Gas phase reactivity observed in an ion trap was used to produce silver clusters protected with thioglycolic acid. Fragmentation pathways as well as optical properties were explored experimentally and theoretically. Sequential losses of SCH2 and CO2 in the ion trap lead to redox reactions with charge transfers between the metal part and the carboxylate and thiolate groups. This allows us to control the number of electrons in the metallic subunit and thus optical properties of the complexes. The presented formation process can be used as a prototype for tuning optical and chemical properties of ligated metal clusters by varying the number of confined electrons within the metallic subunit.
