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

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Pages (from-to)142-148
Number of pages7
JournalChemPhysChem
Volume18
Issue number1
DOIs
Publication statusPublished - 4 Jan 2017

Keywords

  • charge transfer
  • nonlinear optics
  • open-shell singlet
  • radicals
  • redox chemistry

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