Three-Dimensional Polycatenation of a Uranium-Based Metal–Organic Cage: Structural Complexity and Radiation Detection

Abstract

The potential applications of metal-organic cages (MOCs) are mostly achieved through specific host-guest interactions within their cavities. Electronic applications would require an effective electron transport pathway, which has been extensively studied in hybrid organic-inorganic materials with extended structures. These properties have not been considered for MOCs because cage-to-cage interactions in these materials have rarely been examined and are challenging to functionalize. We report here a previously unobserved actinide-based MOC assembled from four hexagonal-bipyramidal-coordinated uranyl ions and six bidentate flexible ligands. Remarkably, each isolated cage is further interlocked with six adjacent ones through mechanical bonds, resulting in the first case of a 0D → 3D f-element polycatenated metal-organic cage, <b>SCU-14</b>. Long-range π-π stacking extending throughout the structure is built via polycatenation, providing a visible carrier transmission path. <b>SCU-14</b> is also an extremely rare case of an intrinsically semiconductive MOC with a wide band gap of 2.61 eV. Combined with the high X-ray attenuation efficiency, <b>SCU-14</b> can effectively convert X-ray photons to electrical current signals and presents a promising sensitivity of 54.93 μC Gy^-1 cm^-2.