Finding all-nonmetal transition-metal-like superatom and its magnetic building block
Finding all-nonmetal transition-metal-like superatom and its magnetic building block
复制标题
寻找全非金属类过渡金属超原子及其磁性构件
DOI：
10.1002/qua.25570
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发表时间：
2018
影响因子：
2.2
通讯作者：
Li Zhi-Ru
中科院分区：
文献类型：
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作者：
Jiang Hui-Hui;He Hui-Min;Li Ying;Wu Di;Liu Jia-Yuan;Yang Hui;Sun Wei-Ming;Zhong Rong-Lin;Zhou Zhong-Jun;Hou Jian-Hua;Wang Jia-Jun;Li Zhi-Ru
在新型超原子化学中，全金属团簇能够模拟非金属原子和简单非金属分子的行为是非常有吸引力的。具有2 P5亚壳层（对应于氯的3 p5）的神奇全金属卤素类超原子Al 13就是最典型的例子。相比之下，如何利用全非金属团簇来模拟磁性过渡金属原子的行为是超原子化学的一个有趣的挑战。对此，基于人类的直觉，我们利用量子化学方法，将Jeltron模型从金属团簇扩展到全非金属团簇，发现三重态下具有特征Jeltron电子构型1 S21 P62 S21 D8的全非金属八面体B6团簇在电子构型、物理和化学上都能模拟具有3s 23 p64 s23 d8电子构型的过渡金属Ni原子的行为。有趣的是，短B-B链长的B6非金属团簇的1 S1 P2 S1 D的特征有序度不同于传统的Jeltron模型中长M-M链长的金属团簇的1 S1 P1 D2 S，这表明非金属团簇对Jeltron轨道有序度的尺寸效应是一种新的. B6是一种新的全非金属过渡金属类镍超原子，自旋矩为2μ B，具有全非金属磁性超原子的性质.为了寻找全非金属磁性超原子的应用，我们将磁性超原子B6包裹在完全氢化的富勒烯中，形成自旋矩为2μB的笼形物B6@C60H60。由于C60 H60笼作为聚合单元可以保持B6的自旋矩，笼形物B6@C60H60是一种新的全非金属磁性超原子结构单元。自然，B6和B6@C60H60的磁性超原子结构可能是亚稳态的。
In novel superatom chemistry, it is very attractive that all‐metal clusters can mimic the behaviors of nonmetal atoms and simple nonmetal molecules. Wizardly all‐metal halogen‐like superatom Al13with 2P5sub shell (corresponding to the 3p5of chlorine) is the most typical example. In contrast, how to mimic the behaviors of magnetic transition‐metal atom using all‐nonmetal cluster is an intriguing challenge for superatom chemistry. In response to this based on human intuition, using quantum chemistry methods and extending jellium model from metal cluster to all‐nonmetal cluster, we have found out that all‐nonmetal octahedral B6cluster with characteristic jellium electron configuration 1S21P62S21D8in the triplet ground state can mimic the behaviors of transition‐metal Ni atom with electron configuration 3s23p64s23d8in electronic configuration, physics and chemistry. Interestingly, the characteristic order of 1S1P2S1D for the B6nonmetal cluster with short B‐B lengths is different from that of the traditional jellium model—1S1P1D2S for metal clusters with long M‐M lengths, which exhibits a novel size effect of nonmetal cluster on jellium orbital ordering. Based on the jellium electron configuration, the B6with the spin moment value of 2μBis a new all‐nonmetal transition‐metal nickel‐like superatom exhibiting a new kind of all‐nonmetal magnetic superatom. Finding the application of the all‐nonmetal magnetic superatom, we encapsulate the magnetic superatom B6inside fully hydrogenated fullerene forming a clathrate B6@C60H60with the spin moment value of 2μB. As the C60H60cage as a polymerization unit can conserve the spin moment of endohedral B6, the clathrate B6@C60H60is a new all‐nonmetal magnetic superatom building block. Naturally, magnetic superatom structures of the B6and B6@C60H60may be metastable.