Controlled Dimerization and Bonding Scheme of Icosahedral M@Au12 (M=Pd, Pt) Superatoms

Targeted syntheses of MM ' Au-36(PET)(24) (M, M '=Pd, Pt; PET=SC2H4Ph) were achieved by hydride-mediated fusion reactions between [MAu8(PPh3)(8)](2+) and [M ' Au-24(PET)(18)](-). Single-crystal X-ray diffraction analysis indicated that the products have bi-icosahedral MM ' Au-21 cores composed of M@Au-12 and M '@Au-12 superatoms. Although the MM ' Au-21 superatomic molecules correspond to O-2 in terms of the number of valence electrons (12 e), the distances between the icosahedrons were larger than that in the bi-icosahedral Au-23 core of Au-38(PET)(24) corresponding to F-2 and the spin state was singlet. These counterintuitive results were explained by a bent bonding model based on tilted (non-orthogonal) bonding interaction between the 1P superatomic orbitals of M@Au-12 and M '@Au-12 superatoms.

Automated summary

Targeted syntheses of MM ' Au-36(PET)(24) were achieved through hydride-mediated fusion reactions, resulting in bi-icosahedral MM ' Au-21 cores composed of M@Au-12 and M '@Au-12 superatoms. Counterintuitive results were explained by a bent bonding model based on tilted bonding interaction between the superatomic orbitals.