Evaluation of Aromaticity for Open-Shell Singlet Dicyclopenta-Fused Acenes and Polyacenes Based on a Magnetically Induced Current

Takanori Nagami, Jun ya Fujiyoshi, Takayoshi Tonami, Ken ichiro Watanabe, Masaki Yamane, Kenji Okada, Ryohei Kishi, Masayoshi Nakano, Benoît Champagne, Vincent Liégeois

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

The aromaticity of dicyclopenta-fused acenes (DPAs) and polyacenes (PAs) of increasing size has been studied by evaluation with the GIMIC method at the DFT level of the magnetically-induced currents (MICs), and by analyzing their spatial distributions. For these open-shell singlet molecules, spin-restricted and -unrestricted treatments provide very different MICs, the latter ones providing the most reliable solution. These MICs and the differences between spin-restricted and -unrestricted treatments are interpreted in terms of the bond current strengths and the current gradients, which indicate the bond aromaticity and enable the spatial distributions of the diatropic and paratropic currents to be analyzed, respectively. In particular, they allow the rationalization of the MICs in correlation with the odd-electron density distributions and their diradical characters. These calculations demonstrate that 1) in increasingly large PAs the bond current strengths get smaller and smaller than in benzene and get almost similar in the central and terminal rings, 2) for DPAs the MICs increase from dominant paratropic currents and antiaromaticity in the small compounds to diatropic currents and aromaticity in the larger ones, and 3) in the largest DPAs, the central rings are characterized by large diatropic currents and the terminal five-membered rings, for which the odd-electron densities are localized by weak ones.

langue originaleAnglais
Pages (de - à)13457-13466
Nombre de pages10
journalChemistry - A European Journal
Volume24
Numéro de publication51
Les DOIs
étatPublié - 12 sept. 2018

Empreinte digitale

Aromatic polymers
Induced currents
Spatial distribution
Electronic density of states
Benzene
Discrete Fourier transforms
Carrier concentration
Molecules

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    Nagami, Takanori ; Fujiyoshi, Jun ya ; Tonami, Takayoshi ; Watanabe, Ken ichiro ; Yamane, Masaki ; Okada, Kenji ; Kishi, Ryohei ; Nakano, Masayoshi ; Champagne, Benoît ; Liégeois, Vincent. / Evaluation of Aromaticity for Open-Shell Singlet Dicyclopenta-Fused Acenes and Polyacenes Based on a Magnetically Induced Current. Dans: Chemistry - A European Journal. 2018 ; Vol 24, Numéro 51. p. 13457-13466.
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    title = "Evaluation of Aromaticity for Open-Shell Singlet Dicyclopenta-Fused Acenes and Polyacenes Based on a Magnetically Induced Current",
    abstract = "The aromaticity of dicyclopenta-fused acenes (DPAs) and polyacenes (PAs) of increasing size has been studied by evaluation with the GIMIC method at the DFT level of the magnetically-induced currents (MICs), and by analyzing their spatial distributions. For these open-shell singlet molecules, spin-restricted and -unrestricted treatments provide very different MICs, the latter ones providing the most reliable solution. These MICs and the differences between spin-restricted and -unrestricted treatments are interpreted in terms of the bond current strengths and the current gradients, which indicate the bond aromaticity and enable the spatial distributions of the diatropic and paratropic currents to be analyzed, respectively. In particular, they allow the rationalization of the MICs in correlation with the odd-electron density distributions and their diradical characters. These calculations demonstrate that 1) in increasingly large PAs the bond current strengths get smaller and smaller than in benzene and get almost similar in the central and terminal rings, 2) for DPAs the MICs increase from dominant paratropic currents and antiaromaticity in the small compounds to diatropic currents and aromaticity in the larger ones, and 3) in the largest DPAs, the central rings are characterized by large diatropic currents and the terminal five-membered rings, for which the odd-electron densities are localized by weak ones.",
    keywords = "aromaticity, GIMIC, odd-electron density, open-shell systems, spin-unrestricted method",
    author = "Takanori Nagami and Fujiyoshi, {Jun ya} and Takayoshi Tonami and Watanabe, {Ken ichiro} and Masaki Yamane and Kenji Okada and Ryohei Kishi and Masayoshi Nakano and Beno{\^i}t Champagne and Vincent Li{\'e}geois",
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    doi = "10.1002/chem.201802696",
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    Evaluation of Aromaticity for Open-Shell Singlet Dicyclopenta-Fused Acenes and Polyacenes Based on a Magnetically Induced Current. / Nagami, Takanori; Fujiyoshi, Jun ya; Tonami, Takayoshi; Watanabe, Ken ichiro; Yamane, Masaki; Okada, Kenji; Kishi, Ryohei; Nakano, Masayoshi; Champagne, Benoît; Liégeois, Vincent.

