Regulating photosalient behaviour in dynamic metal-organic crystals

Author:

Khan Samim1ORCID,Dutta Basudeb1,Naaz Sanobar1,Choudhury Aditya2,Cazade Pierre-André3,Kiely Emma3,Guerin Sarah3ORCID,Medishetty Raghavender2,Mir Mohammad Hedayetullah1ORCID

Affiliation:

1. Aliah University

2. IIT Bhilai

3. University of Limerick

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 sensing and probes. 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 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) manner. The Zn-based compounds demonstrate photosalient behaviour, wherein crystals show jumping, splitting, rolling, and swelling upon UV irradiation. However, the Cd crystals do not show such behaviour maintaining the original unit cell. Thus the photomechanical behaviour can be induced by choosing a suitable metal ion. The above findings are well 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.

Publisher

Research Square Platform LLC

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