A Change of Pace: Record Photoresponse through Spirooxazine Confinement in a Metal-Organic Matrix.

Abstract

Modern and upcoming high-speed optoelectronics as well as secure data storage or solar energy harvesting technologies integrating stimuli-responsive materials fully rely on the fundamental concept of rapid transitions between discrete states possessing different properties. Relatively slow transition kinetics between those states for commonly used classes of photochromic compounds in solution or bulk solids severely restrict the applicability of stimuli-responsive materials for device development. Herein, we report a multivariate strategy based on a photochromic spirooxazine derivative, coordinatively integrated in the solvent-free confined space of a solid-state matrix, such as a metal-organic framework (MOF), for the first time, resulting in the fastest photoresponse reported for any solid-state material to date. The photoisomerization rate for the developed photochromic material was estimated to be 126 s^-1, surpassing any literature reports to the best of our knowledge. We also shed light on the fundamentals of the correlation between framework topology, the nature of organic linkers, and the presence/absence of organic solvent within the scaffold voids on the material photoresponse using a series of isoreticular frameworks. Overall, the presented conceptual approach allows for tailoring the isomerization kinetics of photochromic molecules in the solid state over a range of 4 orders of magnitude-an unprecedented span that provides a pathway for addressing challenges associated with the response rate and photoisomerization, which are key criteria in stimuli-responsive material development.