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Circularly Polarized Luminescence from New Heteroleptic Eu(III) and Tb(III) Complexes.
Ruggieri, Silvia; Mizzoni, Silvia; Nardon, Chiara; Cavalli, Enrico; Sissa, Cristina; Anselmi, Michele; Cozzi, Pier Giorgio; Gualandi, Andrea; Sanadar, Martina; Melchior, Andrea; Zinna, Francesco; Willis, Oliver G; Di Bari, Lorenzo; Piccinelli, Fabio.
Afiliación
  • Ruggieri S; Luminescent Materials Laboratory, DB, University of Verona, and INSTM, UdR Verona, Strada Le Grazie 15, 37134 Verona, Italy.
  • Mizzoni S; Luminescent Materials Laboratory, DB, University of Verona, and INSTM, UdR Verona, Strada Le Grazie 15, 37134 Verona, Italy.
  • Nardon C; Luminescent Materials Laboratory, DB, University of Verona, and INSTM, UdR Verona, Strada Le Grazie 15, 37134 Verona, Italy.
  • Cavalli E; Department of Chemistry, Life Sciences and Environmental Sustainability, Parma University, Parco Area delle Scienze, 17/a, 43124 Parma, Italy.
  • Sissa C; Department of Chemistry, Life Sciences and Environmental Sustainability, Parma University, Parco Area delle Scienze, 17/a, 43124 Parma, Italy.
  • Anselmi M; Department of Chemistry "G. Ciamician", University of Bologna, via Selmi 2, 40126 Bologna, Italy.
  • Cozzi PG; Department of Chemistry "G. Ciamician", University of Bologna, via Selmi 2, 40126 Bologna, Italy.
  • Gualandi A; Center for Chemical Catalysis - C3, Alma Mater Studiorum - Università di Bologna, Via Selmi 2, 40126 Bologna, Italy.
  • Sanadar M; Department of Chemistry "G. Ciamician", University of Bologna, via Selmi 2, 40126 Bologna, Italy.
  • Melchior A; Center for Chemical Catalysis - C3, Alma Mater Studiorum - Università di Bologna, Via Selmi 2, 40126 Bologna, Italy.
  • Zinna F; Dipartimento Politecnico di Ingegneria e Architettura, Laboratorio di Tecnologie Chimiche, Università di Udine, via Cotonificio 108, 33100 Udine, Italy.
  • Willis OG; Dipartimento Politecnico di Ingegneria e Architettura, Laboratorio di Tecnologie Chimiche, Università di Udine, via Cotonificio 108, 33100 Udine, Italy.
  • Di Bari L; Department of Chemistry and Industrial Chemistry, University of Pisa, via Moruzzi 13, 56124 Pisa, Italy.
  • Piccinelli F; Department of Chemistry and Industrial Chemistry, University of Pisa, via Moruzzi 13, 56124 Pisa, Italy.
Inorg Chem ; 62(23): 8812-8822, 2023 Jun 12.
Article en En | MEDLINE | ID: mdl-37262334
The complexes [Eu(bpcd)(tta)], [Eu(bpcd)(Coum)], and [Tb(bpcd)(Coum)] [tta = 2-thenoyltrifluoroacetyl-acetonate, Coum = 3-acetyl-4-hydroxy-coumarin, and bpcd = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetate] have been synthesized and characterized from photophysical and thermodynamic points of view. The optical and chiroptical properties of these complexes, such as the total luminescence, decay curves of the Ln(III) luminescence, electronic circular dichroism, and circularly polarized luminescence, have been investigated. Interestingly, the number of coordinated solvent (methanol) molecules is sensitive to the nature of the metal ion. This number, estimated by spectroscopy, is >1 for Eu(III)-based complexes and <1 for Tb(III)-based complexes. A possible explanation for this behavior is provided via the study of the minimum energy structure obtained by density functional theory (DFT) calculations on the model complexes of the diamagnetic Y(III) and La(III) counterparts [Y(bpcd)(tta)], [Y(bpcd)(Coum)], and [La(bpcd)(Coum)]. By time-dependent DFT calculations, estimation of donor-acceptor (D-A) distances and of the energy position of the S1 and T1 ligand excited states involved in the antenna effect was possible. These data are useful for rationalizing the different sensitization efficiencies (ηsens) of the antennae toward Eu(III) and Tb(III). The tta ligand is an optimal antenna for sensitizing Eu(III) luminescence, while the Coum ligand sensitizes better Tb(III) luminescence {ϕovl = 55%; ηsens ≥ 55% for the [Tb(bpcd)(Coum)] complex}. Finally, for the [Eu(bpcd)(tta)] complex, a sizable value of glum (0.26) and a good quantum yield (26%) were measured.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2023 Tipo del documento: Article País de afiliación: Italia Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2023 Tipo del documento: Article País de afiliación: Italia Pais de publicación: Estados Unidos