{"title":"揭示氮杂环三羰基铼 (I) 复合物在金属离子作用下的异常行为","authors":"","doi":"10.1016/j.ica.2024.122389","DOIUrl":null,"url":null,"abstract":"<div><div>Three new rhenium phenanthroline tricarbonyl complexes were synthesized and fully characterized to examine changes in their photophysical properties and spectroscopic behavior in the presence of metal ions. To achieve this, the complexes were designed with modifications in both the phenanthroline and the axial ligand. The 4,7–dichloro–1,10–phenanthroline (Cl<sub>2</sub>phen) precursor was functionalized with two units of 1–aza–15–crown–5 (1A15C5) to obtain the complex [Re((A15C5)<sub>2</sub>phen)(CO)<sub>3</sub>Br] (<strong>1</strong>) with the aim to study the spectroscopic perturbations induced by the binding of the metal ions by this receptor. Interestingly, the rhenium complex <strong>1</strong> shows a particular behavior towards Hg(II) and Pb(II), as a result of the halide abstraction assisted by these metal ions. Additionally, in the presence of Cu(II) the interaction and coordination/binding with the macrocycle cavities is also presumed. The chemical reaction assisted by Hg(II) was confirmed by changes in the absorption, emission and FT–IR spectra of [Re(Cl<sub>2</sub>phen)(CO)<sub>3</sub>Br] (<strong>2</strong>) in presence of the heavy metal ion. These obtained profiles had similar patterns to the ones shown by the cationic complex [Re(Cl<sub>2</sub>phen)(CO)<sub>3</sub>(CH<sub>3</sub>CN)]PF<sub>6</sub> (<strong>3</strong>). As final confirmation, this last complex was also studied in the presence of metal ions and its spectra remained unaltered.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Revealing the Unusual behavior of rhenium (I) tricarbonyl complex functionalized with Aza-Macrocycles in response to metal ions\",\"authors\":\"\",\"doi\":\"10.1016/j.ica.2024.122389\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Three new rhenium phenanthroline tricarbonyl complexes were synthesized and fully characterized to examine changes in their photophysical properties and spectroscopic behavior in the presence of metal ions. To achieve this, the complexes were designed with modifications in both the phenanthroline and the axial ligand. The 4,7–dichloro–1,10–phenanthroline (Cl<sub>2</sub>phen) precursor was functionalized with two units of 1–aza–15–crown–5 (1A15C5) to obtain the complex [Re((A15C5)<sub>2</sub>phen)(CO)<sub>3</sub>Br] (<strong>1</strong>) with the aim to study the spectroscopic perturbations induced by the binding of the metal ions by this receptor. Interestingly, the rhenium complex <strong>1</strong> shows a particular behavior towards Hg(II) and Pb(II), as a result of the halide abstraction assisted by these metal ions. Additionally, in the presence of Cu(II) the interaction and coordination/binding with the macrocycle cavities is also presumed. The chemical reaction assisted by Hg(II) was confirmed by changes in the absorption, emission and FT–IR spectra of [Re(Cl<sub>2</sub>phen)(CO)<sub>3</sub>Br] (<strong>2</strong>) in presence of the heavy metal ion. These obtained profiles had similar patterns to the ones shown by the cationic complex [Re(Cl<sub>2</sub>phen)(CO)<sub>3</sub>(CH<sub>3</sub>CN)]PF<sub>6</sub> (<strong>3</strong>). As final confirmation, this last complex was also studied in the presence of metal ions and its spectra remained unaltered.</div></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-24\",\"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/S0020169324004808\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324004808","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Revealing the Unusual behavior of rhenium (I) tricarbonyl complex functionalized with Aza-Macrocycles in response to metal ions
Three new rhenium phenanthroline tricarbonyl complexes were synthesized and fully characterized to examine changes in their photophysical properties and spectroscopic behavior in the presence of metal ions. To achieve this, the complexes were designed with modifications in both the phenanthroline and the axial ligand. The 4,7–dichloro–1,10–phenanthroline (Cl2phen) precursor was functionalized with two units of 1–aza–15–crown–5 (1A15C5) to obtain the complex [Re((A15C5)2phen)(CO)3Br] (1) with the aim to study the spectroscopic perturbations induced by the binding of the metal ions by this receptor. Interestingly, the rhenium complex 1 shows a particular behavior towards Hg(II) and Pb(II), as a result of the halide abstraction assisted by these metal ions. Additionally, in the presence of Cu(II) the interaction and coordination/binding with the macrocycle cavities is also presumed. The chemical reaction assisted by Hg(II) was confirmed by changes in the absorption, emission and FT–IR spectra of [Re(Cl2phen)(CO)3Br] (2) in presence of the heavy metal ion. These obtained profiles had similar patterns to the ones shown by the cationic complex [Re(Cl2phen)(CO)3(CH3CN)]PF6 (3). As final confirmation, this last complex was also studied in the presence of metal ions and its spectra remained unaltered.
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.