Tuning Nonlinear Optical Properties by Altering the Diradical and Charge-Transfer Characteristics of Chichibabin's Hydrocarbon Derivatives

Kotaro Fukuda, Yuta Suzuki, Hiroshi Matsui, Takanori Nagami, Yasutaka Kitagawa, Benoît Champagne, Kenji Kamada, Yohsuke Yamamoto, Masayoshi Nakano

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Heteroatomic derivatives of Chichibabin's hydrocarbon are explored theoretically to highlight the relationship between the electronic structure and nonlinear optical (NLO) properties. The results show that the systems are divided into two classes: one that has intermediate electronic structure between two main contributing resonance structures, and a second with an electronic structure that is approximated by only one resonance structure. It is found that the former class of derivatives exhibits approximately one-order larger static second hyperpolarizability (γ) than the latter class, because of either their intermediate diradical or charge-transfer (CT) characteristics. The asymmetric systems are further scrutinized by using the static electric field model, which shows that the intermediate CT character is essential for the very large enhancement of γ in the asymmetric systems. These results not only clarify the structure–property relationships of open-shell singlet NLO compounds with redox switching properties, but also shed light on a new and unexplored class of closed-shell NLO systems generated by the introduction of intermediate CT nature into open-shell singlet systems.

langue originaleAnglais
Pages (de - à)142-148
Nombre de pages7
journalChemPhysChem
Volume18
Numéro de publication1
Les DOIs
étatPublié - 4 janv. 2017

Empreinte digitale

Hydrocarbons
Electronic structure
Charge transfer
Optical properties
Tuning
hydrocarbons
tuning
charge transfer
Derivatives
optical properties
electronic structure
Optical systems
Electric fields
electric fields
augmentation

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    title = "Tuning Nonlinear Optical Properties by Altering the Diradical and Charge-Transfer Characteristics of Chichibabin's Hydrocarbon Derivatives",
    abstract = "Heteroatomic derivatives of Chichibabin's hydrocarbon are explored theoretically to highlight the relationship between the electronic structure and nonlinear optical (NLO) properties. The results show that the systems are divided into two classes: one that has intermediate electronic structure between two main contributing resonance structures, and a second with an electronic structure that is approximated by only one resonance structure. It is found that the former class of derivatives exhibits approximately one-order larger static second hyperpolarizability (γ) than the latter class, because of either their intermediate diradical or charge-transfer (CT) characteristics. The asymmetric systems are further scrutinized by using the static electric field model, which shows that the intermediate CT character is essential for the very large enhancement of γ in the asymmetric systems. These results not only clarify the structure–property relationships of open-shell singlet NLO compounds with redox switching properties, but also shed light on a new and unexplored class of closed-shell NLO systems generated by the introduction of intermediate CT nature into open-shell singlet systems.",
    keywords = "charge transfer, nonlinear optics, open-shell singlet, radicals, redox chemistry",
    author = "Kotaro Fukuda and Yuta Suzuki and Hiroshi Matsui and Takanori Nagami and Yasutaka Kitagawa and Beno{\^i}t Champagne and Kenji Kamada and Yohsuke Yamamoto and Masayoshi Nakano",
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    Tuning Nonlinear Optical Properties by Altering the Diradical and Charge-Transfer Characteristics of Chichibabin's Hydrocarbon Derivatives. / Fukuda, Kotaro; Suzuki, Yuta; Matsui, Hiroshi; Nagami, Takanori; Kitagawa, Yasutaka; Champagne, Benoît; Kamada, Kenji; Yamamoto, Yohsuke; Nakano, Masayoshi.

    Dans: ChemPhysChem, Vol 18, Numéro 1, 04.01.2017, p. 142-148.

    Résultats de recherche: Contribution à un journal/une revueArticle

    TY - JOUR

    T1 - Tuning Nonlinear Optical Properties by Altering the Diradical and Charge-Transfer Characteristics of Chichibabin's Hydrocarbon Derivatives

    AU - Fukuda, Kotaro

    AU - Suzuki, Yuta

    AU - Matsui, Hiroshi

    AU - Nagami, Takanori

    AU - Kitagawa, Yasutaka

    AU - Champagne, Benoît

    AU - Kamada, Kenji

    AU - Yamamoto, Yohsuke

    AU - Nakano, Masayoshi

    PY - 2017/1/4

    Y1 - 2017/1/4

    N2 - Heteroatomic derivatives of Chichibabin's hydrocarbon are explored theoretically to highlight the relationship between the electronic structure and nonlinear optical (NLO) properties. The results show that the systems are divided into two classes: one that has intermediate electronic structure between two main contributing resonance structures, and a second with an electronic structure that is approximated by only one resonance structure. It is found that the former class of derivatives exhibits approximately one-order larger static second hyperpolarizability (γ) than the latter class, because of either their intermediate diradical or charge-transfer (CT) characteristics. The asymmetric systems are further scrutinized by using the static electric field model, which shows that the intermediate CT character is essential for the very large enhancement of γ in the asymmetric systems. These results not only clarify the structure–property relationships of open-shell singlet NLO compounds with redox switching properties, but also shed light on a new and unexplored class of closed-shell NLO systems generated by the introduction of intermediate CT nature into open-shell singlet systems.

    AB - Heteroatomic derivatives of Chichibabin's hydrocarbon are explored theoretically to highlight the relationship between the electronic structure and nonlinear optical (NLO) properties. The results show that the systems are divided into two classes: one that has intermediate electronic structure between two main contributing resonance structures, and a second with an electronic structure that is approximated by only one resonance structure. It is found that the former class of derivatives exhibits approximately one-order larger static second hyperpolarizability (γ) than the latter class, because of either their intermediate diradical or charge-transfer (CT) characteristics. The asymmetric systems are further scrutinized by using the static electric field model, which shows that the intermediate CT character is essential for the very large enhancement of γ in the asymmetric systems. These results not only clarify the structure–property relationships of open-shell singlet NLO compounds with redox switching properties, but also shed light on a new and unexplored class of closed-shell NLO systems generated by the introduction of intermediate CT nature into open-shell singlet systems.

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