Cheng Shi-Bo, Berkdemir Cuneyt, Castleman A W
Departments of Chemistry and.
Departments of Chemistry and Department of Physics, Yildiz Technical University, Istanbul 34210, Turkey.
Proc Natl Acad Sci U S A. 2015 Apr 21;112(16):4941-5. doi: 10.1073/pnas.1504714112. Epub 2015 Apr 6.
Rare earth elements (REs) consist of a very important group in the periodic table that is vital to many modern technologies. The mining process, however, is extremely damaging to the environment, making them low yield and very expensive. Therefore, mimicking the properties of REs in a superatom framework is especially valuable but at the same time, technically challenging and requiring advanced concepts about manipulating properties of atom/molecular complexes. Herein, by using photoelectron imaging spectroscopy, we provide original idea and direct experimental evidence that chosen boron-doped clusters could mimic the magnetic characteristics of REs. Specifically, the neutral LaB and NdB clusters are found to have similar unpaired electrons and magnetic moments as their isovalent REs (namely Nd and Eu, respectively), opening up the great possibility in accomplishing rare earth mimicry. Extension of the superatom concept into the rare earth group not only further shows the power and advance of this concept but also, will stimulate more efforts to explore new superatomic clusters to mimic the chemistry of these heavy atoms, which will be of great importance in designing novel building blocks in the application of cluster-assembled nanomaterials. Additionally, based on these experimental findings, a novel "magic boron" counting rule is proposed to estimate the numbers of unpaired electrons in diatomic LnB clusters.
稀土元素(REs)在元素周期表中是非常重要的一类元素,对许多现代技术至关重要。然而,其开采过程对环境破坏极大,导致产量低且成本高昂。因此,在超原子框架中模拟稀土元素的性质具有特别重要的价值,但同时在技术上具有挑战性,需要有关操纵原子/分子复合物性质的先进概念。在此,通过使用光电子成像光谱,我们提供了原创思路和直接实验证据,表明所选择的硼掺杂团簇可以模拟稀土元素的磁特性。具体而言,发现中性的LaB和NdB团簇分别具有与其等价位稀土元素(即Nd和Eu)相似的未成对电子和磁矩,这为实现稀土模拟开辟了很大的可能性。将超原子概念扩展到稀土元素组不仅进一步展示了这一概念的强大力量和先进性,而且还将激发更多努力去探索新的超原子团簇以模拟这些重原子的化学性质,这对于在团簇组装纳米材料应用中设计新型构建块具有重要意义。此外,基于这些实验结果,提出了一种新颖的“神奇硼”计数规则,用于估计双原子LnB团簇中未成对电子的数量。