Luminescent europium(iii) and terbium(iii) complexes of beta-diketonate and substituted terpyridine ligands: synthesis, crystal structures and elucidation of energy transfer pathways: Synthesis, crystal structures and elucidation of energy transfer pathways

Zafar Abbas, Srikanth Dasari, María J. Beltrán-Leiva, Plinio Cantero-López, Dayán Páez-Hernández, Ramiro Arratia-Pérez, Ray J. Butcher, Ashis K. Patra

Resultado de la investigación: Article

Resumen

In this work, we synthesized and structurally characterized a series of six coordinatively saturated EuIII and TbIII complexes: [Ln(R-TPY)(TTA)3] (1-6), having three β-diketonate ligands i.e.TTA = 1,1,1-trifluoro-3-(2-theonyl)acetone, and one judiciously substituted terpyridine derivative (R-TPY), viz. [Eu(FTPY)(TTA)3] (1), [Tb(FTPY)(TTA)3] (2), [Eu(TTPY)(TTA)3] (3), [Tb(TTPY)(TTA)3] (4), [Eu(PTPY)(TTA)3] (5) and [Tb(PTPY)(TTA)3] (6), where FTPY = 4′-(2-furyl)-2,2′:6′,2′′-terpyridine, TTPY = 4′-(2-thienyl)-2,2′:6′,2′′-terpyridine, and PTPY = 4′-(2-pyrolyl)-2,2′:6′,2′′-terpyridine. The complexes were synthesized and structurally characterized by X-ray crystallography and various other physicochemical and spectroscopic methods to realize their optical properties and energy transfer pathways from dual antennae. The structural characterization of the complexes shows discrete nine-coordinated {LnN3O6} geometry originating from six oxygen donors of three monoanioninc β-diketonate ligands and three nitrogens from a tridentate terpyridine derivative (R-TPY). We elucidate the energy transfer (ET) pathways from two coordinating antennae moieties (i.e.R-TPY and TTA) in these complexes using relativistic multiconfigurational methods. For this purpose, a theoretical analysis was performed through a method that consists of a fragmentation scheme, wherein all the constituent fragments (TTA, R-TPY and LnIII) were treated at the same level of theory. These calculations were based on scalar relativistic time-dependent density functional theory (SR-TDDFT) and the multireference complete active space self-consistent field (CASSCF/PT2) technique to construct the respective energy level diagrams and determine the most probable ET pathways. Possible pathways were elucidated from the optimum energy difference between the ligand-centered triplet (3T) states and the emissive excited states of the LnIII fragments. These calculations and energy transfer pathways were in good agreement with the experimental photophysical data and explain the involvement of several parallel energy transfer pathways to varying extent in these luminescent LnIII complexes.

Idioma originalEnglish
Páginas (desde-hasta)15139-15152
Número de páginas14
PublicaciónNew Journal of Chemistry
Volumen43
N.º38
DOI
EstadoPublished - 14 oct 2019

Huella dactilar

Terbium
Europium
Energy transfer
Crystal structure
Ligands
Antennas
Derivatives
X ray crystallography
Acetone
Excited states
Electron energy levels
Density functional theory
Nitrogen
Optical properties
Oxygen
Geometry
europium-thenoyltrifluoroacetone

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

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@article{833fdfe09d744e5298319410980ef22d,
title = "Luminescent europium(iii) and terbium(iii) complexes of beta-diketonate and substituted terpyridine ligands: synthesis, crystal structures and elucidation of energy transfer pathways: Synthesis, crystal structures and elucidation of energy transfer pathways",
abstract = "In this work, we synthesized and structurally characterized a series of six coordinatively saturated EuIII and TbIII complexes: [Ln(R-TPY)(TTA)3] (1-6), having three β-diketonate ligands i.e.TTA = 1,1,1-trifluoro-3-(2-theonyl)acetone, and one judiciously substituted terpyridine derivative (R-TPY), viz. [Eu(FTPY)(TTA)3] (1), [Tb(FTPY)(TTA)3] (2), [Eu(TTPY)(TTA)3] (3), [Tb(TTPY)(TTA)3] (4), [Eu(PTPY)(TTA)3] (5) and [Tb(PTPY)(TTA)3] (6), where FTPY = 4′-(2-furyl)-2,2′:6′,2′′-terpyridine, TTPY = 4′-(2-thienyl)-2,2′:6′,2′′-terpyridine, and PTPY = 4′-(2-pyrolyl)-2,2′:6′,2′′-terpyridine. The complexes were synthesized and structurally characterized by X-ray crystallography and various other physicochemical and spectroscopic methods to realize their optical properties and energy transfer pathways from dual antennae. The structural characterization of the complexes shows discrete nine-coordinated {LnN3O6} geometry originating from six oxygen donors of three monoanioninc β-diketonate ligands and three nitrogens from a tridentate terpyridine derivative (R-TPY). We elucidate the energy transfer (ET) pathways from two coordinating antennae moieties (i.e.R-TPY and TTA) in these complexes using relativistic multiconfigurational methods. For this purpose, a theoretical analysis was performed through a method that consists of a fragmentation scheme, wherein all the constituent fragments (TTA, R-TPY and LnIII) were treated at the same level of theory. These calculations were based on scalar relativistic time-dependent density functional theory (SR-TDDFT) and the multireference complete active space self-consistent field (CASSCF/PT2) technique to construct the respective energy level diagrams and determine the most probable ET pathways. Possible pathways were elucidated from the optimum energy difference between the ligand-centered triplet (3T) states and the emissive excited states of the LnIII fragments. These calculations and energy transfer pathways were in good agreement with the experimental photophysical data and explain the involvement of several parallel energy transfer pathways to varying extent in these luminescent LnIII complexes.",
author = "Zafar Abbas and Srikanth Dasari and Beltr{\'a}n-Leiva, {Mar{\'i}a J.} and Plinio Cantero-L{\'o}pez and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ramiro Arratia-P{\'e}rez and Butcher, {Ray J.} and Patra, {Ashis K.}",
year = "2019",
month = "10",
day = "14",
doi = "10.1039/c9nj02838b",
language = "English",
volume = "43",
pages = "15139--15152",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
number = "38",

}

TY - JOUR

T1 - Luminescent europium(iii) and terbium(iii) complexes of beta-diketonate and substituted terpyridine ligands: synthesis, crystal structures and elucidation of energy transfer pathways

T2 - Synthesis, crystal structures and elucidation of energy transfer pathways

AU - Abbas, Zafar

AU - Dasari, Srikanth

AU - Beltrán-Leiva, María J.

