Electrocrystallization of Monolayer-Protected Gold Clusters : Opening the Door to Quality, Quantity, and New Structures
Antonello, S., Dainese, T., Pan, F., Rissanen, K., & Maran, F. (2017). Electrocrystallization of Monolayer-Protected Gold Clusters : Opening the Door to Quality, Quantity, and New Structures. Journal of the American Chemical Society, 139 (11), 4168-4174. doi:10.1021/jacs.7b00568
Julkaistu sarjassaJournal of the American Chemical Society
© the Authors, 2017. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
Thiolate-protected metal clusters are materials of ever-growing importance in fundamental and applied research. Knowledge of their single-crystal X-ray structures has been instrumental to enable advanced molecular understanding of their intriguing properties. So far, however, a general, reliable, chemically clean approach to prepare single crystals suitable for accurate crystallographic analysis was missing. Here we show that single crystals of thiolate-protected clusters can be grown in large quantity and very high quality by electrocrystallization. This method relies on the fact that charged clusters display a higher solubility in polar solvents than their neutral counterparts. Nucleation of the electrogenerated insoluble clusters directly onto the electrode surface eventually leads to the formation of a dense forest of millimeter-long single crystals. Electrocrystallization of three known Au25(SR)180 clusters is described. A new cluster, Au25(S-nC5H11)18, was also prepared and found to crystallize by forming bundles of millimeter-long Au25 polymers. ...