Atomically precise colloidal metal clusters have attracted much attention due to their usage in biological and biomedical applications, their photophysical properties, and their use in catalytic transformations. Among them, coinage metal nanoclusters are a paradigmatic system stimulating tremendous research trends. While tertiary phosphanes are widely used to stabilize nanoclusters, there are few examples of metal clusters with low-coordinate phosphorus ligands and very few can be isolated. In this context, we developed a synthetic method for the quantitative formation of imidazoliumyl phosphinidenide-bridged coinage-metal clusters starting from tris-silylated phosphonio-phosphanide 1[OTf]. Reaction of the latter with alcohols R-OH (e.g. MeOH, EtOH) in the presence of various coinage-metal(I) sources allows the formal transfer of an [LC-P]- fragment. Reactions with Au(I) sources typically give tetracationic hexanuclear complexes, while those with Cu(I) or Ag(I) sources yield dodecanuclear clusters in which the metal atoms exhibit an anticuboctahedral geometry. The facile exchange of coordinating solvent molecules on the cluster surfaces with polytopic linkers such as 4,4’-bipyridine, biphenyl-4,4’-dicarboxylic acid, or biphenyl-4,4’-disulfonic acid allows the formation of multidimensional frameworks.

Coinage-metal-phosphinidenide clusters: synthesis and assembly to multidimensional frameworks

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ACS Fall 2022

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