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Photoswitchable Molecular Units with Tunable Nonlinear Optical Activity: A Theoretical Investigation

The first-, second-, and third-order molecular nonlinear optical properties, including two-photon absorption of a series of derivatives, involving two dithienylethene (DTE) groups connected by several molecular linkers (bis(ethylene-1,2-dithiolato)Ni- (NiBDT), naphthalene, quasilinear oligothiophene...

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Autores principales: Avramopoulos, Aggelos, Reis, Heribert, Tzeli, Demeter, Zaleśny, Robert, Papadopoulos, Manthos G.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10419997/
https://www.ncbi.nlm.nih.gov/pubmed/37570617
http://dx.doi.org/10.3390/molecules28155646
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author Avramopoulos, Aggelos
Reis, Heribert
Tzeli, Demeter
Zaleśny, Robert
Papadopoulos, Manthos G.
author_facet Avramopoulos, Aggelos
Reis, Heribert
Tzeli, Demeter
Zaleśny, Robert
Papadopoulos, Manthos G.
author_sort Avramopoulos, Aggelos
collection PubMed
description The first-, second-, and third-order molecular nonlinear optical properties, including two-photon absorption of a series of derivatives, involving two dithienylethene (DTE) groups connected by several molecular linkers (bis(ethylene-1,2-dithiolato)Ni- (NiBDT), naphthalene, quasilinear oligothiophene chains), are investigated by employing density functional theory (DFT). These properties can be efficiently controlled by DTE switches, in connection with light of appropriate frequency. NiBDT, as a linker, is associated with a greater contrast, in comparison to naphthalene, between the first and second hyperpolarizabilities of the “open–open” and the “closed–closed” isomers. This is explained by invoking the low-lying excited states of NiBDT. It is shown that the second hyperpolarizability can be used as an index, which follows the structural changes induced by photochromism. Assuming a Förster type transfer mechanism, the intramolecular excited-state energy transfer (EET) mechanism is studied. Two important parameters related to this are computed: the electronic coupling (V(DA)) between the donor and acceptor fragments as well as the overlap between the absorption and emission spectra of the donor and acceptor groups. NiBDT as a linker is associated with a low electronic coupling, V(DA), value. We found that V(DA) is affected by molecular geometry. Our results predict that the linker strongly influences the communication between the open–closed DTE groups. The sensitivity of the molecular nonlinear optical properties could assist with identification of molecular isomers.
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spelling pubmed-104199972023-08-12 Photoswitchable Molecular Units with Tunable Nonlinear Optical Activity: A Theoretical Investigation Avramopoulos, Aggelos Reis, Heribert Tzeli, Demeter Zaleśny, Robert Papadopoulos, Manthos G. Molecules Article The first-, second-, and third-order molecular nonlinear optical properties, including two-photon absorption of a series of derivatives, involving two dithienylethene (DTE) groups connected by several molecular linkers (bis(ethylene-1,2-dithiolato)Ni- (NiBDT), naphthalene, quasilinear oligothiophene chains), are investigated by employing density functional theory (DFT). These properties can be efficiently controlled by DTE switches, in connection with light of appropriate frequency. NiBDT, as a linker, is associated with a greater contrast, in comparison to naphthalene, between the first and second hyperpolarizabilities of the “open–open” and the “closed–closed” isomers. This is explained by invoking the low-lying excited states of NiBDT. It is shown that the second hyperpolarizability can be used as an index, which follows the structural changes induced by photochromism. Assuming a Förster type transfer mechanism, the intramolecular excited-state energy transfer (EET) mechanism is studied. Two important parameters related to this are computed: the electronic coupling (V(DA)) between the donor and acceptor fragments as well as the overlap between the absorption and emission spectra of the donor and acceptor groups. NiBDT as a linker is associated with a low electronic coupling, V(DA), value. We found that V(DA) is affected by molecular geometry. Our results predict that the linker strongly influences the communication between the open–closed DTE groups. The sensitivity of the molecular nonlinear optical properties could assist with identification of molecular isomers. MDPI 2023-07-26 /pmc/articles/PMC10419997/ /pubmed/37570617 http://dx.doi.org/10.3390/molecules28155646 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Avramopoulos, Aggelos
Reis, Heribert
Tzeli, Demeter
Zaleśny, Robert
Papadopoulos, Manthos G.
Photoswitchable Molecular Units with Tunable Nonlinear Optical Activity: A Theoretical Investigation
title Photoswitchable Molecular Units with Tunable Nonlinear Optical Activity: A Theoretical Investigation
title_full Photoswitchable Molecular Units with Tunable Nonlinear Optical Activity: A Theoretical Investigation
title_fullStr Photoswitchable Molecular Units with Tunable Nonlinear Optical Activity: A Theoretical Investigation
title_full_unstemmed Photoswitchable Molecular Units with Tunable Nonlinear Optical Activity: A Theoretical Investigation
title_short Photoswitchable Molecular Units with Tunable Nonlinear Optical Activity: A Theoretical Investigation
title_sort photoswitchable molecular units with tunable nonlinear optical activity: a theoretical investigation
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10419997/
https://www.ncbi.nlm.nih.gov/pubmed/37570617
http://dx.doi.org/10.3390/molecules28155646
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