    Dans: Chemistry - A European Journal, Vol 24, Numéro 51, 12.09.2018, p. 13457-13466.

    Résultats de recherche: Contribution à un journal/une revueArticle

    TY - JOUR

    T1 - Evaluation of Aromaticity for Open-Shell Singlet Dicyclopenta-Fused Acenes and Polyacenes Based on a Magnetically Induced Current

    AU - Nagami, Takanori

    AU - Fujiyoshi, Jun ya

    AU - Tonami, Takayoshi

    AU - Watanabe, Ken ichiro

    AU - Yamane, Masaki

    AU - Okada, Kenji

    AU - Kishi, Ryohei

    AU - Nakano, Masayoshi

    AU - Champagne, Benoît

    AU - Liégeois, Vincent

    PY - 2018/9/12

    Y1 - 2018/9/12

    N2 - The aromaticity of dicyclopenta-fused acenes (DPAs) and polyacenes (PAs) of increasing size has been studied by evaluation with the GIMIC method at the DFT level of the magnetically-induced currents (MICs), and by analyzing their spatial distributions. For these open-shell singlet molecules, spin-restricted and -unrestricted treatments provide very different MICs, the latter ones providing the most reliable solution. These MICs and the differences between spin-restricted and -unrestricted treatments are interpreted in terms of the bond current strengths and the current gradients, which indicate the bond aromaticity and enable the spatial distributions of the diatropic and paratropic currents to be analyzed, respectively. In particular, they allow the rationalization of the MICs in correlation with the odd-electron density distributions and their diradical characters. These calculations demonstrate that 1) in increasingly large PAs the bond current strengths get smaller and smaller than in benzene and get almost similar in the central and terminal rings, 2) for DPAs the MICs increase from dominant paratropic currents and antiaromaticity in the small compounds to diatropic currents and aromaticity in the larger ones, and 3) in the largest DPAs, the central rings are characterized by large diatropic currents and the terminal five-membered rings, for which the odd-electron densities are localized by weak ones.

    AB - The aromaticity of dicyclopenta-fused acenes (DPAs) and polyacenes (PAs) of increasing size has been studied by evaluation with the GIMIC method at the DFT level of the magnetically-induced currents (MICs), and by analyzing their spatial distributions. For these open-shell singlet molecules, spin-restricted and -unrestricted treatments provide very different MICs, the latter ones providing the most reliable solution. These MICs and the differences between spin-restricted and -unrestricted treatments are interpreted in terms of the bond current strengths and the current gradients, which indicate the bond aromaticity and enable the spatial distributions of the diatropic and paratropic currents to be analyzed, respectively. In particular, they allow the rationalization of the MICs in correlation with the odd-electron density distributions and their diradical characters. These calculations demonstrate that 1) in increasingly large PAs the bond current strengths get smaller and smaller than in benzene and get almost similar in the central and terminal rings, 2) for DPAs the MICs increase from dominant paratropic currents and antiaromaticity in the small compounds to diatropic currents and aromaticity in the larger ones, and 3) in the largest DPAs, the central rings are characterized by large diatropic currents and the terminal five-membered rings, for which the odd-electron densities are localized by weak ones.

    KW - aromaticity

    KW - GIMIC

    KW - odd-electron density

    KW - open-shell systems

    KW - spin-unrestricted method

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    DO - 10.1002/chem.201802696

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    JF - Chemistry: A European Journal

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