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

doi:10.1002/cptc.201600039

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

Unit of theoretical and structural physico-chemistry

Research output: Contribution to journal › Article › peer-review

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 language	English
Pages (from-to)	93-101
Number of pages	9
Journal	ChemPhotoChem
Volume	1
Issue number	3
DOIs	https://doi.org/10.1002/cptc.201600039
Publication status	Published - 1 Mar 2017

Keywords

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

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10.1002/cptc.201600039

http://dx.doi.org/10.1002/cptc.201600039

Cite this

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

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.",

keywords = "hyperpolarizabilities, hyper-Rayleigh scattering, nonlinear optics, quantum chemical calculations, push–pull chromophores, nonlinear optics, push–pull chromophores, quantum chemical calculations, hyperpolarizabilities, hyper-Rayleigh scattering",

author = "Fr{\'e}d{\'e}ric Castet and Timoth{\'e}e Lerychard and Kornelia Pielak and Gy{\"o}rgy Szal{\'o}ki and Cl{\'e}ment Dalinot and Philippe Leriche and Lionel Sanguinet and Beno{\^i}t Champagne and Vincent Rodriguez",

note = "Funding Information: K. P. thanks the R{\'e}gion Aquitaine (INMERON Project, convention 2014-1R10102-00002867) and the University of Namur for her PhD grant. This work was supported by funds from the Belgian Government (IUAP No P7/5 “Functional Supramolecular Systems”), and the Francqui Foundation. It has also been done in the frame of the Centre of Excellence LAPHIA (Investments for the future: Programme IdEx Bordeaux—LAPHIA (ANR-10-IDEX-03-02)). V.R. is grateful to F. Adamietz for HRS experimental support and technical developments, as well as to the CNRS and the R{\'e}gion Aquitaine for funding supports. Figure 8 was drawn by using the DrawMol software, developed at the University of Namur by Dr. V. Li{\'e}geois. The calculations were performed on the computers of the “Consortium des {\'E}quipements de Calcul Intensif”, including those of the Technological Platform of High-Performance Computing, for which we gratefully acknowledge the financial support of the FNRS-FRFC (Convention Nos. 2.4.617.07.F and 2.5020.11) as well as on the “M{\'e}socentre de Calcul Intensif Aquitain” (MCIA) of the University of Bordeaux, financed by the Conseil R{\'e}gional d'Aquitaine and the French Ministry of Research and Technology. Funding Information: . K. P. thanks the R{\'e}gion Aquitaine (INMERON Project, convention 2014‐1R10102‐00002867) and the University of Namur for her PhD grant. This work was supported by funds from the Belgian Government (IUAP No P7/5 “Functional Supramolecular Systems”), and the Francqui Foundation. It has also been done in the frame of the Centre of Excellence LAPHIA (Investments for the future: Programme IdEx Bordeaux—LAPHIA (ANR‐10‐IDEX‐03‐02)). V.R. is grateful to F. Adamietz for HRS experimental support and technical developments, as well as to the CNRS and the R{\'e}gion Aquitaine for funding supports. Figure 8 was drawn by using the DrawMol software, developed at the University of Namur by Dr. V. Li{\'e}geois. The calculations were performed on the computers of the “Consortium des {\'E}quipements de Calcul Intensif”, including those of the Technological Platform of High‐Performance Computing, for which we gratefully acknowledge the financial support of the FNRS‐FRFC (Convention Nos. 2.4.617.07.F and 2.5020.11) as well as on the “M{\'e}socentre de Calcul Intensif Aquitain” (MCIA) of the University of Bordeaux, financed by the Conseil R{\'e}gional d'Aquitaine and the French Ministry of Research and Technology Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Castet, Frédéric

AU - Lerychard, Timothée

AU - Pielak, Kornelia

AU - Szalóki, György

AU - Dalinot, Clément

AU - Leriche, Philippe

AU - Sanguinet, Lionel

AU - Champagne, Benoît

AU - Rodriguez, Vincent

N1 - Funding Information: K. P. thanks the Région Aquitaine (INMERON Project, convention 2014-1R10102-00002867) and the University of Namur for her PhD grant. This work was supported by funds from the Belgian Government (IUAP No P7/5 “Functional Supramolecular Systems”), and the Francqui Foundation. It has also been done in the frame of the Centre of Excellence LAPHIA (Investments for the future: Programme IdEx Bordeaux—LAPHIA (ANR-10-IDEX-03-02)). V.R. is grateful to F. Adamietz for HRS experimental support and technical developments, as well as to the CNRS and the Région Aquitaine for funding supports. Figure 8 was drawn by using the DrawMol software, developed at the University of Namur by Dr. V. Liégeois. The calculations were performed on the computers of the “Consortium des Équipements de Calcul Intensif”, including those of the Technological Platform of High-Performance Computing, for which we gratefully acknowledge the financial support of the FNRS-FRFC (Convention Nos. 2.4.617.07.F and 2.5020.11) as well as on the “Mésocentre de Calcul Intensif Aquitain” (MCIA) of the University of Bordeaux, financed by the Conseil Régional d'Aquitaine and the French Ministry of Research and Technology. Funding Information: . K. P. thanks the Région Aquitaine (INMERON Project, convention 2014‐1R10102‐00002867) and the University of Namur for her PhD grant. This work was supported by funds from the Belgian Government (IUAP No P7/5 “Functional Supramolecular Systems”), and the Francqui Foundation. It has also been done in the frame of the Centre of Excellence LAPHIA (Investments for the future: Programme IdEx Bordeaux—LAPHIA (ANR‐10‐IDEX‐03‐02)). V.R. is grateful to F. Adamietz for HRS experimental support and technical developments, as well as to the CNRS and the Région Aquitaine for funding supports. Figure 8 was drawn by using the DrawMol software, developed at the University of Namur by Dr. V. Liégeois. The calculations were performed on the computers of the “Consortium des Équipements de Calcul Intensif”, including those of the Technological Platform of High‐Performance Computing, for which we gratefully acknowledge the financial support of the FNRS‐FRFC (Convention Nos. 2.4.617.07.F and 2.5020.11) as well as on the “Mésocentre de Calcul Intensif Aquitain” (MCIA) of the University of Bordeaux, financed by the Conseil Régional d'Aquitaine and the French Ministry of Research and Technology Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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N2 - 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.

AB - 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.

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

KW - nonlinear optics

KW - push–pull chromophores

KW - quantum chemical calculations

KW - hyperpolarizabilities

KW - hyper-Rayleigh scattering

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U2 - 10.1002/cptc.201600039

DO - 10.1002/cptc.201600039

M3 - Article

SN - 2367-0932

VL - 1

SP - 93

EP - 101

JO - ChemPhotoChem

JF - ChemPhotoChem

IS - 3

ER -

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

Abstract

Keywords

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“Simulation of multi-states nanometric switches for nonlinear optical application”

INMERON: Interrupteurs Nanométriques Multi Etats à Réponses Optiques Non linéaires

Subvention - Professeur de recherche Francqui

High Performance Computing Technology Platform

Cite this

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

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Projects

“Simulation of multi-states nanometric switches for nonlinear optical application”

INMERON: Interrupteurs Nanométriques Multi Etats à Réponses Optiques Non linéaires

Subvention - Professeur de recherche Francqui

Equipment

High Performance Computing Technology Platform

Cite this