title: Building Diatomic and Triatomic Superatom Molecules.
abstract: 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.
authors.affiliation: Department of Chemistry, Columbia University , New York, New York 10027 United States.
authors.forename: Anouck M
authors.initials: AM
authors.lastname: Champsaur
authors.affiliation: Department of Chemistry, Columbia University , New York, New York 10027 United States.
authors.forename: Alexandra
authors.initials: A
authors.lastname: Velian
authors.affiliation: Department of Chemistry, Columbia University , New York, New York 10027 United States.
authors.forename: Daniel W
authors.initials: DW
authors.lastname: Paley
authors.affiliation: Department of Chemistry, Columbia University , New York, New York 10027 United States.
authors.forename: Bonnie
authors.initials: B
authors.lastname: Choi
authors.affiliation: Department of Chemistry, Columbia University , New York, New York 10027 United States.
authors.forename: Xavier
authors.initials: X
authors.lastname: Roy
authors.affiliation: Department of Chemistry, Columbia University , New York, New York 10027 United States.
authors.forename: Michael L
authors.initials: ML
authors.lastname: Steigerwald
authors.affiliation: Department of Chemistry, Columbia University , New York, New York 10027 United States.
authors.forename: Colin
authors.initials: C
authors.lastname: Nuckolls
keywords: Superatoms; nanoscale atoms; nanoscale building blocks; superatom molecules