Insights into bonding interactions and excitation energies of 3d-4f mixed lanthanide transition metal macrocyclic complexes

Walter A. Rabanal-León, Juliana A. Murillo-López, Ramiro Arratia-Pérez

Research output: Contribution to journalArticle

Abstract

In this contribution, a computational study of equatorial bound tetranuclear macrocycle (butylene linked) [LnZnII 3(HOMBu)]3+ (Ln = La3+, Ce3+) complexes was carried out. Here, the electronic structure, bonding interaction and excitation energies were studied within the relativistic density functional theory framework. From the electronic structure analysis, the frontier molecular orbitals (FMOs) were strongly localized in the d-orbitals of the Zn centers and the f-orbitals of the lanthanide ions. Besides, the inner MOs were found to exhibit a π-character from the organic part of the macrocyclic chain. EDA-NOCV was used as a tool for evaluating the bonding interaction, taking the trinuclear metallomacrocycle (ZnII 3HOMBu) and the lanthanide center as fragments. This analysis showed that the interaction between these fragments was slightly covalent; with this covalency being the result of a charge transfer from the metallomacrocyclic ring to the lanthanide. This phenomenon was observed in the deformation density channels obtained from the EDA-NOCV study; in which π- and σ-charge transfer was observed. Finally, the TD-DFT study of the excitation energies evidenced three sets of bands: the first set with the highest intensity represented the ligand to metal charge transfer bands; the second set could be attributed to the 3d-4f electronic transitions between the metal centers; and the third set represented the f-f bands found for the open-shell cerium complex. This class of complexes accomplishes the "antenna effect" principle, which states that highly absorptive transition-metal (TM) complexes can be used to enhance the luminescence of poorly emissive systems, and are introduced in this study as self-sensitizer bimetallic d-f systems with potential applications in near infra-red (NIR) technologies.

Original languageEnglish
Pages (from-to)33218-33225
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume18
Issue number48
DOIs
Publication statusPublished - 2016

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Lanthanoid Series Elements
Excitation energy
Metal complexes
Transition metals
Charge transfer
transition metals
charge transfer
Electronic structure
Metals
fragments
electronic structure
excitation
Cerium
orbitals
Coordination Complexes
interactions
butenes
Molecular orbitals
cerium
Discrete Fourier transforms

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Insights into bonding interactions and excitation energies of 3d-4f mixed lanthanide transition metal macrocyclic complexes",
abstract = "In this contribution, a computational study of equatorial bound tetranuclear macrocycle (butylene linked) [LnZnII 3(HOMBu)]3+ (Ln = La3+, Ce3+) complexes was carried out. Here, the electronic structure, bonding interaction and excitation energies were studied within the relativistic density functional theory framework. From the electronic structure analysis, the frontier molecular orbitals (FMOs) were strongly localized in the d-orbitals of the Zn centers and the f-orbitals of the lanthanide ions. Besides, the inner MOs were found to exhibit a π-character from the organic part of the macrocyclic chain. EDA-NOCV was used as a tool for evaluating the bonding interaction, taking the trinuclear metallomacrocycle (ZnII 3HOMBu) and the lanthanide center as fragments. This analysis showed that the interaction between these fragments was slightly covalent; with this covalency being the result of a charge transfer from the metallomacrocyclic ring to the lanthanide. This phenomenon was observed in the deformation density channels obtained from the EDA-NOCV study; in which π- and σ-charge transfer was observed. Finally, the TD-DFT study of the excitation energies evidenced three sets of bands: the first set with the highest intensity represented the ligand to metal charge transfer bands; the second set could be attributed to the 3d-4f electronic transitions between the metal centers; and the third set represented the f-f bands found for the open-shell cerium complex. This class of complexes accomplishes the {"}antenna effect{"} principle, which states that highly absorptive transition-metal (TM) complexes can be used to enhance the luminescence of poorly emissive systems, and are introduced in this study as self-sensitizer bimetallic d-f systems with potential applications in near infra-red (NIR) technologies.",
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Insights into bonding interactions and excitation energies of 3d-4f mixed lanthanide transition metal macrocyclic complexes. / Rabanal-León, Walter A.; Murillo-López, Juliana A.; Arratia-Pérez, Ramiro.

In: Physical Chemistry Chemical Physics, Vol. 18, No. 48, 2016, p. 33218-33225.

Research output: Contribution to journalArticle

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T1 - Insights into bonding interactions and excitation energies of 3d-4f mixed lanthanide transition metal macrocyclic complexes

AU - Rabanal-León, Walter A.

AU - Murillo-López, Juliana A.

AU - Arratia-Pérez, Ramiro

PY - 2016

Y1 - 2016

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AB - In this contribution, a computational study of equatorial bound tetranuclear macrocycle (butylene linked) [LnZnII 3(HOMBu)]3+ (Ln = La3+, Ce3+) complexes was carried out. Here, the electronic structure, bonding interaction and excitation energies were studied within the relativistic density functional theory framework. From the electronic structure analysis, the frontier molecular orbitals (FMOs) were strongly localized in the d-orbitals of the Zn centers and the f-orbitals of the lanthanide ions. Besides, the inner MOs were found to exhibit a π-character from the organic part of the macrocyclic chain. EDA-NOCV was used as a tool for evaluating the bonding interaction, taking the trinuclear metallomacrocycle (ZnII 3HOMBu) and the lanthanide center as fragments. This analysis showed that the interaction between these fragments was slightly covalent; with this covalency being the result of a charge transfer from the metallomacrocyclic ring to the lanthanide. This phenomenon was observed in the deformation density channels obtained from the EDA-NOCV study; in which π- and σ-charge transfer was observed. Finally, the TD-DFT study of the excitation energies evidenced three sets of bands: the first set with the highest intensity represented the ligand to metal charge transfer bands; the second set could be attributed to the 3d-4f electronic transitions between the metal centers; and the third set represented the f-f bands found for the open-shell cerium complex. This class of complexes accomplishes the "antenna effect" principle, which states that highly absorptive transition-metal (TM) complexes can be used to enhance the luminescence of poorly emissive systems, and are introduced in this study as self-sensitizer bimetallic d-f systems with potential applications in near infra-red (NIR) technologies.

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SN - 1463-9076

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