Theoretical Method for an Accurate Elucidation of Energy Transfer Pathways in Europium(III) Complexes with Dipyridophenazine (dppz) Ligand

One More Step in the Study of the Molecular Antenna Effect

María J. Beltrán-Leiva, Plinio Cantero-López, César Zúñiga, Ana Bulhões-Figueira, Dayán Páez-Hernández, Ramiro Arratia-Pérez

    Research output: Contribution to journalArticle

    12 Citations (Scopus)

    Abstract

    A theoretical protocol to study the sensitization and emission mechanism in lanthanide compounds on the basis of multireference CASSCF/PT2 calculations is proposed and applied to [Eu(NO3)3(dppz-CN)] and [Eu(NO3)3(dppz-NO2)] compounds synthesized and characterized herein. The method consists of a fragmentation scheme where both the ligand and the lanthanide fragments were calculated separately but at the same level of theory, using ab initio wave-function-based methods which are adequate for the treatment of quasi-degenerate states. This is based on the fact that the absorption is ligand-localized and the emission is europium-centered. This characteristic allowed us to describe the most probable energy transfer pathways that take place in the complexes, which involved an ISC between the S1 to T1 ligand states, energy transfer to 5D2 in the lanthanide fragment, and further 5D07FJ emission. For both compounds, the triplet and 5D2 states were determined at the CASPT2 level to be around ∼26000 and ∼22400 cm-1, respectively. This difference is in the optimal range for the energy transfer process. Finally, the emissive state 5D0 was found at ∼18000 cm-1 and the emission bands in the range 550-700 nm, in quite good agreement with the experimental results.

    Original languageEnglish
    Pages (from-to)9200-9208
    Number of pages9
    JournalInorganic Chemistry
    Volume56
    Issue number15
    DOIs
    Publication statusPublished - 7 Aug 2017

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    Europium
    Lanthanoid Series Elements
    europium
    Energy transfer
    antennas
    energy transfer
    Antennas
    Ligands
    ligands
    fragments
    Wave functions
    atomic energy levels
    fragmentation
    wave functions

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Inorganic Chemistry

    Cite this

    @article{4c69f1df246542388b709048c1ec18d2,
    title = "Theoretical Method for an Accurate Elucidation of Energy Transfer Pathways in Europium(III) Complexes with Dipyridophenazine (dppz) Ligand: One More Step in the Study of the Molecular Antenna Effect",
    abstract = "A theoretical protocol to study the sensitization and emission mechanism in lanthanide compounds on the basis of multireference CASSCF/PT2 calculations is proposed and applied to [Eu(NO3)3(dppz-CN)] and [Eu(NO3)3(dppz-NO2)] compounds synthesized and characterized herein. The method consists of a fragmentation scheme where both the ligand and the lanthanide fragments were calculated separately but at the same level of theory, using ab initio wave-function-based methods which are adequate for the treatment of quasi-degenerate states. This is based on the fact that the absorption is ligand-localized and the emission is europium-centered. This characteristic allowed us to describe the most probable energy transfer pathways that take place in the complexes, which involved an ISC between the S1 to T1 ligand states, energy transfer to 5D2 in the lanthanide fragment, and further 5D0 → 7FJ emission. For both compounds, the triplet and 5D2 states were determined at the CASPT2 level to be around ∼26000 and ∼22400 cm-1, respectively. This difference is in the optimal range for the energy transfer process. Finally, the emissive state 5D0 was found at ∼18000 cm-1 and the emission bands in the range 550-700 nm, in quite good agreement with the experimental results.",
    author = "Beltr{\'a}n-Leiva, {Mar{\'i}a J.} and Plinio Cantero-L{\'o}pez and C{\'e}sar Z{\'u}{\~n}iga and Ana Bulh{\~o}es-Figueira and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ramiro Arratia-P{\'e}rez",
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    language = "English",
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    pages = "9200--9208",
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    Theoretical Method for an Accurate Elucidation of Energy Transfer Pathways in Europium(III) Complexes with Dipyridophenazine (dppz) Ligand : One More Step in the Study of the Molecular Antenna Effect. / Beltrán-Leiva, María J.; Cantero-López, Plinio; Zúñiga, César; Bulhões-Figueira, Ana; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro.

    In: Inorganic Chemistry, Vol. 56, No. 15, 07.08.2017, p. 9200-9208.

    Research output: Contribution to journalArticle

    TY - JOUR

    T1 - Theoretical Method for an Accurate Elucidation of Energy Transfer Pathways in Europium(III) Complexes with Dipyridophenazine (dppz) Ligand

    T2 - One More Step in the Study of the Molecular Antenna Effect

    AU - Beltrán-Leiva, María J.

    AU - Cantero-López, Plinio

    AU - Zúñiga, César

    AU - Bulhões-Figueira, Ana

    AU - Páez-Hernández, Dayán

    AU - Arratia-Pérez, Ramiro

    PY - 2017/8/7

    Y1 - 2017/8/7

    N2 - A theoretical protocol to study the sensitization and emission mechanism in lanthanide compounds on the basis of multireference CASSCF/PT2 calculations is proposed and applied to [Eu(NO3)3(dppz-CN)] and [Eu(NO3)3(dppz-NO2)] compounds synthesized and characterized herein. The method consists of a fragmentation scheme where both the ligand and the lanthanide fragments were calculated separately but at the same level of theory, using ab initio wave-function-based methods which are adequate for the treatment of quasi-degenerate states. This is based on the fact that the absorption is ligand-localized and the emission is europium-centered. This characteristic allowed us to describe the most probable energy transfer pathways that take place in the complexes, which involved an ISC between the S1 to T1 ligand states, energy transfer to 5D2 in the lanthanide fragment, and further 5D0 → 7FJ emission. For both compounds, the triplet and 5D2 states were determined at the CASPT2 level to be around ∼26000 and ∼22400 cm-1, respectively. This difference is in the optimal range for the energy transfer process. Finally, the emissive state 5D0 was found at ∼18000 cm-1 and the emission bands in the range 550-700 nm, in quite good agreement with the experimental results.

    AB - A theoretical protocol to study the sensitization and emission mechanism in lanthanide compounds on the basis of multireference CASSCF/PT2 calculations is proposed and applied to [Eu(NO3)3(dppz-CN)] and [Eu(NO3)3(dppz-NO2)] compounds synthesized and characterized herein. The method consists of a fragmentation scheme where both the ligand and the lanthanide fragments were calculated separately but at the same level of theory, using ab initio wave-function-based methods which are adequate for the treatment of quasi-degenerate states. This is based on the fact that the absorption is ligand-localized and the emission is europium-centered. This characteristic allowed us to describe the most probable energy transfer pathways that take place in the complexes, which involved an ISC between the S1 to T1 ligand states, energy transfer to 5D2 in the lanthanide fragment, and further 5D0 → 7FJ emission. For both compounds, the triplet and 5D2 states were determined at the CASPT2 level to be around ∼26000 and ∼22400 cm-1, respectively. This difference is in the optimal range for the energy transfer process. Finally, the emissive state 5D0 was found at ∼18000 cm-1 and the emission bands in the range 550-700 nm, in quite good agreement with the experimental results.

    UR - http://www.scopus.com/inward/record.url?scp=85027032381&partnerID=8YFLogxK

    U2 - 10.1021/acs.inorgchem.7b01221

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    EP - 9208

    JO - Inorganic Chemistry

    JF - Inorganic Chemistry

    SN - 0020-1669

    IS - 15

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