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

Abstract

Targeted syntheses of MM′Au36(PET)24 (M, M′=Pd, Pt; PET=SC2H4Ph) were achieved by hydride‐mediated fusion reactions between [MAu8(PPh3)8]2+ and [M′Au24(PET)18]−. Single‐crystal X‐ray diffraction analysis indicated that the products have bi‐icosahedral MM′Au21 cores composed of M@Au12 and M′@Au12 superatoms. Although the MM′Au21 superatomic molecules correspond to O2 in terms of the number of valence electrons (12 e), the distances between the icosahedrons were larger than that in the bi‐icosahedral Au23 core of Au38(PET)24 corresponding to F2 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@Au12 and M′@Au12 superatoms.

A new insight into the push‐pull effect of substituents via the stilbene‐like model compounds

“…Push‐pull effect of substituents is an important concept, which is often employed to improve the properties of organic compounds [1–24], such as UV absorption [4, 15], fluorescence emission [6, 16], intramolecular charge transfer [1, 3, 14], nonlinear optical properties [5, 13], photovoltaic performance [10], organic light‐emitting diode [19], and so on. If we input the word “push‐pull effect” into the Web of Science, we will obtain more than 100,000 items, which implies that the push‐pull effect of substituents is widely used in physics and chemistry.…”