Intermetalloid Clusters: Molecules and Solids in a Dialogue

Atom‐precise, ligand‐stabilized metalloid clusters have emerged as outstanding model systems to study fundamental structure and bonding situations of compositionally related molecules and extended solid phases. However, this fascinating field of research is still largely restricted to homometallic and pseudo‐heterometallic systems of closely related d‐block metals. In this review, we will highlight our own and others’ efforts to project the structural and compositional diversity of intermetallics with dissimilar d‐ and p‐block metal combinations, particularly the Zintl and Hume‐Rothery phases, onto the molecular level in order to bridge the still gaping chasm between heterometallic molecular coordination chemistry and solid‐state intermetallics. Herein, fundamental synthetic approaches, as well as structural and electronic properties of thus accessible “molecular alloys” will be addressed, and placed against their exceptional position as intermediates on the way to nanomaterials.