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Optical Properties of Disilane-Bridged Donor–Acceptor Architectures: Strong Effect of Substituents on Fluorescence and Nonlinear Optical Properties

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posted on 28.01.2015, 00:00 by Masaki Shimada, Yoshinori Yamanoi, Tomonori Matsushita, Takashi Kondo, Eiji Nishibori, Akari Hatakeyama, Kunihisa Sugimoto, Hiroshi Nishihara
A series of disilane-bridged donor–acceptor architectures 19 containing strong electron-donating and -withdrawing substituents were designed and synthesized in acceptable yields. The substituents substantially affected the fluorescence and nonlinear optical properties of the compounds. In the solid state, the compounds showed purple–blue fluorescence (λem = 360–420 nm) with high quantum yields (up to 0.81). Compound 3, which had p-N,N-dimethylamino and o-cyano substituents, exhibited optical second harmonic generation (activity 2.9 times that of urea, calculated molecular hyperpolarizability β = 1.6 × 10–30 esu) in the powder state. Density functional theory calculations for the ground and excited states indicated that both the locally excited state and the intramolecular charge transfer excited state make important contributions to the luminescence behavior.