Building Diatomic and Triatomic Superatom Molecules

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• 作者：Anouck M. Champsaur ; Alexandra Velian ; Daniel W. Paley ; Bonnie Choi ; Xavier Roy ; Michael L. Steigerwald ; Colin Nuckolls
• 刊名：Nano Letters
• 出版年：2016
• 出版时间：August 10, 2016
• 年：2016
• 卷：16
• 期：8
• 页码：5273-5277
• 全文大小：364K
• 年卷期：0
• ISSN：1530-6992

文摘

In this study, we have developed a method to create Co₆Se₈ superatoms in which we program the metal–ligand bonds. We exclusively form the Co₆Se₈ core under simple reaction conditions with a facile separation of products that contain differential substitution of the core. The combination of Co₂(CO)₈ and PR₃ with excess Se gives the differentially and directionally substituted superatoms, Co₆Se₈(CO)_x(PR₃)_(6–x). The CO groups on the superatom can be exchanged quantitatively with phosphines and isonitriles. Substitution of the CO allows us to manipulate the type and length of chemical bridge between two redox-active superatomic centers in order to modulate intersuperatomic coupling. Linking two superatoms together allows us to form the simplest superatom molecule: a diatomic molecule. We extend the superatom molecule concept to link three superatoms together in a linear arrangement to form acyclic triatomic molecules. These superatom molecules have a rich electrochemical profile and chart a clear path to a whole family of superatom molecules with new and unusual collective properties.