2021•The Journal of Physical Chemistry ARequires access

A Substituent Effect on Two-Photon Absorption of Diphenylacetylene Derivatives with an Electron-Donating/Withdrawing Group

Tetsuro Ishii, Tasuku Isozaki, Sho Kinoshita, Ryo Takeuchi, Wataru Kashihara, Tadashi Suzuki

Abstract

Two-photon absorption for diphenylacetylene derivatives with an electron-donating (ED) or electron-withdrawing (EW) group (DPA-Rs) was investigated by high-sensitivity optical-probing photoacoustic spectroscopy. Two-photon absorption spectra and two-photon absorption cross sections σ (2) for DPA-Rs were successfully obtained. Two-photon absorption spectra of DPA-Rs with stronger ED or EW groups display more significant red-shifts and larger σ (2) values. Simulated two-photon absorption spectra, using time-dependent density functional theory within the Tamm–Dancoff approximation, compared well with the experimental spectra. Based on the three-state model, the substituent effect on the two-photon absorption for DPA-Rs was expected to manifest in the transition dipole moments and detuning energies. Information obtained from investigating the monosubstituent effect on two-photon absorption of DPA is critical for an improved understanding of two-photon absorption.

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Key concepts: Diphenylacetylene, Substituent, Two-photon absorption, Absorption (acoustics), Chemistry, Absorption spectroscopy, Dipole, Photochemistry