Giant enhancement of the second hyperpolarizabilities of open-shell singlet polyaromatic diphenalenyl diradicaloids by an external electric field and donor-acceptor substitution

Masayoshi Nakano, Takuya Minami, Kyohei Yoneda, Shabbir Muhammad, Ryohei Kishi, Yasuteru Shigeta, Takashi Kubo, Léa Rougier, Benoit Champagne, Kenji Kamada, Koji Ohta

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Résumé

Switching on an external electric field (F) along the electron correlation direction produces a giant enhancement of the second hyperpolarizability γ in a polyaromatic diradicaloid having intermediate diradical character. This has been evidenced by carrying out spin-unrestricted density functional theory calculations with the LC-UBLYP long-range corrected exchange-correlation functional for the s-indaceno[1,2,3-cd;5,6,7-c′d′]diphenalene (IDPL) diradical compound in comparison to a closed-shell analogue of similar size composed of two pyrene moieties (PY2). For IDPL, the field-induced enhancement ratio is estimated to reach 4 orders of magnitude for an electric field of 0.0077 a.u., whereas it is less than a factor of 2 for PY2. Moreover, an enhancement is also observed by substituting both-end phenalenyl rings of IDPL with donor (NH2)/acceptor (NO2) groups, but this enhancement is limited to about 2 orders of magnitude. These enhancements are associated with a reduction of the diradical character (and therefore an improved thermal stability) as well as with the appearance of substantial type-I contributions to γ.

langue originaleAnglais
Pages (de - à)1094-1098
Nombre de pages5
journalJournal of Physical Chemistry Letters
Volume2
Numéro de publication9
Les DOIs
étatPublié - 5 mai 2011

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Substitution reactions
Electric fields
substitutes
Electron correlations
electric fields
augmentation
Pyrene
Density functional theory
Thermodynamic stability
pyrenes
thermal stability
analogs
density functional theory
rings
electrons
Direction compound
pyrene

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Nakano, Masayoshi ; Minami, Takuya ; Yoneda, Kyohei ; Muhammad, Shabbir ; Kishi, Ryohei ; Shigeta, Yasuteru ; Kubo, Takashi ; Rougier, Léa ; Champagne, Benoit ; Kamada, Kenji ; Ohta, Koji. / Giant enhancement of the second hyperpolarizabilities of open-shell singlet polyaromatic diphenalenyl diradicaloids by an external electric field and donor-acceptor substitution. Dans: Journal of Physical Chemistry Letters. 2011 ; Vol 2, Numéro 9. p. 1094-1098.
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abstract = "Switching on an external electric field (F) along the electron correlation direction produces a giant enhancement of the second hyperpolarizability γ in a polyaromatic diradicaloid having intermediate diradical character. This has been evidenced by carrying out spin-unrestricted density functional theory calculations with the LC-UBLYP long-range corrected exchange-correlation functional for the s-indaceno[1,2,3-cd;5,6,7-c′d′]diphenalene (IDPL) diradical compound in comparison to a closed-shell analogue of similar size composed of two pyrene moieties (PY2). For IDPL, the field-induced enhancement ratio is estimated to reach 4 orders of magnitude for an electric field of 0.0077 a.u., whereas it is less than a factor of 2 for PY2. Moreover, an enhancement is also observed by substituting both-end phenalenyl rings of IDPL with donor (NH2)/acceptor (NO2) groups, but this enhancement is limited to about 2 orders of magnitude. These enhancements are associated with a reduction of the diradical character (and therefore an improved thermal stability) as well as with the appearance of substantial type-I contributions to γ.",
author = "Masayoshi Nakano and Takuya Minami and Kyohei Yoneda and Shabbir Muhammad and Ryohei Kishi and Yasuteru Shigeta and Takashi Kubo and L{\'e}a Rougier and Benoit Champagne and Kenji Kamada and Koji Ohta",
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Giant enhancement of the second hyperpolarizabilities of open-shell singlet polyaromatic diphenalenyl diradicaloids by an external electric field and donor-acceptor substitution. / Nakano, Masayoshi; Minami, Takuya; Yoneda, Kyohei; Muhammad, Shabbir; Kishi, Ryohei; Shigeta, Yasuteru; Kubo, Takashi; Rougier, Léa; Champagne, Benoit; Kamada, Kenji; Ohta, Koji.

Dans: Journal of Physical Chemistry Letters, Vol 2, Numéro 9, 05.05.2011, p. 1094-1098.

Résultats de recherche: Contribution à un journal/une revueArticle

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T1 - Giant enhancement of the second hyperpolarizabilities of open-shell singlet polyaromatic diphenalenyl diradicaloids by an external electric field and donor-acceptor substitution

AU - Nakano, Masayoshi

AU - Minami, Takuya

AU - Yoneda, Kyohei

AU - Muhammad, Shabbir

AU - Kishi, Ryohei

AU - Shigeta, Yasuteru

AU - Kubo, Takashi

AU - Rougier, Léa

AU - Champagne, Benoit

AU - Kamada, Kenji

AU - Ohta, Koji

PY - 2011/5/5

Y1 - 2011/5/5

N2 - Switching on an external electric field (F) along the electron correlation direction produces a giant enhancement of the second hyperpolarizability γ in a polyaromatic diradicaloid having intermediate diradical character. This has been evidenced by carrying out spin-unrestricted density functional theory calculations with the LC-UBLYP long-range corrected exchange-correlation functional for the s-indaceno[1,2,3-cd;5,6,7-c′d′]diphenalene (IDPL) diradical compound in comparison to a closed-shell analogue of similar size composed of two pyrene moieties (PY2). For IDPL, the field-induced enhancement ratio is estimated to reach 4 orders of magnitude for an electric field of 0.0077 a.u., whereas it is less than a factor of 2 for PY2. Moreover, an enhancement is also observed by substituting both-end phenalenyl rings of IDPL with donor (NH2)/acceptor (NO2) groups, but this enhancement is limited to about 2 orders of magnitude. These enhancements are associated with a reduction of the diradical character (and therefore an improved thermal stability) as well as with the appearance of substantial type-I contributions to γ.

AB - Switching on an external electric field (F) along the electron correlation direction produces a giant enhancement of the second hyperpolarizability γ in a polyaromatic diradicaloid having intermediate diradical character. This has been evidenced by carrying out spin-unrestricted density functional theory calculations with the LC-UBLYP long-range corrected exchange-correlation functional for the s-indaceno[1,2,3-cd;5,6,7-c′d′]diphenalene (IDPL) diradical compound in comparison to a closed-shell analogue of similar size composed of two pyrene moieties (PY2). For IDPL, the field-induced enhancement ratio is estimated to reach 4 orders of magnitude for an electric field of 0.0077 a.u., whereas it is less than a factor of 2 for PY2. Moreover, an enhancement is also observed by substituting both-end phenalenyl rings of IDPL with donor (NH2)/acceptor (NO2) groups, but this enhancement is limited to about 2 orders of magnitude. These enhancements are associated with a reduction of the diradical character (and therefore an improved thermal stability) as well as with the appearance of substantial type-I contributions to γ.

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