The effect of metal centers on the electronic transitions of HOMO- and heteronuclear Ru(Ⅱ) and Os(Ⅱ) complexes with 2,3,5,6-tetrakis(2-pyridyl) pyrazine: A combined theoretical and experimental study
{"title":"The effect of metal centers on the electronic transitions of HOMO- and heteronuclear Ru(Ⅱ) and Os(Ⅱ) complexes with 2,3,5,6-tetrakis(2-pyridyl) pyrazine: A combined theoretical and experimental study","authors":"","doi":"10.1016/j.ica.2024.122383","DOIUrl":null,"url":null,"abstract":"<div><p>This study investigates the impact of the type and arrangement of metal centers on the electronic transitions of multimetallic complexes through a combined experimental and computational approach. At first, homo- and hetero-metallic [Mn(TPPZ)<sub>n+1</sub>]<sup>2n+</sup> complexes (M = Ru(Ⅱ) and Os(Ⅱ), TPPZ = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, and n = 1 and 2) were synthesized and fully characterized. Then, density functional theory (DFT) and time-dependent DFT calculations were performed to explore the geometries, electronic structures, excited states, and spectroscopic properties of mono-, bi-, and trimetallic complexes. The comparison between experimental and computational spectra of mono- and bimetallic complexes showed excellent agreement, particularly in peak intensities and absorption energies. The visible region bands were attributed to metal-to-ligand charge-transfer (MLCT) transitions. This study offers insights into how the quantity, type, and arrangement of metal centers influence the frontier orbital energy levels and electronic spectra in homo- and heteronuclear complexes.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004742/pdfft?md5=18f871d8b66137fe7809251b6f44d560&pid=1-s2.0-S0020169324004742-main.pdf","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324004742","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
This study investigates the impact of the type and arrangement of metal centers on the electronic transitions of multimetallic complexes through a combined experimental and computational approach. At first, homo- and hetero-metallic [Mn(TPPZ)n+1]2n+ complexes (M = Ru(Ⅱ) and Os(Ⅱ), TPPZ = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, and n = 1 and 2) were synthesized and fully characterized. Then, density functional theory (DFT) and time-dependent DFT calculations were performed to explore the geometries, electronic structures, excited states, and spectroscopic properties of mono-, bi-, and trimetallic complexes. The comparison between experimental and computational spectra of mono- and bimetallic complexes showed excellent agreement, particularly in peak intensities and absorption energies. The visible region bands were attributed to metal-to-ligand charge-transfer (MLCT) transitions. This study offers insights into how the quantity, type, and arrangement of metal centers influence the frontier orbital energy levels and electronic spectra in homo- and heteronuclear complexes.
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.