei Liu","doi":"10.1021/acs.jpca.4c04909","DOIUrl":null,"url":null,"abstract":"<p><p>Precise detection of Al<sup>3+</sup> with the aid of a fluorescence sensor is of fundamental importance in the fields of water pollution control and food safety. A comprehensive understanding of the photophysical process of the sensor as well as its underlying detection mechanism is a precondition for the design of highly efficient sensors. This contribution performs a thorough investigation of the ratiometric fluorescence sensing mechanism of an Al<sup>3+</sup> sensor with the aid of density functional theory and time-dependent density functional theory. Two excited-state intramolecular proton transfer (ESIPT) processes are observed on the S<sub>1</sub> state potential energy surface, which leads to emission around 565 nm. A twisted intramolecular charge transfer state is observed after one of the ESIPT processes via cis-trans isomerization of the C═N bond. However, the large energy barrier hinders its occurrence, which is quite unusual. Al<sup>3+</sup> is found to form three strong coordination bonds with the sensor, which eliminates ESIPT processes and induces a significant blue shift of the emission spectrum to 480 nm. The origination of the sensor's selectivity is also uncovered by investigating the interaction between the sensor and interfering metal ions.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"9362-9370"},"PeriodicalIF":2.7000,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpca.4c04909","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/10/17 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Precise detection of Al3+ with the aid of a fluorescence sensor is of fundamental importance in the fields of water pollution control and food safety. A comprehensive understanding of the photophysical process of the sensor as well as its underlying detection mechanism is a precondition for the design of highly efficient sensors. This contribution performs a thorough investigation of the ratiometric fluorescence sensing mechanism of an Al3+ sensor with the aid of density functional theory and time-dependent density functional theory. Two excited-state intramolecular proton transfer (ESIPT) processes are observed on the S1 state potential energy surface, which leads to emission around 565 nm. A twisted intramolecular charge transfer state is observed after one of the ESIPT processes via cis-trans isomerization of the C═N bond. However, the large energy barrier hinders its occurrence, which is quite unusual. Al3+ is found to form three strong coordination bonds with the sensor, which eliminates ESIPT processes and induces a significant blue shift of the emission spectrum to 480 nm. The origination of the sensor's selectivity is also uncovered by investigating the interaction between the sensor and interfering metal ions.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.