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Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange

Modulating the stimulus-responsiveness of a luminescent crystal is challenging owing to the complex interdependent nature of its controlling factors, such as molecular structure, molecular conformation, crystal packing, optical properties, and amorphization behavior. Herein, we demonstrate a halogen...

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Detalles Bibliográficos
Autores principales: Takewaki, Yoshika, Ogawa, Takuji, Tani, Yosuke
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8793743/
https://www.ncbi.nlm.nih.gov/pubmed/35096775
http://dx.doi.org/10.3389/fchem.2021.812593
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author Takewaki, Yoshika
Ogawa, Takuji
Tani, Yosuke
author_facet Takewaki, Yoshika
Ogawa, Takuji
Tani, Yosuke
author_sort Takewaki, Yoshika
collection PubMed
description Modulating the stimulus-responsiveness of a luminescent crystal is challenging owing to the complex interdependent nature of its controlling factors, such as molecular structure, molecular conformation, crystal packing, optical properties, and amorphization behavior. Herein, we demonstrate a halogen-exchange approach that disentangles this problem, thereby realizing the modulation of room-temperature phosphorescence-to-phosphorescence mechanochromism. Replacing the bromine atoms in a brominated thienyl diketone with chlorine atoms afforded isostructural crystals; i.e., molecules with different halogen atoms exhibited the same molecular conformation and crystal packing. Consequently, amorphization behavior toward mechanical stimulation was also the same, and the phosphorescence of amorphous states originated from the same conformer of each diketone. In contrast, the phosphorescence properties of each conformer were modulated differently, which is ascribable to heavy atom effects, resulting in the modulation of the mechanochromism. Thus, halogen exchange is a promising approach for modulating the stimulus-responsive photofunctions of crystals involving spin-forbidden processes.
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spelling pubmed-87937432022-01-28 Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange Takewaki, Yoshika Ogawa, Takuji Tani, Yosuke Front Chem Chemistry Modulating the stimulus-responsiveness of a luminescent crystal is challenging owing to the complex interdependent nature of its controlling factors, such as molecular structure, molecular conformation, crystal packing, optical properties, and amorphization behavior. Herein, we demonstrate a halogen-exchange approach that disentangles this problem, thereby realizing the modulation of room-temperature phosphorescence-to-phosphorescence mechanochromism. Replacing the bromine atoms in a brominated thienyl diketone with chlorine atoms afforded isostructural crystals; i.e., molecules with different halogen atoms exhibited the same molecular conformation and crystal packing. Consequently, amorphization behavior toward mechanical stimulation was also the same, and the phosphorescence of amorphous states originated from the same conformer of each diketone. In contrast, the phosphorescence properties of each conformer were modulated differently, which is ascribable to heavy atom effects, resulting in the modulation of the mechanochromism. Thus, halogen exchange is a promising approach for modulating the stimulus-responsive photofunctions of crystals involving spin-forbidden processes. Frontiers Media S.A. 2022-01-13 /pmc/articles/PMC8793743/ /pubmed/35096775 http://dx.doi.org/10.3389/fchem.2021.812593 Text en Copyright © 2022 Takewaki, Ogawa and Tani. https://creativecommons.org/licenses/by/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
spellingShingle Chemistry
Takewaki, Yoshika
Ogawa, Takuji
Tani, Yosuke
Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange
title Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange
title_full Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange
title_fullStr Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange
title_full_unstemmed Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange
title_short Modulating Room-Temperature Phosphorescence-To-Phosphorescence Mechanochromism by Halogen Exchange
title_sort modulating room-temperature phosphorescence-to-phosphorescence mechanochromism by halogen exchange
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8793743/
https://www.ncbi.nlm.nih.gov/pubmed/35096775
http://dx.doi.org/10.3389/fchem.2021.812593
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