Mass Spectrometry of Small Bimetal Monolayer-Protected Clusters

Monolayer-protected clusters were prepared by procedures like those yielding Au25L18 (where L = −SCH2CH2Ph = −SC2Ph) but using, instead, mixtures of Au and Pd salts, as starting materials, with the intent of creating and characterizing Au25−xMxL18 clusters. Isolation of small nanoparticle product followed by partial ligand exchange to introduce thiolated poly(ethylene glycol) (SPEG = −S(CH2CH2O)5CH3) into the nanoparticle ligand shell enabled characterization of the Au25−xMxL18 content by positive mode electrospray ionization mass spectrometry (ESI-MS). For synthetic feed mole ratios of Au:Pd of 9:1 and 13:12, electrospray spectra of the PEGylated MPCs showed that the reaction and isolation produce a mixture of Au25(SC2Ph)18 and a mono-Pd nanoparticle Au24Pd(SC2Ph)18. A higher proportion of the mono-Pd nanoparticle is produced by the 13:12 mole ratio, and also when the thiol:metal ratio was lowered, according to ESI-MS and MALDI-TOF-MS. As the nanoparticle mixture is enriched, by solvent fractionations, in Au24Pd(SC2Ph)18 relative to Au25(SC2Ph)18, the distinctive optical and electrochemical signatures of Au25(SC2Ph)18 are replaced by Au24Pd(SC2Ph)18 nanoparticle responses, which are very different, even though only one Au atom is replaced by a Pd atom.