Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design

In the search for new nonlinear optical (NLO) switching devices, expanded porphyrins have emerged as ideal candidates thanks to their tunable chemical and photophysical properties. Introducing meso-substituents to these macrocycles is a successful strategy to enhance the NLO contrasts. Despite its p...

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Autores principales:	Eline Desmedt, Tatiana Woller, Jos L. Teunissen, Freija De Vleeschouwer, Mercedes Alonso
Formato:	article
Lenguaje:	EN
Publicado:	Frontiers Media S.A. 2021
Materias:	(time-dependent) density functional theory nonlinear optical properties molecular switches expanded porphyrins inverse design best-first search algorithm Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/e3a4deec6ef948e08b3c97e6103e5f9b
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spelling	oai:doaj.org-article:e3a4deec6ef948e08b3c97e6103e5f9b2021-12-03T05:14:40ZFine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design2296-264610.3389/fchem.2021.786036https://doaj.org/article/e3a4deec6ef948e08b3c97e6103e5f9b2021-12-01T00:00:00Zhttps://www.frontiersin.org/articles/10.3389/fchem.2021.786036/fullhttps://doaj.org/toc/2296-2646In the search for new nonlinear optical (NLO) switching devices, expanded porphyrins have emerged as ideal candidates thanks to their tunable chemical and photophysical properties. Introducing meso-substituents to these macrocycles is a successful strategy to enhance the NLO contrasts. Despite its potential, the influence of meso-substitution on their structural and geometrical properties has been scarcely investigated. In this work, we pursue to grasp the underlying pivotal concepts for the fine-tuning of the NLO contrasts of hexaphyrin-based molecular switches, with a particular focus on the first hyperpolarizability related to the hyper-Rayleigh scattering (βHRS). Building further on these concepts, we also aim to develop a rational design protocol. Starting from the (un)substituted hexaphyrins with various π-conjugation topologies and redox states, structure-property relationships are established linking aromaticity, photophysical properties and βHRS responses. Ultimately, inverse molecular design using the best-first search algorithm is applied on the most favorable switches with the aim to further explore the combinatorial chemical compound space of meso-substituted hexaphyrins in search of high-contrast NLO switches. Two definitions of the figure-of-merit of the switch performance were used as target objectives in the optimization problem. Several meso-substitution patterns and their underlying characteristics are identified, uncovering molecular symmetry and the electronic nature of the substituents as the key players for fine-tuning the βHRS values and NLO contrasts of hexaphyrin-based switches.Eline DesmedtTatiana WollerJos L. TeunissenFreija De VleeschouwerMercedes AlonsoFrontiers Media S.A.article(time-dependent) density functional theorynonlinear optical propertiesmolecular switchesexpanded porphyrinsinverse designbest-first search algorithmChemistryQD1-999ENFrontiers in Chemistry, Vol 9 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	(time-dependent) density functional theory nonlinear optical properties molecular switches expanded porphyrins inverse design best-first search algorithm Chemistry QD1-999
spellingShingle	(time-dependent) density functional theory nonlinear optical properties molecular switches expanded porphyrins inverse design best-first search algorithm Chemistry QD1-999 Eline Desmedt Tatiana Woller Jos L. Teunissen Freija De Vleeschouwer Mercedes Alonso Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design
description	In the search for new nonlinear optical (NLO) switching devices, expanded porphyrins have emerged as ideal candidates thanks to their tunable chemical and photophysical properties. Introducing meso-substituents to these macrocycles is a successful strategy to enhance the NLO contrasts. Despite its potential, the influence of meso-substitution on their structural and geometrical properties has been scarcely investigated. In this work, we pursue to grasp the underlying pivotal concepts for the fine-tuning of the NLO contrasts of hexaphyrin-based molecular switches, with a particular focus on the first hyperpolarizability related to the hyper-Rayleigh scattering (βHRS). Building further on these concepts, we also aim to develop a rational design protocol. Starting from the (un)substituted hexaphyrins with various π-conjugation topologies and redox states, structure-property relationships are established linking aromaticity, photophysical properties and βHRS responses. Ultimately, inverse molecular design using the best-first search algorithm is applied on the most favorable switches with the aim to further explore the combinatorial chemical compound space of meso-substituted hexaphyrins in search of high-contrast NLO switches. Two definitions of the figure-of-merit of the switch performance were used as target objectives in the optimization problem. Several meso-substitution patterns and their underlying characteristics are identified, uncovering molecular symmetry and the electronic nature of the substituents as the key players for fine-tuning the βHRS values and NLO contrasts of hexaphyrin-based switches.
format	article
author	Eline Desmedt Tatiana Woller Jos L. Teunissen Freija De Vleeschouwer Mercedes Alonso
author_facet	Eline Desmedt Tatiana Woller Jos L. Teunissen Freija De Vleeschouwer Mercedes Alonso
author_sort	Eline Desmedt
title	Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design
title_short	Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design
title_full	Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design
title_fullStr	Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design
title_full_unstemmed	Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design
title_sort	fine-tuning of nonlinear optical contrasts of hexaphyrin-based molecular switches using inverse design
publisher	Frontiers Media S.A.
publishDate	2021
url	https://doaj.org/article/e3a4deec6ef948e08b3c97e6103e5f9b
work_keys_str_mv	AT elinedesmedt finetuningofnonlinearopticalcontrastsofhexaphyrinbasedmolecularswitchesusinginversedesign AT tatianawoller finetuningofnonlinearopticalcontrastsofhexaphyrinbasedmolecularswitchesusinginversedesign AT joslteunissen finetuningofnonlinearopticalcontrastsofhexaphyrinbasedmolecularswitchesusinginversedesign AT freijadevleeschouwer finetuningofnonlinearopticalcontrastsofhexaphyrinbasedmolecularswitchesusinginversedesign AT mercedesalonso finetuningofnonlinearopticalcontrastsofhexaphyrinbasedmolecularswitchesusinginversedesign
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Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design

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