Autor: |
Samim Khan, Basudeb Dutta, Sanobar Naaz, Aditya Choudhury, Pierre-Andre Cazade, Emma Kiely, Sarah Guerin, Raghavender Medishetty, Mohammad Hedayetullah Mir |
Jazyk: |
angličtina |
Rok vydání: |
2023 |
Předmět: |
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Zdroj: |
Communications Chemistry, Vol 6, Iss 1, Pp 1-9 (2023) |
Druh dokumentu: |
article |
ISSN: |
2399-3669 |
DOI: |
10.1038/s42004-023-00951-0 |
Popis: |
Abstract 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. |
Databáze: |
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