A cationic thorium–organic framework with triple single-crystal-to-single-crystal transformation peculiarities for ultrasensitive anion recognition

Abstract

Single-crystal-to-single-crystal transformation of metal–organic frameworks has been met with great interest, as it allows for the creation of new materials in a stepwise manner and direct visualization of structural transitions when subjected to external stimuli. However, it remains a peculiarity among numerous metal–organic frameworks, particularly for the ones constructed from tetravalent metal cations. Herein, we present a cationic thorium–organic framework displaying unprecedented triple single-crystal-to-single-crystal transformations in organic solvents, water, and NaIO₃ solution. Notably, both the interpenetration conversion and topological change driven by the SC–SC transformation have remained elusive for thorium–organic frameworks. Moreover, the single-crystal-to-single-crystal transition in NaIO₃ solution can efficiently and selectively turn the ligand-based emission off, leading to the lowest limit of detection (0.107 μg kg⁻¹) of iodate, one of the primary species of long-lived fission product ¹²⁹I in aqueous medium, among all luminescent sensors.