The ability to crystallize so-called “magic” metal nanoclusters has yielded significant insight into the geometric structures of these nanoscale building blocks, but a lack of similarly precise experimental probes of electronic structure and reactivity impedes the development of quantitative descriptions of these aspects of nanocluster chemistry.  I will discuss our efforts to adapt mass-selective spectroscopic techniques and reactivity studies, originally developed to study molecular clusters, to ligand-protected metal nanoclusters.  We use mass spectrometry to separate clusters of exactly chosen composition from a polydisperse mixture, and study them in vacuo using vibrational and electronic spectroscopy and variable-temperature reactivity studies.  The absolute separation afforded by these techniques, as well as the exact control over the physical and chemical environment of the nanoclusters, allows us to examine their properties and reactivity as a function of their chemical identity.  I will show examples of electronic spectra at the limit of spectral resolution for both magic gold clusters as well as polydisperse mixtures, and discuss subtle solvatochromic shifts and ligand- and reactant-induced perturbations to the cluster electronic structure.  <br/>

Atomically-precise nanocluster electronic structure and reactivity from atomically-imprecise syntheses

2019 Fall National Meeting

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