How Dimerization Through a Spiro Junction Modifies the Nonlinear Optical Properties of a Push–Pull Organic Dye: Insights from Theory and Hyper-Rayleigh Scattering

Frédéric Castet, Timothée Lerychard, Kornelia Pielak, György Szalóki, Clément Dalinot, Philippe Leriche, Lionel Sanguinet, Benoît Champagne, Vincent Rodriguez

Research output: Contribution to journalArticle

Abstract

The second-order nonlinear optical (NLO) properties of a push–pull monomer, as well as of its dimer composed of two monomeric units connected through a non-conjugated spiro junction, are investigated by means of hyper-Rayleigh scattering (HRS) and quantum chemical calculations. It is shown that dimerization to form a molecule with an orthogonal geometry enhances the first hyperpolarizability by circa 20 % and induces a decrease of the dipolar character of the HRS response. Theoretical calculations correlate well with experimental measurements and allow an in-depth rationalization of the impact of the spiro linkage on the NLO properties through a detailed analysis of the relevant electronic excited states.
Original languageEnglish
Pages (from-to)93-101
Number of pages9
JournalChemPhotoChem
Volume1
Issue number3
DOIs
Publication statusPublished - 2017

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Rayleigh scattering
Dimerization
Coloring Agents
Optical properties
Excited states
Dimers
Monomers
Molecules
Geometry

Keywords

  • hyperpolarizabilities, hyper-Rayleigh scattering, nonlinear optics, quantum chemical calculations, push–pull chromophores

Cite this

Castet, Frédéric ; Lerychard, Timothée ; Pielak, Kornelia ; Szalóki, György ; Dalinot, Clément ; Leriche, Philippe ; Sanguinet, Lionel ; Champagne, Benoît ; Rodriguez, Vincent. / How Dimerization Through a Spiro Junction Modifies the Nonlinear Optical Properties of a Push–Pull Organic Dye: Insights from Theory and Hyper-Rayleigh Scattering. In: ChemPhotoChem. 2017 ; Vol. 1, No. 3. pp. 93-101.
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abstract = "The second-order nonlinear optical (NLO) properties of a push–pull monomer, as well as of its dimer composed of two monomeric units connected through a non-conjugated spiro junction, are investigated by means of hyper-Rayleigh scattering (HRS) and quantum chemical calculations. It is shown that dimerization to form a molecule with an orthogonal geometry enhances the first hyperpolarizability by circa 20 {\%} and induces a decrease of the dipolar character of the HRS response. Theoretical calculations correlate well with experimental measurements and allow an in-depth rationalization of the impact of the spiro linkage on the NLO properties through a detailed analysis of the relevant electronic excited states.",
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How Dimerization Through a Spiro Junction Modifies the Nonlinear Optical Properties of a Push–Pull Organic Dye: Insights from Theory and Hyper-Rayleigh Scattering. / Castet, Frédéric; Lerychard, Timothée; Pielak, Kornelia; Szalóki, György; Dalinot, Clément; Leriche, Philippe; Sanguinet, Lionel; Champagne, Benoît; Rodriguez, Vincent.

In: ChemPhotoChem, Vol. 1, No. 3, 2017, p. 93-101.

Research output: Contribution to journalArticle

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AU - Castet, Frédéric

AU - Lerychard, Timothée

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AU - Szalóki, György

AU - Dalinot, Clément

AU - Leriche, Philippe

AU - Sanguinet, Lionel

AU - Champagne, Benoît

AU - Rodriguez, Vincent

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KW - hyperpolarizabilities, hyper-Rayleigh scattering, nonlinear optics, quantum chemical calculations, push–pull chromophores

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