This review is devoted to metal cluster synthesis in solution via radiolytic reduction of ionic precursors under the proper conditions. The size and structure of the final particles are described in relation to the nucleation and growth mechanism of the process with a special interest in oligomers and nanometric-sized particles. The influence of either a polymeric surfactant or a ligand or a support is described. The role of a chemical electron donor in the development of cluster size is explained. Particular attention is paid to the formation of bimetallic clusters and to the synthesis conditions required to obtain either a core-shell or an alloyed structure in relation to a possible intermetal electron transfer.
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