Electron and Spin Delocalization in [Co6Se8(PEt3)6]0/+1 Superatoms

Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representat...

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Bibliographic Details
Published in:Chemphyschem 2024-01, Vol.25 (2), p.e202300064-n/a
Main Authors: Xu, Yunyao, Chen, Jia, Aydt, Alexander P., Zhang, Lichirui, Sergeyev, Ivan, Keeler, Eric G., Choi, Bonnie, He, Shoushou, Reichman, David R., Friesner, Richard A., Nuckolls, Colin, Steigerwald, Michael L., Roy, Xavier, McDermott, Ann E.
Format: Article
Language:English
Subjects:
Aromaticity
cluster aromaticity
Diamagnetism
Electron spin
Electronic structure
Ligands
Magnetic properties
Molecular clusters
Molecular orbitals
NMR
Nuclear magnetic resonance
Paramagnetism
quantum calculations
spin/electron delocalization
SSNMR
superatomic solid
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Summary:Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co6Se8(PEt3)6. We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co6Se8] core while ligands function as an insulated shell. 59Co SSNMR measurements on the core and 31P, 13C on the ligands show that the neutral Co6Se8(PEt3)6 is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross‐validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co6Se8(PEt3)6]+1 is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single‐electron devices. Multinuclear NMR and quantum calculation reveal the atom‐like feature of a metal chalcogenide cluster, a superatom as the valence electrons/spins delocalize over the entire inorganic core and are insulated by its ligand shell.
ISSN:1439-4235
1439-7641
DOI:10.1002/cphc.202300064