Unravelling the sensing mechanism of bis-urea macrocycle-based anion receptor: a theoretical study

Supramolecular Materials Pub Date : 2025-06-06 DOI:10.1016/j.supmat.2025.100111

G.S. Gopika Krishnan, K. Muraleedharan

{"title":"Unravelling the sensing mechanism of bis-urea macrocycle-based anion receptor: a theoretical study","authors":"G.S. Gopika Krishnan, K. Muraleedharan","doi":"10.1016/j.supmat.2025.100111","DOIUrl":null,"url":null,"abstract":"<div><div>Understanding how the bis-urea macrocycle molecules can sense different invited anionic substances is becoming increasingly crucial. In this context, we have theoretically studied a new host-guest such as the interaction of 7,13-dibromo-1,4,8,11-tetraazacyclotetradecane-5,12‑dione (BUM) with the anions like SO42−, SO32−, CH3COO−, NO2−, and NO3−. DFT and TD-DFT are used to calculate thermodynamics, electronic structure, electric-field induced properties, and photo-physical characteristics in order to investigate the mechanism of selective sensing of these anions. The free energy change (ΔGads) and adsorption energies (Eads) suggest that these anionic interactions are thermodynamically feasible with strong to moderate adsorption energy with the receptor. The conductivity and sensitivity between the anions can be improved by the external electric field regulated investigation. Because of the intramolecular charge transfer transitions, internal conversions, and related configurational modifications, BUM-SO32− exhibits good fluorescence in the BUM-anion complexes, indicating its significance for practical utility.</div></div>","PeriodicalId":101187,"journal":{"name":"Supramolecular Materials","volume":"4 ","pages":"Article 100111"},"PeriodicalIF":0.0000,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Supramolecular Materials","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2667240525000200","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}

引用次数: 0

Abstract

Understanding how the bis-urea macrocycle molecules can sense different invited anionic substances is becoming increasingly crucial. In this context, we have theoretically studied a new host-guest such as the interaction of 7,13-dibromo-1,4,8,11-tetraazacyclotetradecane-5,12‑dione (BUM) with the anions like SO₄²⁻, SO₃²⁻, CH₃COO⁻, NO₂⁻, and NO₃⁻. DFT and TD-DFT are used to calculate thermodynamics, electronic structure, electric-field induced properties, and photo-physical characteristics in order to investigate the mechanism of selective sensing of these anions. The free energy change (ΔG_ads) and adsorption energies (E_ads) suggest that these anionic interactions are thermodynamically feasible with strong to moderate adsorption energy with the receptor. The conductivity and sensitivity between the anions can be improved by the external electric field regulated investigation. Because of the intramolecular charge transfer transitions, internal conversions, and related configurational modifications, BUM-SO₃²⁻ exhibits good fluorescence in the BUM-anion complexes, indicating its significance for practical utility.

Abstract Image

查看原文本刊更多论文

双尿素大环阴离子受体传感机制的理论研究

了解双尿素大环分子如何感知不同的邀请阴离子物质变得越来越重要。在此背景下，我们从理论上研究了7,13-二溴-1,4,8,11-四氮杂环十四烷-5,12 -二酮（BUM）与阴离子SO42−、SO32−、CH3COO−、NO2−和NO3−的相互作用。利用DFT和TD-DFT计算了这些阴离子的热力学、电子结构、电场诱导性质和光物理特性，以研究这些阴离子的选择性感应机制。自由能变化（ΔGads）和吸附能（Eads）表明，这些阴离子相互作用在热力学上是可行的，与受体具有强到中等的吸附能。通过外加电场调节研究可以提高阴离子间的电导率和灵敏度。由于分子内电荷转移跃迁、内部转换和相关的构型修饰，BUM-SO32−在bum -阴离子配合物中表现出良好的荧光，表明其具有实际应用意义。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Supramolecular Materials

CiteScore

6.70

自引率

0.00%

发文量