Third‐Order Nonlinear Optical Properties of One‐Dimensional Quinoidal Oligothiophene Derivatives Involving Phenoxyl Groups

نویسندگان

  • Ryohei Kishi
  • Tsubasa Katsurayama
  • Shoki Ochi
  • Akihiro Makino
  • Naoyuki Matsushita
  • Michika Saito
  • Takanori Nagami
  • Jun-Ya Fujiyoshi
  • Masayoshi Nakano
چکیده

The diradical characters (y) and third-order nonlinear optical (NLO) properties of open-shell quinoidal oligothiophene derivatives with phenoxyl groups, and the corresponding reduced (hydrogenated)-state oligomers, are investigated by using the broken-symmetry density functional theory method. The oxidized (dehydrogenated) states are predicted to have an open-shell singlet ground state and their y values increase with the number of units. Static second hyperpolarizabilities (γ) of the open-shell oligomers with intermediate y are shown to be enhanced significantly compared with those of the closed-shell analogues. Furthermore, owing to the effective diradical distances, the γ values of open-shell oligomers are found to exceed that of s-indaceno[1,2,3-cd;5,6,7-c'd']diphenalene, which is known as an organic molecule with the largest two-photon absorption cross-section in this size of the pure hydrocarbons. This feature extends the range of efficient open-shell third-order NLO materials to a novel class of one-dimensional conjugated oligomers with redox-based high tunability of third-order NLO properties.

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عنوان ژورنال:

دوره 6  شماره 

صفحات  -

تاریخ انتشار 2017