Nonlinear Optical Responses of Self-Assembled Monolayers Fonctionalized with Indolino-Oxazolidine Photoswitches

Kornelia Pielak, C Tonnelé, Jean Deviers, L Muccioli, Benoît Champagne, Frédéric Castet

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Abstract

A computational approach combining molecular dynamic simulations and density functional theory (DFT) calculations is implemented to evaluate the second-order nonlinear optical (NLO) responses of photoresponsive self-assembled monolayers (SAMs) based on indolino–oxazolidine molecular switches. These numerical simulations provide a complete atomistic picture of the morphology of the SAMs, revealing a high degree of positional disorder and an almost isotropic orientation of the chromophores. Subsequent DFT calculations, carried out to evaluate the average first hyperpolarizability of indolino–oxazolidine switches within the SAM, predict that the structural disorder does not significantly reduce the NLO contrast compared to that of the isolated molecules. Chromophores in the SAM can assume a limited number of specific conformations, due to the high rotational barrier that characterize the conjugated bonds along the indolino/oxazolidine-dyene-thiophene sequence. A notable exception is the rotation about the thiophene–thioalkyl bond, which is not only almost free, but also strongly correlated with the magnitude of the first hyperpolarizability. Controlling this rotation by chemical design could thus be a viable strategy to optimize the SAMs NLO response and the performance of photoresponsive devices based on indolino/oxazolidine switches.
Original languageEnglish
JournalPhysical chemistry chemical physics : PCCP
Volume20
Publication statusPublished - 2018

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Self assembled monolayers
switches
chromophores
disorders
density functional theory
Switches
Chromophores
Density functional theory
thiophenes
simulation
Thiophenes
molecular dynamics
Computer simulation
Conformations
Molecular dynamics
oxazolidine
molecules
Molecules

Cite this

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title = "Nonlinear Optical Responses of Self-Assembled Monolayers Fonctionalized with Indolino-Oxazolidine Photoswitches",
abstract = "A computational approach combining molecular dynamic simulations and density functional theory (DFT) calculations is implemented to evaluate the second-order nonlinear optical (NLO) responses of photoresponsive self-assembled monolayers (SAMs) based on indolino–oxazolidine molecular switches. These numerical simulations provide a complete atomistic picture of the morphology of the SAMs, revealing a high degree of positional disorder and an almost isotropic orientation of the chromophores. Subsequent DFT calculations, carried out to evaluate the average first hyperpolarizability of indolino–oxazolidine switches within the SAM, predict that the structural disorder does not significantly reduce the NLO contrast compared to that of the isolated molecules. Chromophores in the SAM can assume a limited number of specific conformations, due to the high rotational barrier that characterize the conjugated bonds along the indolino/oxazolidine-dyene-thiophene sequence. A notable exception is the rotation about the thiophene–thioalkyl bond, which is not only almost free, but also strongly correlated with the magnitude of the first hyperpolarizability. Controlling this rotation by chemical design could thus be a viable strategy to optimize the SAMs NLO response and the performance of photoresponsive devices based on indolino/oxazolidine switches.",
author = "Kornelia Pielak and C Tonnel{\'e} and Jean Deviers and L Muccioli and Beno{\^i}t Champagne and Fr{\'e}d{\'e}ric Castet",
year = "2018",
language = "English",
volume = "20",
journal = "Physical chemistry chemical physics : PCCP",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Nonlinear Optical Responses of Self-Assembled Monolayers Fonctionalized with Indolino-Oxazolidine Photoswitches

AU - Pielak, Kornelia

AU - Tonnelé, C

AU - Deviers, Jean

AU - Muccioli, L

AU - Champagne, Benoît

AU - Castet, Frédéric

PY - 2018

Y1 - 2018

N2 - A computational approach combining molecular dynamic simulations and density functional theory (DFT) calculations is implemented to evaluate the second-order nonlinear optical (NLO) responses of photoresponsive self-assembled monolayers (SAMs) based on indolino–oxazolidine molecular switches. These numerical simulations provide a complete atomistic picture of the morphology of the SAMs, revealing a high degree of positional disorder and an almost isotropic orientation of the chromophores. Subsequent DFT calculations, carried out to evaluate the average first hyperpolarizability of indolino–oxazolidine switches within the SAM, predict that the structural disorder does not significantly reduce the NLO contrast compared to that of the isolated molecules. Chromophores in the SAM can assume a limited number of specific conformations, due to the high rotational barrier that characterize the conjugated bonds along the indolino/oxazolidine-dyene-thiophene sequence. A notable exception is the rotation about the thiophene–thioalkyl bond, which is not only almost free, but also strongly correlated with the magnitude of the first hyperpolarizability. Controlling this rotation by chemical design could thus be a viable strategy to optimize the SAMs NLO response and the performance of photoresponsive devices based on indolino/oxazolidine switches.

AB - A computational approach combining molecular dynamic simulations and density functional theory (DFT) calculations is implemented to evaluate the second-order nonlinear optical (NLO) responses of photoresponsive self-assembled monolayers (SAMs) based on indolino–oxazolidine molecular switches. These numerical simulations provide a complete atomistic picture of the morphology of the SAMs, revealing a high degree of positional disorder and an almost isotropic orientation of the chromophores. Subsequent DFT calculations, carried out to evaluate the average first hyperpolarizability of indolino–oxazolidine switches within the SAM, predict that the structural disorder does not significantly reduce the NLO contrast compared to that of the isolated molecules. Chromophores in the SAM can assume a limited number of specific conformations, due to the high rotational barrier that characterize the conjugated bonds along the indolino/oxazolidine-dyene-thiophene sequence. A notable exception is the rotation about the thiophene–thioalkyl bond, which is not only almost free, but also strongly correlated with the magnitude of the first hyperpolarizability. Controlling this rotation by chemical design could thus be a viable strategy to optimize the SAMs NLO response and the performance of photoresponsive devices based on indolino/oxazolidine switches.

M3 - Article

VL - 20

JO - Physical chemistry chemical physics : PCCP

JF - Physical chemistry chemical physics : PCCP

SN - 1463-9076

ER -