Department of Chemistry, Columbia University, New York 10027, USA.
Department of Physics, Columbia University, New York 10027, USA.
Nat Chem. 2017 Dec;9(12):1170-1174. doi: 10.1038/nchem.2844. Epub 2017 Aug 14.
The controlled introduction of impurities into the crystal lattice of solid-state compounds is a cornerstone of materials science. Intercalation, the insertion of guest atoms, ions or molecules between the atomic layers of a host structure, can produce novel electronic, magnetic and optical properties in many materials. Here we describe an intercalation compound in which the host [CoTe(PPr)][C], formed from the binary assembly of atomically precise molecular clusters, is a superatomic analogue of traditional layered atomic compounds. We find that tetracyanoethylene (TCNE) can be inserted into the superstructure through a single-crystal-to-single-crystal transformation. Using electronic absorption spectroscopy, electrical transport measurements and electronic structure calculations, we demonstrate that the intercalation is driven by the exchange of charge between the host [CoTe(PPr)][C] and the intercalant TCNE. These results show that intercalation is a powerful approach to manipulate the material properties of superatomic crystals.
将杂质受控引入到固态化合物的晶格中是材料科学的基石。插层，即将客体原子、离子或分子插入到主体结构的原子层之间，可以在许多材料中产生新颖的电子、磁性和光学性质。在这里，我们描述了一种插层化合物，其中主体[CoTe(PPr)][C]由原子精确的分子簇二元组装而成，是传统层状原子化合物的超原子类似物。我们发现，四氰乙烯（TCNE）可以通过单晶到单晶的转变插入到超结构中。通过电子吸收光谱、电输运测量和电子结构计算，我们证明插层是由主体[CoTe(PPr)][C]和插层剂 TCNE 之间的电荷交换驱动的。这些结果表明，插层是一种操纵超原子晶体材料性质的强大方法。
