Regulating photosalient behavior in dynamic metal-organic crystals
Samim Khan, Basudeb Dutta, Sanobar Naaz, Aditya Choudhury, Pierre‐André Cazade, Emma Kiely, Sarah Guerin, Raghavender Medishetty, Mohammad Hedayetullah Mir
Abstract
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.