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Diradicalology in third-order nonlinear optical systems: Second hyperpolarizabilities of acetylene-linked phenalenyl-based superpolyenes

Authors

  • Masayoshi Nakano,

    Corresponding author
    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
    • Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Ryohei Kishi,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Hitoshi Fukui,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Takuya Minami,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Kyohei Yoneda,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Shu Minamide,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Yudai Inoue,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Taishi Yamada,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Soichi Ito,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Shabbir Muhammad,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Yasuteru Shigeta,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Takashi Kubo,

    1. Department of Chemistry, Graduate School of Science, Osaka University Toyonaka, Osaka 560-0043, Japan
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  • Benoît Champagne

    1. Laboratoire de Chimie Théorique (LCT), Facultés Universitaires Notre-Dame de la Paix (FUNDP), Rue de Bruxelles, 61, Namur B-5000, Belgium
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Abstract

From the viewpoint of “diradical character,” referred to as “diradicalology,” we investigate the second hyperpolarizability γ—the molecular third-order nonlinear optical (NLO) property—of one-dimensional supermolecular systems composed of acetylene-linked phenalenyl/pyrene rings using long-range corrected spin-unrestricted density functional theory. It turns out that the pyrene-based superpolyenes (Py-n) behave like closed-shell systems, whereas phenalenyl-based superpolyenes (Ph1-n and Ph2-n) have different diradical characters depending on the linked form, that is, Ph1-n and Ph2-n have intermediate and pure diradical characters, respectively. In comparison with Py-n and Ph2-n, the longitudinal γ of Ph1-n is significantly larger, and it displays larger enhancement as a function of system size. Substitutions to the terminal rings by donor (NH2) and acceptor (NO2) groups further enhance γ in Ph1-n, more than in Ph2-n and Py-n. These results are in agreement with the structure–property relationships derived for open-shell NLO systems with symmetric and asymmetric charge distributions (Nakano et al., J. Chem. Phys. 2010, 133, 154302). © 2012 Wiley Periodicals, Inc.

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