{"title":"A theoretical comprehension of photophysical processes in Cu2+ sensing by 1,7-di(2-pyridyl)bispyrazolo[3,4-b:4′,3′-e]pyridines","authors":"Ivan E. Romero , Gustavo Cabrera , Jaime Portilla","doi":"10.1016/j.molstruc.2024.140891","DOIUrl":null,"url":null,"abstract":"<div><div>Due to its simplicity and sensitivity, metal ion sensing by fluorescent probes has a high biological and ecological impact, and several preliminary applications for Cu<sup>2+</sup> have been found. However, the poor understanding of photophysical phenomena by which probes work has led to the growth of unhelpful literature. In this way, 4-aryl-1,7-di(pyridin-2-yl)bispyrazolo[3,4-<em>b</em>:4′,3′-<em>e</em>]pyridines <strong>Py<sub>2</sub>BP<sub>2</sub>a-c</strong> were studied as tridentate ligands in developing the probe <strong>Py<sub>2</sub>BP<sub>2</sub>a</strong> (Ar = Ph, LODCu<sup>2+</sup> = 26 nM); thus, this previous work is completed herein by DFT/TD-DFT studies to understand the sensing process. The basal and first excited state of <strong>Py<sub>2</sub>BP<sub>2</sub>a-c</strong> (Ar: Ph, 4-An, 4-Py) and the parent l,4,7-triphenylbispyrazolo[3,4-<em>b</em>:3′,4′-<em>e</em>]pyridine <strong>Ph<sub>3</sub>BP<sub>2</sub></strong> were optimised. Results suggest that the probes' fluorescence is due to a twisted intramolecular charge transfer (TICT) and ICT processes around the 4-aryl and 1,7-dipyridin-2-yl groups; likewise, the fluorescence turn-off in the presence of Cu<sup>2+</sup> by probe <strong>Py<sub>2</sub>BP<sub>2</sub>b</strong> is due to a photoinduced electron transfer (PET) process, favouring a ligand-to-metal charge transfer (LMCT). These findings enhance our understanding of the sensing process and open new possibilities for its applications in various fields.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1324 ","pages":"Article 140891"},"PeriodicalIF":4.0000,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Structure","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022286024033982","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Due to its simplicity and sensitivity, metal ion sensing by fluorescent probes has a high biological and ecological impact, and several preliminary applications for Cu2+ have been found. However, the poor understanding of photophysical phenomena by which probes work has led to the growth of unhelpful literature. In this way, 4-aryl-1,7-di(pyridin-2-yl)bispyrazolo[3,4-b:4′,3′-e]pyridines Py2BP2a-c were studied as tridentate ligands in developing the probe Py2BP2a (Ar = Ph, LODCu2+ = 26 nM); thus, this previous work is completed herein by DFT/TD-DFT studies to understand the sensing process. The basal and first excited state of Py2BP2a-c (Ar: Ph, 4-An, 4-Py) and the parent l,4,7-triphenylbispyrazolo[3,4-b:3′,4′-e]pyridine Ph3BP2 were optimised. Results suggest that the probes' fluorescence is due to a twisted intramolecular charge transfer (TICT) and ICT processes around the 4-aryl and 1,7-dipyridin-2-yl groups; likewise, the fluorescence turn-off in the presence of Cu2+ by probe Py2BP2b is due to a photoinduced electron transfer (PET) process, favouring a ligand-to-metal charge transfer (LMCT). These findings enhance our understanding of the sensing process and open new possibilities for its applications in various fields.
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