Stimuli-responsive photoswitch–actinide binding: a match made in MOFs
Kyoung Chul Park, Jaewoong Lim, Grace C. Thaggard, Buddhima K. P. Maldeni Kankanamalage, Ingrid Lehman‐Andino, Yuan Liu, Jennii M. Burrell, Corey R. Martin, An T. Ta, Andrew B. Greytak, Jake Amoroso, David D. DiPrete, Mark D. Smith, Simon R. Phillpot, Natalia B. Shustova
Abstract
photochromic moieties, realized through probing thermodynamics and kinetics aspects, including changes in photoswitch isomerization constants upon metal coordination and enthalpies associated with the synergistic actinide-switch photochromic processes. A comprehensive analysis of the presented concept was executed through evaluation of data acquired through a multivariate strategy involving isothermal titration calorimetry, crystallography, spectroscopy, and theoretical modeling on the example of actinide-containing compounds based on thorium(iv)-, and uranium(iv, vi), as well as transuranic elements such as plutonium(iv) in solution and within a metal-organic framework (MOF) matrix for the first time. Overall, the presented concept could usher in an alternative direction in stimuli-responsive actinide-based platforms that could be adapted to confront current and upcoming challenges in f-block chemistry.