Articles producció científica> Química Física i Inorgànica

Computer-aided design of short-lived phosphorescent Ru(II) polarity probes

  • Identification data

    Identifier: imarina:4138809
    Authors:
    Ielasi GAlcover GCasellas Jde Graaf COrellana GReguero M
    Abstract:
    © 2018 Elsevier Ltd Fluorescent polarity probes are usually based on intramolecular charge transfer excited states of selected dyes, the behavior of which in different solvents is traditionally rationalized by the well-known Lippert-Mataga treatment of the “general solvents effect”. Less often transition metal coordination complexes are used as luminescent probes, even though the spectroscopic properties of these dyes are usually dependent on the environment. This is the case of Ru(II) polypyridyls, which are good candidates to develop robust sensitive polarity probes because of their lowest-lying metal-to-ligand charge transfer triplet emissive state, provided their chelating ligands structure is judiciously tuned. The aim of this work has been to design a computational strategy to forecast the behavior of polarity-sensitive Ru(II) complexes without the need to prepare a large set of candidates. In particular, we have analysed a number of complexes derived from [Ru(bpy)3]2+ by introducing different pairs of substituents in the 4,4′ positions of one of the three equivalent 2,2′-bipyridine (bpy) moieties. In this way, we have investigated if a direct relationship may be established between the electronic features of the substituent and the Stokes shift sensitivity to the solvent polarity. Our computational data satisfactorily agree with our experimental results, but they demonstrate that only by explicitly performing the calculation of the Stokes shift in different media for each candidate, it is possible to select the best Ru(II) dyes to be used as polarity probes.
  • Others:

    Author, as appears in the article.: Ielasi G; Alcover G; Casellas J; de Graaf C; Orellana G; Reguero M
    Department: Química Física i Inorgànica
    URV's Author/s: CASELLAS CARBO, JOAN / De Graaf, Cornelis / Reguero de la Poza, Maria del Mar
    Keywords: Solvent effects Solvent Ruthenium(ii) Ru(ii) polypyridyl complexes Pyrene Preferential solvation Polarity probes Photophysics Photochemistry Luminescence Fluorescence Dpi calculations Dft calculations Density-functional theory Complexes Charge-transfer
    Abstract: © 2018 Elsevier Ltd Fluorescent polarity probes are usually based on intramolecular charge transfer excited states of selected dyes, the behavior of which in different solvents is traditionally rationalized by the well-known Lippert-Mataga treatment of the “general solvents effect”. Less often transition metal coordination complexes are used as luminescent probes, even though the spectroscopic properties of these dyes are usually dependent on the environment. This is the case of Ru(II) polypyridyls, which are good candidates to develop robust sensitive polarity probes because of their lowest-lying metal-to-ligand charge transfer triplet emissive state, provided their chelating ligands structure is judiciously tuned. The aim of this work has been to design a computational strategy to forecast the behavior of polarity-sensitive Ru(II) complexes without the need to prepare a large set of candidates. In particular, we have analysed a number of complexes derived from [Ru(bpy)3]2+ by introducing different pairs of substituents in the 4,4′ positions of one of the three equivalent 2,2′-bipyridine (bpy) moieties. In this way, we have investigated if a direct relationship may be established between the electronic features of the substituent and the Stokes shift sensitivity to the solvent polarity. Our computational data satisfactorily agree with our experimental results, but they demonstrate that only by explicitly performing the calculation of the Stokes shift in different media for each candidate, it is possible to select the best Ru(II) dyes to be used as polarity probes.
    Thematic Areas: Saúde coletiva Química Process chemistry and technology Materials science, textiles Materiais Interdisciplinar Geociências General chemical engineering Farmacia Engineering, chemical Engenharias iv Engenharias iii Engenharias ii Engenharias i Ciências biológicas ii Ciência de alimentos Chemistry, applied Chemical engineering (miscellaneous) Chemical engineering (all) Biotecnología Biodiversidade Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 01437208
    Author's mail: coen.degraaf@urv.cat mar.reguero@urv.cat
    Author identifier: 0000-0001-8114-6658 0000-0001-9668-8265
    Record's date: 2023-12-16
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://www.sciencedirect.com/science/article/abs/pii/S0143720818312518
    Papper original source: Dyes And Pigments. 162 168-176
    APA: Ielasi G; Alcover G; Casellas J; de Graaf C; Orellana G; Reguero M (2019). Computer-aided design of short-lived phosphorescent Ru(II) polarity probes. Dyes And Pigments, 162(), 168-176. DOI: 10.1016/j.dyepig.2018.10.015
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1016/j.dyepig.2018.10.015
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2019
    Publication Type: Journal Publications
  • Keywords:

    Chemical Engineering (Miscellaneous),Chemistry, Applied,Engineering, Chemical,Materials Science, Textiles,Process Chemistry and Technology
    Solvent effects
    Solvent
    Ruthenium(ii)
    Ru(ii) polypyridyl complexes
    Pyrene
    Preferential solvation
    Polarity probes
    Photophysics
    Photochemistry
    Luminescence
    Fluorescence
    Dpi calculations
    Dft calculations
    Density-functional theory
    Complexes
    Charge-transfer
    Saúde coletiva
    Química
    Process chemistry and technology
    Materials science, textiles
    Materiais
    Interdisciplinar
    Geociências
    General chemical engineering
    Farmacia
    Engineering, chemical
    Engenharias iv
    Engenharias iii
    Engenharias ii
    Engenharias i
    Ciências biológicas ii
    Ciência de alimentos
    Chemistry, applied
    Chemical engineering (miscellaneous)
    Chemical engineering (all)
    Biotecnología
    Biodiversidade
    Astronomia / física
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