From Mononuclear Complexes to Molecular Nanoparticles: The Buildup of Atomically Precise Heterometallic Rhodium Carbonyl Nanoclusters.

Chemical research in synthesizing metal nanoparticles has been a major topic in the last two decades, as nanoparticles can be of great interest in many fields such as biology, catalysis, and nanotechnology. However, as their chemical and physical properties are size-dependent, the reliable preparation of nanoparticles at a molecular level is highly desirable. Despite the remarkable advances in recent years in the preparation of thiolate- or p-MBA or PA-protected gold and silver nanoclusters ( p-MBA = p-mercaptobenzoic acid; PA = phenylalkynyl), as well as the large palladium clusters protected by carbonyl and phosphine ligands that initially dominated the field, the synthesis of monodispersed and atomically precise nanoparticles still represents a great challenge for chemists. Carbonyl cluster compounds of high nuclearity have become more and more part of a niche chemistry, probably owing to their handling issues and expensive synthesis. However, even in large size, they are known at a molecular level and therefore can play a relevant role in understanding the structures of nanoparticles in general. For instance the icosahedral pattern, proper of large gold nanoparticles, is also found in some Au-Fe carbonyl cluster compounds. Rh clusters in general can also be employed as precursors in homo- and heterogeneous catalysis, and the possibility of doping them with other elements at the molecular level is an important additional feature. The fact that they can be obtained as large crystalline species, with dimensions of about 2 nm, allows one to place them not only in the nanometric regime, but also in the ultrafine-metal-nanoparticle category, which lately has been attracting growing attention. In fact, such small nanoparticles possess an even higher density of active catalytic sites than their larger (up to 100 nm) equivalents, hence enhancing atom efficiency and reducing the cost of precious-metal catalysts. Finally, the clusters' well-defined morphology could, in principle, contribute to expand the studies on the shape effects of nanocatalysts. In this Account, we want to provide the scientific community with some insights on the preparation of rhodium-containing carbonyl compounds of increasing nuclearity. Among them, we present the synthesis and molecular structures of two new heterometallic nanoclusters, namely, [RhGe(CO)] and [RhAu(CO)], which have been obtained by reacting a rhodium-cluster precursor with Ge(II) and Au(III) salts. The growth of such clusters is induced by redox mechanisms, which allow going from mononuclear complexes up to clusters with over 20 metal atoms, thus entering the nanosized regime.