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Quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies

Photomechanically reconfigurable elastic single crystals are the key elements for contactless, timely controllable and spatially resolved transduction of light into work from the nanoscale to the macroscale. The deformation in such single-crystal actuators is observed and usually attributed to aniso...

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Autores principales: Chizhik, Stanislav, Sidelnikov, Anatoly, Zakharov, Boris, Naumov, Panče, Boldyreva, Elena
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5903420/
https://www.ncbi.nlm.nih.gov/pubmed/29719705
http://dx.doi.org/10.1039/c7sc04863g
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author Chizhik, Stanislav
Sidelnikov, Anatoly
Zakharov, Boris
Naumov, Panče
Boldyreva, Elena
author_facet Chizhik, Stanislav
Sidelnikov, Anatoly
Zakharov, Boris
Naumov, Panče
Boldyreva, Elena
author_sort Chizhik, Stanislav
collection PubMed
description Photomechanically reconfigurable elastic single crystals are the key elements for contactless, timely controllable and spatially resolved transduction of light into work from the nanoscale to the macroscale. The deformation in such single-crystal actuators is observed and usually attributed to anisotropy in their structure induced by the external stimulus. Yet, the actual intrinsic and external factors that affect the mechanical response remain poorly understood, and the lack of rigorous models stands as the main impediment towards benchmarking of these materials against each other and with much better developed soft actuators based on polymers, liquid crystals and elastomers. Here, experimental approaches for precise measurement of macroscopic strain in a single crystal bent by means of a solid-state transformation induced by light are developed and used to extract the related temperature-dependent kinetic parameters. The experimental results are compared against an overarching mathematical model based on the combined consideration of light transport, chemical transformation and elastic deformation that does not require fitting of any empirical information. It is demonstrated that for a thermally reversible photoreactive bending crystal, the kinetic constants of the forward (photochemical) reaction and the reverse (thermal) reaction, as well as their temperature dependence, can be extracted with high accuracy. The improved kinematic model of crystal bending takes into account the feedback effect, which is often neglected but becomes increasingly important at the late stages of the photochemical reaction in a single crystal. The results provide the most rigorous and exact mathematical description of photoinduced bending of a single crystal to date.
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spelling pubmed-59034202018-05-01 Quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies Chizhik, Stanislav Sidelnikov, Anatoly Zakharov, Boris Naumov, Panče Boldyreva, Elena Chem Sci Chemistry Photomechanically reconfigurable elastic single crystals are the key elements for contactless, timely controllable and spatially resolved transduction of light into work from the nanoscale to the macroscale. The deformation in such single-crystal actuators is observed and usually attributed to anisotropy in their structure induced by the external stimulus. Yet, the actual intrinsic and external factors that affect the mechanical response remain poorly understood, and the lack of rigorous models stands as the main impediment towards benchmarking of these materials against each other and with much better developed soft actuators based on polymers, liquid crystals and elastomers. Here, experimental approaches for precise measurement of macroscopic strain in a single crystal bent by means of a solid-state transformation induced by light are developed and used to extract the related temperature-dependent kinetic parameters. The experimental results are compared against an overarching mathematical model based on the combined consideration of light transport, chemical transformation and elastic deformation that does not require fitting of any empirical information. It is demonstrated that for a thermally reversible photoreactive bending crystal, the kinetic constants of the forward (photochemical) reaction and the reverse (thermal) reaction, as well as their temperature dependence, can be extracted with high accuracy. The improved kinematic model of crystal bending takes into account the feedback effect, which is often neglected but becomes increasingly important at the late stages of the photochemical reaction in a single crystal. The results provide the most rigorous and exact mathematical description of photoinduced bending of a single crystal to date. Royal Society of Chemistry 2018-01-22 /pmc/articles/PMC5903420/ /pubmed/29719705 http://dx.doi.org/10.1039/c7sc04863g Text en This journal is © The Royal Society of Chemistry 2018 http://creativecommons.org/licenses/by/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0)
spellingShingle Chemistry
Chizhik, Stanislav
Sidelnikov, Anatoly
Zakharov, Boris
Naumov, Panče
Boldyreva, Elena
Quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies
title Quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies
title_full Quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies
title_fullStr Quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies
title_full_unstemmed Quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies
title_short Quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies
title_sort quantification of photoinduced bending of dynamic molecular crystals: from macroscopic strain to kinetic constants and activation energies
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5903420/
https://www.ncbi.nlm.nih.gov/pubmed/29719705
http://dx.doi.org/10.1039/c7sc04863g
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