A theoretical study on quasi-one-dimensional open-shell singlet ladder oligomers: multi-radical nature, aromaticity and second hyperpolarizability

Kotaro Fukuda, Jun Ya Fujiyoshi, Hiroshi Matsui, Takanori Nagami, Shota Takamuku, Yasutaka Kitagawa, Benoît Champagne, Masayoshi Nakano

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Quasi-one-dimensional open-shell ladder oligomers composed of fully conjugated five- and six-membered rings are investigated to describe their open-shell singlet character and their third-order nonlinear optical (NLO) responses using density functional theory calculations. The nature of the repeating structures is shown to modify the multi-radical nature described by multiple diradical characters, the bond-length alternation, and the local aromaticity. The calculation of the third-order NLO properties ([gamma], the second hyperpolarizability) reveals that the open-shell ladder oligomers with small multiple diradical characters exhibit the largest [gamma] values. At the infinite chain length limit, the static [gamma] value per fused-ring is estimated to reach about 3.6 times that of polyacene, and about half that of all-trans-polyacetylene. The present study gives the first detailed clarification of the multi-radical character and the local aromaticity in real multi-radical ladder oligomers, and the first demonstration that these oligomers are efficient NLO candidates with both large [gamma] and high rigidity.
langueAnglais
Pages779-789
Nombre de pages11
journalOrganic Chemistry Frontiers
Volume4
Les DOIs
étatPublié - 2017

Empreinte digitale

Ladders
Oligomers
Polyacetylenes
Bond length
Chain length
Rigidity
Density functional theory
Demonstrations
Optical properties

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    title = "A theoretical study on quasi-one-dimensional open-shell singlet ladder oligomers: multi-radical nature, aromaticity and second hyperpolarizability",
    abstract = "Quasi-one-dimensional open-shell ladder oligomers composed of fully conjugated five- and six-membered rings are investigated to describe their open-shell singlet character and their third-order nonlinear optical (NLO) responses using density functional theory calculations. The nature of the repeating structures is shown to modify the multi-radical nature described by multiple diradical characters, the bond-length alternation, and the local aromaticity. The calculation of the third-order NLO properties ([gamma], the second hyperpolarizability) reveals that the open-shell ladder oligomers with small multiple diradical characters exhibit the largest [gamma] values. At the infinite chain length limit, the static [gamma] value per fused-ring is estimated to reach about 3.6 times that of polyacene, and about half that of all-trans-polyacetylene. The present study gives the first detailed clarification of the multi-radical character and the local aromaticity in real multi-radical ladder oligomers, and the first demonstration that these oligomers are efficient NLO candidates with both large [gamma] and high rigidity.",
    keywords = "open-shell singlet, multi radical nature, aromaticity, second hyperpolarisabillity",
    author = "Kotaro Fukuda and Fujiyoshi, {Jun Ya} and Hiroshi Matsui and Takanori Nagami and Shota Takamuku and Yasutaka Kitagawa and Beno{\^i}t Champagne and Masayoshi Nakano",
    year = "2017",
    doi = "10.1039/C7QO00108H",
    language = "English",
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    journal = "Organic Chemistry Frontiers",
    issn = "2052-4129",
    publisher = "Royal Society of Chemistry (RSC)",

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    A theoretical study on quasi-one-dimensional open-shell singlet ladder oligomers: multi-radical nature, aromaticity and second hyperpolarizability. / Fukuda, Kotaro; Fujiyoshi, Jun Ya; Matsui, Hiroshi; Nagami, Takanori; Takamuku, Shota; Kitagawa, Yasutaka; Champagne, Benoît; Nakano, Masayoshi.

    Dans: Organic Chemistry Frontiers, Vol 4, 2017, p. 779-789.

    Résultats de recherche: Contribution à un journal/une revueArticle

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    T1 - A theoretical study on quasi-one-dimensional open-shell singlet ladder oligomers: multi-radical nature, aromaticity and second hyperpolarizability

    AU - Fukuda,Kotaro

    AU - Fujiyoshi,Jun Ya

    AU - Matsui,Hiroshi

    AU - Nagami,Takanori

    AU - Takamuku,Shota

    AU - Kitagawa,Yasutaka

    AU - Champagne,Benoît

    AU - Nakano,Masayoshi

    PY - 2017

    Y1 - 2017

    N2 - Quasi-one-dimensional open-shell ladder oligomers composed of fully conjugated five- and six-membered rings are investigated to describe their open-shell singlet character and their third-order nonlinear optical (NLO) responses using density functional theory calculations. The nature of the repeating structures is shown to modify the multi-radical nature described by multiple diradical characters, the bond-length alternation, and the local aromaticity. The calculation of the third-order NLO properties ([gamma], the second hyperpolarizability) reveals that the open-shell ladder oligomers with small multiple diradical characters exhibit the largest [gamma] values. At the infinite chain length limit, the static [gamma] value per fused-ring is estimated to reach about 3.6 times that of polyacene, and about half that of all-trans-polyacetylene. The present study gives the first detailed clarification of the multi-radical character and the local aromaticity in real multi-radical ladder oligomers, and the first demonstration that these oligomers are efficient NLO candidates with both large [gamma] and high rigidity.

    AB - Quasi-one-dimensional open-shell ladder oligomers composed of fully conjugated five- and six-membered rings are investigated to describe their open-shell singlet character and their third-order nonlinear optical (NLO) responses using density functional theory calculations. The nature of the repeating structures is shown to modify the multi-radical nature described by multiple diradical characters, the bond-length alternation, and the local aromaticity. The calculation of the third-order NLO properties ([gamma], the second hyperpolarizability) reveals that the open-shell ladder oligomers with small multiple diradical characters exhibit the largest [gamma] values. At the infinite chain length limit, the static [gamma] value per fused-ring is estimated to reach about 3.6 times that of polyacene, and about half that of all-trans-polyacetylene. The present study gives the first detailed clarification of the multi-radical character and the local aromaticity in real multi-radical ladder oligomers, and the first demonstration that these oligomers are efficient NLO candidates with both large [gamma] and high rigidity.

    KW - open-shell singlet

    KW - multi radical nature

    KW - aromaticity

    KW - second hyperpolarisabillity

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    JO - Organic Chemistry Frontiers

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