Vibrational Properties of Thiolate-Protected Gold Nanoclusters.

Over recent years, the field of thiolate-protected gold nanoclusters has made remarkable progress. The successful determination of the structure of some of these clusters by X-ray crystallography was a milestone in this field. X-ray crystallography is arguably the most important technique in the field up to now, and it enabled the study of structure evolution as a function of cluster size. It also shed light on the structure of the Au-S interface. Recently, it has been realized that thiolate-protected gold clusters are very dynamic systems. Metal atoms and ligands can exchange easily between clusters. Furthermore, the adsorbed ligands bear conformational dynamics. Such dynamic effects call for experimental methods that can cope with it. Future efforts in this field will be directed toward applications of thiolate-protected clusters, and many of them will rely on dissolved clusters. Therefore, structure determination in solution is an important issue, though it is very challenging. The structure of the metal core and the Au-S interface is not expected to change in solution with respect to the crystal. However, the structure of the adsorbed ligand itself is sensitive to the environment and may be different in the solid state and in solution, as has been shown in fact in the past. It is this (dynamic) structure of the ligand that determines the interaction between the cluster and its environment, which is crucial, for example, for sensing applications. Vibrational spectroscopy is a promising technique to characterize thiolate-protected clusters in different environments. A vibrational spectrum is sensitive to structure (conformation) although this information is often "hidden" in the spectrum, requiring detailed analysis and support from theory to be deciphered. Compared to other techniques like UV-vis spectroscopy and mass spectrometry, vibrational spectroscopy was not extensively used in the field of thiolate-protected clusters, but we believe that the technique will be very valuable for the future developments in the field. We have used vibrational spectroscopy to investigate thiolate-protected gold clusters for mainly two lines of research. In the first, we studied in detail the low energy region of the vibrational spectrum, in particular the Au-S vibrational modes, in order to understand the structure sensitivity. It emerges that the Au-S vibrational spectrum is indeed sensitive to the structure of the interface but also to other factors, especially the organic part of the thiol, in a complex way. The ability to directly correlate structure, from X-ray crystallography, and vibrational spectra for thiolate-protected clusters, should lead to a database that will help in the future the structure determination of the Au-S interface by vibrational spectroscopy for systems where direct structure determination is not possible, for example, for flat surfaces. A second line of research focused on the determination of the structure of the adsorbed ligands for dissolved clusters. Such information is mostly extracted by the comparison of theoretical and calculated spectra for different conformers. In this respect, vibrational circular dichroism (VCD) is particularly powerful as it strongly depends on the conformation, more than conventional infrared spectroscopy. VCD can be applied to chiral nonracemic compounds, and it is a sensitive probe for chirality. Using this method, it was possible to demonstrate that a cluster can transfer its chirality to achiral thiolate ligands. In this Account, we summarize the possibilities and challenges of vibrational spectroscopy in the field of thiolate-protected clusters.