From Small Metal Clusters to Molecular Nanoarchitectures with a Core–Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co₃₈As₁₂(CO)₅₀]^4–

Roberto Della Pergola,Luigi Garlaschelli,Piero Macchi,Irene Facchinetti,Riccardo Ruffο,Stefano Racioppi,Angelo Sironi

Inorganic Chemistry（2022）

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摘要

The cluster [Co38As12(CO)50]4- was obtained by pyrolysis of [Co6As(CO)16]-. The metal cage features a closed-packed core inside a Co/As shell that progressively deforms from a cubic face-centered symmetry. The redox and acid-base reactivities were determined by cyclic voltammetry and spectrophotometric titrations. The calculated electron density revealed the shell-constrained distribution of the atomic charges, induced by the presence of arsenic.

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molecular nanoarchitectures,small metal clusters,core–shell structure,solid-state

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From Small Metal Clusters to Molecular Nanoarchitectures with a Core–Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co38As12(CO)50]4–

From Small Metal Clusters to Molecular Nanoarchitectures with a Core–Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co₃₈As₁₂(CO)₅₀]^4–