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Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene–Vinylheptafulvene Photochrome Pair

[Image: see text] The UV–vis absorption characteristics and nonlinear optical properties of a series of substituted dihydroazulene (DHA)/vinylheptafulvene (VHF) photoswitches are investigated by applying quantum calculations. Introduction of substituents at the seven-membered ring resulted in signif...

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Autores principales: Bayach, Imene, Al-Faiyz, Yasair S. S., Alkhalifah, Mohammed A., Almutlaq, Nadiah, Ayub, Khurshid, Sheikh, Nadeem S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9558242/
https://www.ncbi.nlm.nih.gov/pubmed/36249387
http://dx.doi.org/10.1021/acsomega.2c04231
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author Bayach, Imene
Al-Faiyz, Yasair S. S.
Alkhalifah, Mohammed A.
Almutlaq, Nadiah
Ayub, Khurshid
Sheikh, Nadeem S.
author_facet Bayach, Imene
Al-Faiyz, Yasair S. S.
Alkhalifah, Mohammed A.
Almutlaq, Nadiah
Ayub, Khurshid
Sheikh, Nadeem S.
author_sort Bayach, Imene
collection PubMed
description [Image: see text] The UV–vis absorption characteristics and nonlinear optical properties of a series of substituted dihydroazulene (DHA)/vinylheptafulvene (VHF) photoswitches are investigated by applying quantum calculations. Introduction of substituents at the seven-membered ring resulted in significant changes in their absorption properties depending on the nature and position of the substituent. Electron-donating groups at positions 5, 6, 7, and 8 generally exhibited red shifts with respect to the parent compound. However, the steric effect at positions 8a and 4 is responsible for the loss of planarity and conjugation, which generally leads to blue shifts. In contrast, any electron-withdrawing group, particularly at positions 8a and 4, would cause a blue shift. The presence of bulky groups at position 8a results in a loss of planarity and, as a result, a decrease in electronic conjugation within the molecule, resulting in a blue shift in the maximum absorption. When it comes to halogens, the red shift is directly correlated to the nucleophilicity; the higher the nucleophilicity, the larger the red shift. Regarding hyperpolarizability, the charge separation induces higher hyperpolarizabilities for all substituted VHFs compared to the corresponding DHAs, resulting in a much higher NLO response. In addition, for all DHA and VHF, the highest values of hyperpolarizabilities are calculated for 6-substituted systems. Finally, the objective of this detailed theoretical investigation is to continue exploring the photophysical properties of DHA–VHF through structural modifications.
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spelling pubmed-95582422022-10-14 Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene–Vinylheptafulvene Photochrome Pair Bayach, Imene Al-Faiyz, Yasair S. S. Alkhalifah, Mohammed A. Almutlaq, Nadiah Ayub, Khurshid Sheikh, Nadeem S. ACS Omega [Image: see text] The UV–vis absorption characteristics and nonlinear optical properties of a series of substituted dihydroazulene (DHA)/vinylheptafulvene (VHF) photoswitches are investigated by applying quantum calculations. Introduction of substituents at the seven-membered ring resulted in significant changes in their absorption properties depending on the nature and position of the substituent. Electron-donating groups at positions 5, 6, 7, and 8 generally exhibited red shifts with respect to the parent compound. However, the steric effect at positions 8a and 4 is responsible for the loss of planarity and conjugation, which generally leads to blue shifts. In contrast, any electron-withdrawing group, particularly at positions 8a and 4, would cause a blue shift. The presence of bulky groups at position 8a results in a loss of planarity and, as a result, a decrease in electronic conjugation within the molecule, resulting in a blue shift in the maximum absorption. When it comes to halogens, the red shift is directly correlated to the nucleophilicity; the higher the nucleophilicity, the larger the red shift. Regarding hyperpolarizability, the charge separation induces higher hyperpolarizabilities for all substituted VHFs compared to the corresponding DHAs, resulting in a much higher NLO response. In addition, for all DHA and VHF, the highest values of hyperpolarizabilities are calculated for 6-substituted systems. Finally, the objective of this detailed theoretical investigation is to continue exploring the photophysical properties of DHA–VHF through structural modifications. American Chemical Society 2022-09-27 /pmc/articles/PMC9558242/ /pubmed/36249387 http://dx.doi.org/10.1021/acsomega.2c04231 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Bayach, Imene
Al-Faiyz, Yasair S. S.
Alkhalifah, Mohammed A.
Almutlaq, Nadiah
Ayub, Khurshid
Sheikh, Nadeem S.
Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene–Vinylheptafulvene Photochrome Pair
title Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene–Vinylheptafulvene Photochrome Pair
title_full Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene–Vinylheptafulvene Photochrome Pair
title_fullStr Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene–Vinylheptafulvene Photochrome Pair
title_full_unstemmed Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene–Vinylheptafulvene Photochrome Pair
title_short Phototunable Absorption and Nonlinear Optical Properties of Thermally Stable Dihydroazulene–Vinylheptafulvene Photochrome Pair
title_sort phototunable absorption and nonlinear optical properties of thermally stable dihydroazulene–vinylheptafulvene photochrome pair
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9558242/
https://www.ncbi.nlm.nih.gov/pubmed/36249387
http://dx.doi.org/10.1021/acsomega.2c04231
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