{"title":"Superiority of imidazolium over triazole moiety in bis-heteroleptic ruthenium(II) complex toward selective sensing of phosphates","authors":"","doi":"10.1016/j.ica.2024.122311","DOIUrl":null,"url":null,"abstract":"<div><p>A new phosphorescent ruthenium-based receptor, designated as <strong>Ru-1,</strong> functionalized with imidazolium as an anion-binding moiety was synthesized and characterized for selective recognition and sensing of H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and HP<sub>2</sub>O<sub>7</sub><sup>3−</sup>. The binding affinity of <strong>Ru-1</strong> towards numerous anions was assessed using UV–visible and phosphorescent spectroscopic techniques in CH<sub>3</sub>CN solvents. Notably, phosphate and pyrophosphate exhibited superior binding constants compared to other anions, with measured binding constants (K<sub>a</sub>) of 7.95 × 10<sup>4</sup> and 4.78 × 10<sup>4</sup> M<sup>−1</sup> respectively. Moreover, discernible blue shifts of 25 nm and 28 nm respectively, corresponding to H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and HP<sub>2</sub>O<sub>7</sub><sup>3−</sup> and significant enhancements in photoluminescence intensities by ∼5-fold and ∼4-fold, respectively were observed with H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and HP<sub>2</sub>O<sub>7</sub><sup>3−</sup>. Despite the existence of excess other anions, <strong>Ru-1</strong> demonstrated selectivity towards these ions, facilitating sensitive detection with a limit of detection (LOD) of 0.045 µM for H<sub>2</sub>PO<sub>4</sub><sup>−</sup> and 0.017 µM for HP<sub>2</sub>O<sub>7</sub><sup>3−</sup>. In the presence of H<sub>2</sub>PO<sub>4</sub><sup>−</sup>, the lifetime of <strong>Ru-1</strong> was amplified noticeably from 0.2329 μs to 0.7914 μs, whereas exposure to HP<sub>2</sub>O<sub>7</sub><sup>3−</sup> resulted in an observed increase of 0.7465 μs. Furthermore, comparative photophysical studies revealed that the imidazolium moiety-based <strong>Ru-1</strong> receptor outperformed the triazole-based <strong>Ru-2</strong> receptor in terms of excited state lifetime, binding constant, and detection limit of the anions.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S002016932400402X","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
A new phosphorescent ruthenium-based receptor, designated as Ru-1, functionalized with imidazolium as an anion-binding moiety was synthesized and characterized for selective recognition and sensing of H2PO4− and HP2O73−. The binding affinity of Ru-1 towards numerous anions was assessed using UV–visible and phosphorescent spectroscopic techniques in CH3CN solvents. Notably, phosphate and pyrophosphate exhibited superior binding constants compared to other anions, with measured binding constants (Ka) of 7.95 × 104 and 4.78 × 104 M−1 respectively. Moreover, discernible blue shifts of 25 nm and 28 nm respectively, corresponding to H2PO4− and HP2O73− and significant enhancements in photoluminescence intensities by ∼5-fold and ∼4-fold, respectively were observed with H2PO4− and HP2O73−. Despite the existence of excess other anions, Ru-1 demonstrated selectivity towards these ions, facilitating sensitive detection with a limit of detection (LOD) of 0.045 µM for H2PO4− and 0.017 µM for HP2O73−. In the presence of H2PO4−, the lifetime of Ru-1 was amplified noticeably from 0.2329 μs to 0.7914 μs, whereas exposure to HP2O73− resulted in an observed increase of 0.7465 μs. Furthermore, comparative photophysical studies revealed that the imidazolium moiety-based Ru-1 receptor outperformed the triazole-based Ru-2 receptor in terms of excited state lifetime, binding constant, and detection limit of the anions.
期刊介绍:
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.