Nonlinear Optical Contrast in Azobenzene-Based Self-assembled Monolayers

Claire Tonnelé, Benoît Champagne, Luca Muccioli, Frédéric Castet

Research output: Contribution to journalArticle

Abstract

Conjugated organic photochromes such as azobenzene derivatives can show remarkable nonlinear optical (NLO) properties and rapid responses, two essential requirements for the realization of optoelectronic switching devices. These applications also require the control of the molecular organization over the micrometric scale, which in principle can be achieved by arranging chromophore units in self-assembled monolayers (SAMs). To rationalize the interplay between the NLO responses of isolated molecules and those of photoresponsive materials, we implement here a computational approach combining molecular dynamics simulations and DFT calculations for predicting the NLO responses of azobenzene-based SAMs with different surface densities. We show that collective switching of the chromophores is indeed possible, even though trans → cis photoisomerization yields decrease when increasing the chromophore concentration. The magnitude of the second-order NLO response of trans SAMs is dominated by the component normal to the surface, which is considerably larger than the parallel one and significantly increases with the packing density. Photoswitching has the neat effect of halving the first hyperpolarizability, allowing for large NLO contrasts exploitable for storing and reading information in selected portions of the surface.

Original languageEnglish
Pages (from-to)6759-6769
Number of pages11
JournalChemistry of Materials
Volume31
Issue number17
DOIs
Publication statusPublished - 10 Sep 2019

Fingerprint

Azobenzene
Self assembled monolayers
Chromophores
Photoisomerization
Discrete Fourier transforms
Optoelectronic devices
Molecular dynamics
Optical properties
Derivatives
Molecules
Computer simulation
azobenzene

Cite this

Tonnelé, Claire ; Champagne, Benoît ; Muccioli, Luca ; Castet, Frédéric. / Nonlinear Optical Contrast in Azobenzene-Based Self-assembled Monolayers. In: Chemistry of Materials. 2019 ; Vol. 31, No. 17. pp. 6759-6769.
@article{192f1816a11f4f649f6f558e11d42323,
title = "Nonlinear Optical Contrast in Azobenzene-Based Self-assembled Monolayers",
abstract = "Conjugated organic photochromes such as azobenzene derivatives can show remarkable nonlinear optical (NLO) properties and rapid responses, two essential requirements for the realization of optoelectronic switching devices. These applications also require the control of the molecular organization over the micrometric scale, which in principle can be achieved by arranging chromophore units in self-assembled monolayers (SAMs). To rationalize the interplay between the NLO responses of isolated molecules and those of photoresponsive materials, we implement here a computational approach combining molecular dynamics simulations and DFT calculations for predicting the NLO responses of azobenzene-based SAMs with different surface densities. We show that collective switching of the chromophores is indeed possible, even though trans → cis photoisomerization yields decrease when increasing the chromophore concentration. The magnitude of the second-order NLO response of trans SAMs is dominated by the component normal to the surface, which is considerably larger than the parallel one and significantly increases with the packing density. Photoswitching has the neat effect of halving the first hyperpolarizability, allowing for large NLO contrasts exploitable for storing and reading information in selected portions of the surface.",
author = "Claire Tonnel{\'e} and Beno{\^i}t Champagne and Luca Muccioli and Fr{\'e}d{\'e}ric Castet",
year = "2019",
month = "9",
day = "10",
doi = "https://doi.org/10.1021/acs.chemmater.9b01241",
language = "English",
volume = "31",
pages = "6759--6769",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "17",

}

Nonlinear Optical Contrast in Azobenzene-Based Self-assembled Monolayers. / Tonnelé, Claire; Champagne, Benoît; Muccioli, Luca; Castet, Frédéric.

In: Chemistry of Materials, Vol. 31, No. 17, 10.09.2019, p. 6759-6769.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Nonlinear Optical Contrast in Azobenzene-Based Self-assembled Monolayers

AU - Tonnelé, Claire

AU - Champagne, Benoît

AU - Muccioli, Luca

AU - Castet, Frédéric

PY - 2019/9/10

Y1 - 2019/9/10

N2 - Conjugated organic photochromes such as azobenzene derivatives can show remarkable nonlinear optical (NLO) properties and rapid responses, two essential requirements for the realization of optoelectronic switching devices. These applications also require the control of the molecular organization over the micrometric scale, which in principle can be achieved by arranging chromophore units in self-assembled monolayers (SAMs). To rationalize the interplay between the NLO responses of isolated molecules and those of photoresponsive materials, we implement here a computational approach combining molecular dynamics simulations and DFT calculations for predicting the NLO responses of azobenzene-based SAMs with different surface densities. We show that collective switching of the chromophores is indeed possible, even though trans → cis photoisomerization yields decrease when increasing the chromophore concentration. The magnitude of the second-order NLO response of trans SAMs is dominated by the component normal to the surface, which is considerably larger than the parallel one and significantly increases with the packing density. Photoswitching has the neat effect of halving the first hyperpolarizability, allowing for large NLO contrasts exploitable for storing and reading information in selected portions of the surface.

AB - Conjugated organic photochromes such as azobenzene derivatives can show remarkable nonlinear optical (NLO) properties and rapid responses, two essential requirements for the realization of optoelectronic switching devices. These applications also require the control of the molecular organization over the micrometric scale, which in principle can be achieved by arranging chromophore units in self-assembled monolayers (SAMs). To rationalize the interplay between the NLO responses of isolated molecules and those of photoresponsive materials, we implement here a computational approach combining molecular dynamics simulations and DFT calculations for predicting the NLO responses of azobenzene-based SAMs with different surface densities. We show that collective switching of the chromophores is indeed possible, even though trans → cis photoisomerization yields decrease when increasing the chromophore concentration. The magnitude of the second-order NLO response of trans SAMs is dominated by the component normal to the surface, which is considerably larger than the parallel one and significantly increases with the packing density. Photoswitching has the neat effect of halving the first hyperpolarizability, allowing for large NLO contrasts exploitable for storing and reading information in selected portions of the surface.

UR - http://www.scopus.com/inward/record.url?scp=85070345299&partnerID=8YFLogxK

U2 - https://doi.org/10.1021/acs.chemmater.9b01241

DO - https://doi.org/10.1021/acs.chemmater.9b01241

M3 - Article

VL - 31

SP - 6759

EP - 6769

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 17

ER -