Theoretical investigation of curved π-conjugated fullerene flakes: open-shell character, aromaticity, and third-order nonlinear optical property

Kotaro Fukuda, Jun Ya Fujiyoshi, Yuka Minamida, Takanori Nagami, Hiroshi Matsui, Soichi Ito, Ryohei Kishi, Yasutaka Kitagawa, Benoît Champagne, Masayoshi Nakano

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Open-shell singlet nature, aromaticity, and second hyperpolarizabilities of two kinds of curved π-conjugated fragments of C60 fullerene, called C60 flakes, together with their corresponding planar analogues are theoretically investigated. It is found that one curved system, A-1, exhibits intermediate open-shell singlet nature, while the other structure, B-1, and the two corresponding planar systems possess a closed-shell ground state. The variation of the open-shell singlet nature is explained by the number of Clar's sextets in the resonance structures, which is associated with the local aromaticity, as quantified by the NICS0 values. The calculated orientationally averaged second hyperpolarizabilities show that the intermediate open-shell singlet system A-1 exhibits the best performance, and that the other curved system B-1 is the worst among the four C60 flakes, whereas all systems exhibit better performance than the original spherical C60 system. This tendency suggests that a lower dimensionality in the π-conjugated structure is beneficial to the construction of efficient nonlinear optical molecules. The present results not only show that the open-shell singlet system A-1 is a performant nonlinear optical molecule, but they also contribute to a deeper understanding of the electronic structure of curved π-conjugated molecules.

langue originaleAnglais
Numéro d'articlee3581
journalJournal of Physical Organic Chemistry
Volume30
Numéro de publication4
Les DOIs
étatPublié - 1 avr. 2017

Empreinte digitale

Fullerenes
flakes
fullerenes
Optical properties
optical properties
Molecules
molecules
Ground state
Electronic structure
tendencies
fragments
analogs
electronic structure
ground state

Citer ceci

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title = "Theoretical investigation of curved π-conjugated fullerene flakes: open-shell character, aromaticity, and third-order nonlinear optical property",
abstract = "Open-shell singlet nature, aromaticity, and second hyperpolarizabilities of two kinds of curved π-conjugated fragments of C60 fullerene, called C60 flakes, together with their corresponding planar analogues are theoretically investigated. It is found that one curved system, A-1, exhibits intermediate open-shell singlet nature, while the other structure, B-1, and the two corresponding planar systems possess a closed-shell ground state. The variation of the open-shell singlet nature is explained by the number of Clar's sextets in the resonance structures, which is associated with the local aromaticity, as quantified by the NICS0 values. The calculated orientationally averaged second hyperpolarizabilities show that the intermediate open-shell singlet system A-1 exhibits the best performance, and that the other curved system B-1 is the worst among the four C60 flakes, whereas all systems exhibit better performance than the original spherical C60 system. This tendency suggests that a lower dimensionality in the π-conjugated structure is beneficial to the construction of efficient nonlinear optical molecules. The present results not only show that the open-shell singlet system A-1 is a performant nonlinear optical molecule, but they also contribute to a deeper understanding of the electronic structure of curved π-conjugated molecules.",
keywords = "curved structure, diradical character, fullerene, open-shell singlet, third-order nonlinear optical property",
author = "Kotaro Fukuda and Fujiyoshi, {Jun Ya} and Yuka Minamida and Takanori Nagami and Hiroshi Matsui and Soichi Ito and Ryohei Kishi and Yasutaka Kitagawa and Beno{\^i}t Champagne and Masayoshi Nakano",
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Theoretical investigation of curved π-conjugated fullerene flakes : open-shell character, aromaticity, and third-order nonlinear optical property. / Fukuda, Kotaro; Fujiyoshi, Jun Ya; Minamida, Yuka; Nagami, Takanori; Matsui, Hiroshi; Ito, Soichi; Kishi, Ryohei; Kitagawa, Yasutaka; Champagne, Benoît; Nakano, Masayoshi.

Dans: Journal of Physical Organic Chemistry, Vol 30, Numéro 4, e3581, 01.04.2017.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Theoretical investigation of curved π-conjugated fullerene flakes

T2 - open-shell character, aromaticity, and third-order nonlinear optical property

AU - Fukuda, Kotaro

AU - Fujiyoshi, Jun Ya

AU - Minamida, Yuka

AU - Nagami, Takanori

AU - Matsui, Hiroshi

AU - Ito, Soichi

AU - Kishi, Ryohei

AU - Kitagawa, Yasutaka

AU - Champagne, Benoît

AU - Nakano, Masayoshi

PY - 2017/4/1

Y1 - 2017/4/1

N2 - Open-shell singlet nature, aromaticity, and second hyperpolarizabilities of two kinds of curved π-conjugated fragments of C60 fullerene, called C60 flakes, together with their corresponding planar analogues are theoretically investigated. It is found that one curved system, A-1, exhibits intermediate open-shell singlet nature, while the other structure, B-1, and the two corresponding planar systems possess a closed-shell ground state. The variation of the open-shell singlet nature is explained by the number of Clar's sextets in the resonance structures, which is associated with the local aromaticity, as quantified by the NICS0 values. The calculated orientationally averaged second hyperpolarizabilities show that the intermediate open-shell singlet system A-1 exhibits the best performance, and that the other curved system B-1 is the worst among the four C60 flakes, whereas all systems exhibit better performance than the original spherical C60 system. This tendency suggests that a lower dimensionality in the π-conjugated structure is beneficial to the construction of efficient nonlinear optical molecules. The present results not only show that the open-shell singlet system A-1 is a performant nonlinear optical molecule, but they also contribute to a deeper understanding of the electronic structure of curved π-conjugated molecules.

AB - Open-shell singlet nature, aromaticity, and second hyperpolarizabilities of two kinds of curved π-conjugated fragments of C60 fullerene, called C60 flakes, together with their corresponding planar analogues are theoretically investigated. It is found that one curved system, A-1, exhibits intermediate open-shell singlet nature, while the other structure, B-1, and the two corresponding planar systems possess a closed-shell ground state. The variation of the open-shell singlet nature is explained by the number of Clar's sextets in the resonance structures, which is associated with the local aromaticity, as quantified by the NICS0 values. The calculated orientationally averaged second hyperpolarizabilities show that the intermediate open-shell singlet system A-1 exhibits the best performance, and that the other curved system B-1 is the worst among the four C60 flakes, whereas all systems exhibit better performance than the original spherical C60 system. This tendency suggests that a lower dimensionality in the π-conjugated structure is beneficial to the construction of efficient nonlinear optical molecules. The present results not only show that the open-shell singlet system A-1 is a performant nonlinear optical molecule, but they also contribute to a deeper understanding of the electronic structure of curved π-conjugated molecules.

KW - curved structure

KW - diradical character

KW - fullerene

KW - open-shell singlet

KW - third-order nonlinear optical property

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