AU - Cantero-López, Plinio

AU - Páez-Hernández, Dayán

AU - Arratia-Pérez, Ramiro

AU - Butcher, Ray J.

AU - Patra, Ashis K.

PY - 2019/10/14

Y1 - 2019/10/14

N2 - In this work, we synthesized and structurally characterized a series of six coordinatively saturated EuIII and TbIII complexes: [Ln(R-TPY)(TTA)3] (1-6), having three β-diketonate ligands i.e.TTA = 1,1,1-trifluoro-3-(2-theonyl)acetone, and one judiciously substituted terpyridine derivative (R-TPY), viz. [Eu(FTPY)(TTA)3] (1), [Tb(FTPY)(TTA)3] (2), [Eu(TTPY)(TTA)3] (3), [Tb(TTPY)(TTA)3] (4), [Eu(PTPY)(TTA)3] (5) and [Tb(PTPY)(TTA)3] (6), where FTPY = 4′-(2-furyl)-2,2′:6′,2′′-terpyridine, TTPY = 4′-(2-thienyl)-2,2′:6′,2′′-terpyridine, and PTPY = 4′-(2-pyrolyl)-2,2′:6′,2′′-terpyridine. The complexes were synthesized and structurally characterized by X-ray crystallography and various other physicochemical and spectroscopic methods to realize their optical properties and energy transfer pathways from dual antennae. The structural characterization of the complexes shows discrete nine-coordinated {LnN3O6} geometry originating from six oxygen donors of three monoanioninc β-diketonate ligands and three nitrogens from a tridentate terpyridine derivative (R-TPY). We elucidate the energy transfer (ET) pathways from two coordinating antennae moieties (i.e.R-TPY and TTA) in these complexes using relativistic multiconfigurational methods. For this purpose, a theoretical analysis was performed through a method that consists of a fragmentation scheme, wherein all the constituent fragments (TTA, R-TPY and LnIII) were treated at the same level of theory. These calculations were based on scalar relativistic time-dependent density functional theory (SR-TDDFT) and the multireference complete active space self-consistent field (CASSCF/PT2) technique to construct the respective energy level diagrams and determine the most probable ET pathways. Possible pathways were elucidated from the optimum energy difference between the ligand-centered triplet (3T) states and the emissive excited states of the LnIII fragments. These calculations and energy transfer pathways were in good agreement with the experimental photophysical data and explain the involvement of several parallel energy transfer pathways to varying extent in these luminescent LnIII complexes.

AB - In this work, we synthesized and structurally characterized a series of six coordinatively saturated EuIII and TbIII complexes: [Ln(R-TPY)(TTA)3] (1-6), having three β-diketonate ligands i.e.TTA = 1,1,1-trifluoro-3-(2-theonyl)acetone, and one judiciously substituted terpyridine derivative (R-TPY), viz. [Eu(FTPY)(TTA)3] (1), [Tb(FTPY)(TTA)3] (2), [Eu(TTPY)(TTA)3] (3), [Tb(TTPY)(TTA)3] (4), [Eu(PTPY)(TTA)3] (5) and [Tb(PTPY)(TTA)3] (6), where FTPY = 4′-(2-furyl)-2,2′:6′,2′′-terpyridine, TTPY = 4′-(2-thienyl)-2,2′:6′,2′′-terpyridine, and PTPY = 4′-(2-pyrolyl)-2,2′:6′,2′′-terpyridine. The complexes were synthesized and structurally characterized by X-ray crystallography and various other physicochemical and spectroscopic methods to realize their optical properties and energy transfer pathways from dual antennae. The structural characterization of the complexes shows discrete nine-coordinated {LnN3O6} geometry originating from six oxygen donors of three monoanioninc β-diketonate ligands and three nitrogens from a tridentate terpyridine derivative (R-TPY). We elucidate the energy transfer (ET) pathways from two coordinating antennae moieties (i.e.R-TPY and TTA) in these complexes using relativistic multiconfigurational methods. For this purpose, a theoretical analysis was performed through a method that consists of a fragmentation scheme, wherein all the constituent fragments (TTA, R-TPY and LnIII) were treated at the same level of theory. These calculations were based on scalar relativistic time-dependent density functional theory (SR-TDDFT) and the multireference complete active space self-consistent field (CASSCF/PT2) technique to construct the respective energy level diagrams and determine the most probable ET pathways. Possible pathways were elucidated from the optimum energy difference between the ligand-centered triplet (3T) states and the emissive excited states of the LnIII fragments. These calculations and energy transfer pathways were in good agreement with the experimental photophysical data and explain the involvement of several parallel energy transfer pathways to varying extent in these luminescent LnIII complexes.

UR - http://www.scopus.com/inward/record.url?scp=85072832069&partnerID=8YFLogxK

U2 - 10.1039/c9nj02838b

DO - 10.1039/c9nj02838b

M3 - Article

AN - SCOPUS:85072832069

VL - 43

SP - 15139

EP - 15152

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 38

ER -