Second hyperpolarizabilities of polycyclic diphenalenyl radicals: Effects of para/ortho-quinoid structures and central ring modification

Masayoshi Nakano, Nozomi Nakagawa, Suguru Ohta, Ryohei Kishi, Takashi Kubo, Kenji Kamada, Koji Ohta, Benoît Champagne, Edith Botek, Hideaki Takahashi, Shin ichi Furukawa, Yasushi Morita, Kazuhiro Nakasuji, Kizashi Yamaguchi

Research output: Contribution to journalArticle

Abstract

We have investigated the structural dependence of static second hyperpolarizabilities (γ) of polycyclic diphenalenyl radicals, i.e., IDPL, as-IDPL and TDPL, using the hybrid density functional theory method. It turns out that the diradical character of as-IDPL (0.923) is larger than that of IDPL (0.770) and is close to 1 (pure diradical state), which supports the fact that the γ of as-IDPL (472 × 103 a.u.) is smaller than that of IDPL (2284 × 103 a.u.). The replacement of a central benzene ring (as-IDPL) by a thiophene ring (TDPL) increases the γ (1375 × 103 a.u.). This is predicted to be caused by the reduction of aromaticity of the central ring and by the hypervalency of the sulfur atom of the thiophene.

Original languageEnglish
Pages (from-to)174-179
Number of pages6
JournalChemical Physics Letters
Volume429
Issue number1-3
DOIs
Publication statusPublished - 29 Sep 2006

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Thiophenes
thiophenes
rings
Benzene
Sulfur
Density functional theory
Atoms
sulfur
benzene
density functional theory
atoms

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Nakano, Masayoshi ; Nakagawa, Nozomi ; Ohta, Suguru ; Kishi, Ryohei ; Kubo, Takashi ; Kamada, Kenji ; Ohta, Koji ; Champagne, Benoît ; Botek, Edith ; Takahashi, Hideaki ; Furukawa, Shin ichi ; Morita, Yasushi ; Nakasuji, Kazuhiro ; Yamaguchi, Kizashi. / Second hyperpolarizabilities of polycyclic diphenalenyl radicals : Effects of para/ortho-quinoid structures and central ring modification. In: Chemical Physics Letters. 2006 ; Vol. 429, No. 1-3. pp. 174-179.
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abstract = "We have investigated the structural dependence of static second hyperpolarizabilities (γ) of polycyclic diphenalenyl radicals, i.e., IDPL, as-IDPL and TDPL, using the hybrid density functional theory method. It turns out that the diradical character of as-IDPL (0.923) is larger than that of IDPL (0.770) and is close to 1 (pure diradical state), which supports the fact that the γ of as-IDPL (472 × 103 a.u.) is smaller than that of IDPL (2284 × 103 a.u.). The replacement of a central benzene ring (as-IDPL) by a thiophene ring (TDPL) increases the γ (1375 × 103 a.u.). This is predicted to be caused by the reduction of aromaticity of the central ring and by the hypervalency of the sulfur atom of the thiophene.",
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Nakano, M, Nakagawa, N, Ohta, S, Kishi, R, Kubo, T, Kamada, K, Ohta, K, Champagne, B, Botek, E, Takahashi, H, Furukawa, SI, Morita, Y, Nakasuji, K & Yamaguchi, K 2006, 'Second hyperpolarizabilities of polycyclic diphenalenyl radicals: Effects of para/ortho-quinoid structures and central ring modification', Chemical Physics Letters, vol. 429, no. 1-3, pp. 174-179. https://doi.org/10.1016/j.cplett.2006.07.065

Second hyperpolarizabilities of polycyclic diphenalenyl radicals : Effects of para/ortho-quinoid structures and central ring modification. / Nakano, Masayoshi; Nakagawa, Nozomi; Ohta, Suguru; Kishi, Ryohei; Kubo, Takashi; Kamada, Kenji; Ohta, Koji; Champagne, Benoît; Botek, Edith; Takahashi, Hideaki; Furukawa, Shin ichi; Morita, Yasushi; Nakasuji, Kazuhiro; Yamaguchi, Kizashi.

In: Chemical Physics Letters, Vol. 429, No. 1-3, 29.09.2006, p. 174-179.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Second hyperpolarizabilities of polycyclic diphenalenyl radicals

T2 - Effects of para/ortho-quinoid structures and central ring modification

AU - Nakano, Masayoshi

AU - Nakagawa, Nozomi

AU - Ohta, Suguru

AU - Kishi, Ryohei

AU - Kubo, Takashi

AU - Kamada, Kenji

AU - Ohta, Koji

AU - Champagne, Benoît

AU - Botek, Edith

AU - Takahashi, Hideaki

AU - Furukawa, Shin ichi

AU - Morita, Yasushi

AU - Nakasuji, Kazuhiro

AU - Yamaguchi, Kizashi

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SP - 174

EP - 179

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

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