Park Kyoung Chul, Lim Jaewoong, Thaggard Grace C, Maldeni Kankanamalage Buddhima K P, Lehman-Andino Ingrid, Liu Yuan, Burrell Jennii M, Martin Corey R, Ta An T, Greytak Andrew B, Amoroso Jake W, DiPrete David D, Smith Mark D, Phillpot Simon R, Shustova Natalia B
University of South Carolina, Department of Chemistry and Biochemistry Columbia South Carolina 29208 USA
Savannah River National Laboratory Aiken South Carolina 29808 USA.
Chem Sci. 2025 Jun 17. doi: 10.1039/d5sc03171k.
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 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.
可切换的锕系元素-配体结合模式的基本原理是设计新平台的核心，这些新平台旨在应对与例如分离用于核医学的纯放射性子体或高效核储备回收方法相关的挑战。本研究首次报道了由外部刺激（光致变色部分）控制的锕系元素结合模式，这是通过探测热力学和动力学方面实现的，包括金属配位时光开关异构化常数的变化以及与协同的锕系元素-开关光致变色过程相关的焓。通过对基于钍（IV）、铀（IV、VI）以及超铀元素如溶液中和金属有机框架（MOF）基质中的钚（IV）的含锕系元素化合物的实例，采用包括等温滴定量热法、晶体学、光谱学和理论建模的多变量策略获取的数据进行评估，对所提出的概念进行了全面分析。总体而言，所提出的概念可能会在基于刺激响应的锕系元素平台上开辟一个替代方向，该方向可用于应对f区化学当前和即将面临的挑战。
