Single-Crystal-to-Single-Crystal [2 + 2] Photocycloaddition Reaction in a Photosalient One-Dimensional Coordination Polymer of Pb(II).

Abstract

In a remarkable example, we report a one-dimensional coordination polymer (CP) of Pb(II) showing photosalient (PS) properties triggered by [2 + 2] cycloaddition of olefinic ligands, which is seldom observed in CPs. Macroscopic rod-shaped crystals show various photomechanical effects such as jumping, splitting, rolling, and breaking upon UV illumination. In this rare example, we could determine the solid-state structure of the 100% dimerized product and three intermediate structures, even after the shattering of crystals into small pieces. Detailed mechanistic investigation from the single-crystal data indicates that the strain generated in the unit cell due to anisotropic expansion played a bigger role for the PS effects. Nucleated growth of the photoproduct crystal created different domains inside the single crystal, which multiplied the already developed stress leading to the photomechanical movements. This example falls in the gray area of a clean single-crystal-to-single-crystal (SCSC) transformation and violent PS effect. Such photochemical behavior has never been reported before.