Institute of Atomic and Molecular Physics, Jilin University, Changchun, 130012, China.
State Key Laboratory of Supermolecular Structure and Materials, Jilin University, Changchun, 130012, China.
Adv Sci (Weinh). 2023 Mar;10(9):e2206899. doi: 10.1002/advs.202206899. Epub 2023 Jan 25.
In this work, a novel discovery that the coinage-metal near-plane superatoms (CM-NPSs) formed by embedding actinide elements into the coinage metal rings can realize the "Z"-type tilted quasi-one-dimensional (1D) direct assembly is reported. This success can be attributed to the strong bonding between the overlapping parts of adjacent superatomic motifs. First-principles calculations reveal that the motifs maintain their geometric and electronic structures robustly during the assembly process. With the accumulation of motifs, the intensity of the absorption peak increases continuously in the ultraviolet-visible (UV-Vis) absorption spectra range of 300-450 nm, resulting in the hyperchromic effect, which is closely related to the degree of the participation of Th atoms. Furthermore, the absorption spectra show a continuously tunable feature in the 450-900 nm range, as the interlayer stacking pattern leads to a pronounced redshift. More importantly, the valence 5f-shells of Th atoms have an increased contribution to the final orbitals of electronic transition, which demonstrates the advantages of the active high angular momentum electrons of actinide elements in spectral properties. These findings provide a valuable reference for the direct artificial assembly of near-plane superatoms and optical properties of superatomic assemblies embedded with rare elements.
在这项工作中，报道了一个新的发现，即通过将锕系元素嵌入金属环中形成的近平面超原子（CM-NPS）可以实现“Z”型倾斜准一维（1D）直接组装。这一成功归因于相邻超原子基元重叠部分之间的强键合。第一性原理计算表明，在组装过程中基元保持其几何和电子结构的稳健性。随着基元的积累，在 300-450nm 的紫外-可见（UV-Vis）吸收光谱范围内，吸收峰的强度连续增加，产生超色效应，这与 Th 原子的参与程度密切相关。此外，吸收光谱在 450-900nm 范围内具有连续可调的特征，因为层间堆积模式导致明显的红移。更重要的是，Th 原子的价 5f 壳层对电子跃迁的最终轨道有更大的贡献，这表明锕系元素的活性高角动量电子在光谱性质方面的优势。这些发现为近平面超原子的直接人工组装和嵌入稀有元素的超原子组装的光学性质提供了有价值的参考。
