title: Electrocrystallization of Monolayer-Protected Gold Clusters: Opening the Door to Quality, Quantity, and New Structures.
abstract: 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)180clusters is described. A new cluster, Au25(S-nC5H11)18, was also prepared and found to crystallize by forming bundles of millimeter-long Au25polymers.
authors.affiliation: Department of Chemistry, University of Padova , via Marzolo 1, 35131 Padova, Italy.
authors.forename: Sabrina
authors.initials: S
authors.lastname: Antonello
authors.affiliation: Department of Chemistry, University of Padova , via Marzolo 1, 35131 Padova, Italy.
authors.forename: Tiziano
authors.initials: T
authors.lastname: Dainese
authors.affiliation: Department of Chemistry, Nanoscience Center, University of Jyvaskyla , P.O. Box 35, 40014 Jyvaskyla, Finland.
authors.forename: Fangfang
authors.initials: F
authors.lastname: Pan
authors.affiliation: Department of Chemistry, Nanoscience Center, University of Jyvaskyla , P.O. Box 35, 40014 Jyvaskyla, Finland.
authors.forename: Kari
authors.identifier: 0000-0002-7282-8419
authors.initials: K
authors.lastname: Rissanen
authors.affiliation: Department of Chemistry, University of Padova , via Marzolo 1, 35131 Padova, Italy.|Department of Chemistry, University of Connecticut , 55 North Eagleville Road, Storrs, Connecticut 06269, United States.
authors.forename: Flavio
authors.identifier: 0000-0002-8627-6491
authors.initials: F
authors.lastname: Maran