Shapeshifting: Ligation by 1,4-cyclohexadiene induces a structural change in Ag 5

Abstract

Relatively little is known about structural transformations of very small metal clusters that result from the adsorption of molecules. Here, the ligand-induced structural transformation of Ag 5 +(g) by 1,4-cyclohexadiene, which is capable of binding metal clusters as a bidentate ligand, is investigated using equilibrium mass spectrometry experiments and theory. Based on the measured sequential ligand binding free energies of Ag n +(cyclohexene) m and Ag n +(1,4-cyclohexadiene) m (n = 3 and 5; m up to 3), it is found that Ag 5 +(1,4-cyclohexadiene) is a particularly stable cluster relative to the other ion-molecule association complexes investigated. These results together with those from ele..