Stimuli-responsive photoswitch–actinide binding: a match made in MOFs
The fundamentals of switchable actinide-ligand binding modes are central for designing new platforms for addressing challenges associated with, for example, isolation of pure radiological daughters for nuclear medicine or methods for efficient nuclear stockpile recycling. This study is the first to report actinide binding modes controlled by an external stimulus <i>via</i> 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.
Authors
- Natalia B. Shustova (ORCID: https://orcid.org/0000-0003-3952-1949)
- Simon R. Phillpot (ORCID: https://orcid.org/0000-0002-7774-6535)
- Grace C. Thaggard (ORCID: https://orcid.org/0000-0003-2390-8997)
- Corey R. Martin (ORCID: https://orcid.org/0000-0003-4124-3618)
- Mark D. Smith (ORCID: https://orcid.org/0000-0001-6977-7131)
- Jaewoong Lim (ORCID: https://orcid.org/0000-0002-4557-0870)
- Kyoung Chul Park
- Jake Amoroso (ORCID: https://orcid.org/0000-0003-3804-487X)
- Ingrid Lehman‐Andino (ORCID: https://orcid.org/0000-0003-3055-9078)
- Buddhima K. P. Maldeni Kankanamalage (ORCID: https://orcid.org/0009-0000-0942-1563)
- Andrew B. Greytak (ORCID: https://orcid.org/0000-0001-8978-6457)
- An T. Ta (ORCID: https://orcid.org/0000-0002-2767-8343)
- Jennii M. Burrell
- Yuan Liu (ORCID: https://orcid.org/0000-0003-3973-4207)
- David D. DiPrete
Institutions
- University of South Carolina (US)
- Savannah River National Laboratory (US)
- University of Florida (US)
Publication Details
- Journal
- Chemical Science
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5sc03171k
- Citations
- 3
- Primary Topic
- Photochromic and Fluorescence Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 1.55
Funders
- National Science Foundation
- U.S. Department of Energy
- Camille and Henry Dreyfus Foundation
- Alexander von Humboldt-Stiftung
- Office of Science
- Office of the Vice President for Research, University of South Carolina
- Division of Materials Research
- Energy Frontier Research Centers