Three-Dimensional Polycatenation of a Uranium-Based Metal-Organic Cage: Structural Complexity and Radiation Detection
Three-Dimensional Polycatenation of a Uranium-Based Metal-Organic Cage: Structural Complexity and Radiation Detection
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DOI：
10.1021/jacs.0c08117
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发表时间：
2020-09-23
影响因子：
15
通讯作者：
Wang, Shuao
中科院分区：
文献类型：
--
作者：
Cheng, Liwei;Liang, Chengyu;Wang, Shuao
金属有机笼（MOCs）的潜在应用主要是通过其腔体内特定的主客体相互作用实现的。电子应用需要有效的电子传输途径，这在具有扩展结构的有机-无机杂化材料中已经得到了广泛的研究。MOC没有考虑这些特性，因为这些材料中的笼与笼之间的相互作用很少被检查，并且功能化具有挑战性。在这里，我们报告了一个以前未观察到的锕系MOC组装从四个六角双锥配位的铀酰离子和六个双齿柔性配体。值得注意的是，每个孤立的笼进一步通过机械键与六个相邻的笼互锁，导致第一种情况下的0 D-> 3D f-元素多链金属有机笼，SCU-14。通过多链连接构建了整个结构中延伸的长距离π-π堆叠，提供了可见的载流子传输路径。SCU-14也是一种极其罕见的本征带隙为2.61 eV的MOC。结合高X射线衰减效率，SCU-14可以有效地将X射线光子转换为电流信号，并呈现出54.93 μ C戈伊（-1）cm（-2）的有希望的灵敏度。
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 pi-pi 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 mu C Gy(-1) cm(-2).