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Regulating photosalient behavior in dynamic metal-organic crystals
Dynamic photoactuating crystals have become a sensation due to their potential applications in developing smart medical devices, molecular machines, artificial muscles, flexible electronics actuators, probes and microrobots. Here we report the synthesis of two iso-structural metal-organic crystals,...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10349121/ https://www.ncbi.nlm.nih.gov/pubmed/37452109 http://dx.doi.org/10.1038/s42004-023-00951-0 |
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author | Khan, Samim Dutta, Basudeb Naaz, Sanobar Choudhury, Aditya Cazade, Pierre-Andre Kiely, Emma Guerin, Sarah Medishetty, Raghavender Mir, Mohammad Hedayetullah |
author_facet | Khan, Samim Dutta, Basudeb Naaz, Sanobar Choudhury, Aditya Cazade, Pierre-Andre Kiely, Emma Guerin, Sarah Medishetty, Raghavender Mir, Mohammad Hedayetullah |
author_sort | Khan, Samim |
collection | PubMed |
description | Dynamic photoactuating crystals have become a sensation due to their potential applications in developing smart medical devices, molecular machines, artificial muscles, flexible electronics actuators, probes and microrobots. Here we report the synthesis of two iso-structural metal-organic crystals, [Zn(4-ohbz)(2)(4-nvp)(2)] (1) and [Cd(4-ohbz)(2)(4-nvp)(2)] (2) {H4-ohbz = 4-hydroxy benzoic acid; 4-nvp = 4-(1-naphthylvinyl)pyridine} which undergo topochemical [2 + 2] cycloaddition under UV irradiation as well as sunlight to generate a dimerized product of discrete metal-complex [Zn(4-ohbz)(2)(rctt-4-pncb)] {rctt-4-pncb = 1,3-bis(4′-pyridyl)-2,4-bis(naphthyl)cyclobutane} (1′) and one-dimensional coordination polymer (1D CP) [Cd(4-ohbz)(2)(rctt-4-pncb)] (2′) respectively, in a single-crystal-to-single-crystal (SCSC) process. The Zn-based compound demonstrates photosalient behaviour, wherein crystals show jumping, splitting, rolling, and swelling upon UV irradiation. However, the Cd-based crystals do not show such behaviour maintaining the initial supramolecular packing and space group. Thus the photomechanical behaviour can be induced by choosing a suitable metal ion. The above findings are thoroughly validated by quantitative density functional theory (DFT) calculations which show that the Zn-based crystal shifts towards an orthorhombic structure to resolve the anisotropic UV-induced mechanical strain. Furthermore, the mechano-structure-property relationship has been established by complimentary nanoindentation measurements, which are in-line with the DFT-predicted single crystal values. |
format | Online Article Text |
id | pubmed-10349121 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-103491212023-07-16 Regulating photosalient behavior in dynamic metal-organic crystals Khan, Samim Dutta, Basudeb Naaz, Sanobar Choudhury, Aditya Cazade, Pierre-Andre Kiely, Emma Guerin, Sarah Medishetty, Raghavender Mir, Mohammad Hedayetullah Commun Chem Article Dynamic photoactuating crystals have become a sensation due to their potential applications in developing smart medical devices, molecular machines, artificial muscles, flexible electronics actuators, probes and microrobots. Here we report the synthesis of two iso-structural metal-organic crystals, [Zn(4-ohbz)(2)(4-nvp)(2)] (1) and [Cd(4-ohbz)(2)(4-nvp)(2)] (2) {H4-ohbz = 4-hydroxy benzoic acid; 4-nvp = 4-(1-naphthylvinyl)pyridine} which undergo topochemical [2 + 2] cycloaddition under UV irradiation as well as sunlight to generate a dimerized product of discrete metal-complex [Zn(4-ohbz)(2)(rctt-4-pncb)] {rctt-4-pncb = 1,3-bis(4′-pyridyl)-2,4-bis(naphthyl)cyclobutane} (1′) and one-dimensional coordination polymer (1D CP) [Cd(4-ohbz)(2)(rctt-4-pncb)] (2′) respectively, in a single-crystal-to-single-crystal (SCSC) process. The Zn-based compound demonstrates photosalient behaviour, wherein crystals show jumping, splitting, rolling, and swelling upon UV irradiation. However, the Cd-based crystals do not show such behaviour maintaining the initial supramolecular packing and space group. Thus the photomechanical behaviour can be induced by choosing a suitable metal ion. The above findings are thoroughly validated by quantitative density functional theory (DFT) calculations which show that the Zn-based crystal shifts towards an orthorhombic structure to resolve the anisotropic UV-induced mechanical strain. Furthermore, the mechano-structure-property relationship has been established by complimentary nanoindentation measurements, which are in-line with the DFT-predicted single crystal values. Nature Publishing Group UK 2023-07-14 /pmc/articles/PMC10349121/ /pubmed/37452109 http://dx.doi.org/10.1038/s42004-023-00951-0 Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Khan, Samim Dutta, Basudeb Naaz, Sanobar Choudhury, Aditya Cazade, Pierre-Andre Kiely, Emma Guerin, Sarah Medishetty, Raghavender Mir, Mohammad Hedayetullah Regulating photosalient behavior in dynamic metal-organic crystals |
title | Regulating photosalient behavior in dynamic metal-organic crystals |
title_full | Regulating photosalient behavior in dynamic metal-organic crystals |
title_fullStr | Regulating photosalient behavior in dynamic metal-organic crystals |
title_full_unstemmed | Regulating photosalient behavior in dynamic metal-organic crystals |
title_short | Regulating photosalient behavior in dynamic metal-organic crystals |
title_sort | regulating photosalient behavior in dynamic metal-organic crystals |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10349121/ https://www.ncbi.nlm.nih.gov/pubmed/37452109 http://dx.doi.org/10.1038/s42004-023-00951-0 |
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