Jahn–Teller effects in Au25(SR)18. Issue 3 (11th December 2015)

• Record Type: Journal Article
• Authors: Tofanelli, Marcus A.; Salorinne, Kirsi; Ni, Thomas W.; Malola, Sami; Newell, Brian; Phillips, Billy; Häkkinen, Hannu; Ackerson, Christopher J.
• Is Part Of: Chemical science. Volume 7:Issue 3(2016:Mar.)
• Page Start: 1882
• Page End: 1890
• Publication Date: 2015-12-11
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c5sc02134k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Jahn–Teller distortions are observed in Au25 (SR)18 by single crystal X-ray crystallography. SQUID magnetometry, DFT theory, and linear optical spectroscopy corroborate the finding. Abstract : The relationship between oxidation state, structure, and magnetism in many molecules is well described by first-order Jahn–Teller distortions. This relationship is not yet well defined for ligated nanoclusters and nanoparticles, especially the nano-technologically relevant gold-thiolate protected metal clusters. Here we interrogate the relationships between structure, magnetism, and oxidation state for the three stable oxidation states, −1, 0 and +1 of the thiolate protected nanocluster Au25 (SR)18 . We present the single crystal X-ray structures of the previously undetermined charge state Au25 (SR)18 +1, as well as a higher quality single crystal structure of the neutral compound Au25 (SR)18 0 . Structural data combined with SQUID magnetometry and DFT theory enable a complete description of the optical and magnetic properties of Au25 (SR)18 in the three oxidation states. In aggregate the data suggests a first-order Jahn–Teller distortion in this compound. The high quality single crystal X-ray structure enables an analysis of the ligand–ligand and ligand–cluster packing interactions that underlie single-crystal formation in thiolate protected metal clusters.