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

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posted on 09.09.2020, 17:05 by Liwei Cheng, Chengyu Liang, Wei Liu, Yaxing Wang, Bin Chen, Hailong Zhang, Yanlong Wang, Zhifang Chai, Shuao Wang
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, SCU-14. Long-range π–π stacking extending throughout the structure is built via polycatenation, providing a visible carrier transmission path. SCU-14 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, SCU-14 can effectively convert X-ray photons to electrical current signals and presents a promising sensitivity of 54.93 μC Gy–1 cm–2.