From Small Metal Clusters to Molecular Nanoarchitectures with a Core-Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co 38 As 12 (CO) 50 ] 4 .

The cluster [Co 38 As 12 (CO) 50 ] 4- was obtained by pyrolysis of [Co 6 As(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.