RESUMEN
The crystal structures of 4 ligand-rotational isomers of Au25 (PET)18 are presented. Two new ligand-rotational isomers are revealed, and two higher-quality structures (allowing complete solution of the ligand shell) of previously solved Au25 (PET)18 clusters are also presented. One of the structures lacks an inversion center, making it the first chiral Au25 (SR)18 structure solved. These structures combined with previously published Au25 (SR)18 structures enable an analysis of the empirical ligand conformation landscape for Au25 (SR)18 clusters. This analysis shows that the dihedral angles within the PET ligand are restricted to certain observable values, and also that the dihedral angle values are interdependent, in a manner reminiscent of biomolecule dihedral angles such as those in proteins and DNA. The influence of ligand conformational isomerism on optical and electronic properties was calculated, revealing that the ligand conformations affect the nanocluster absorption spectrum, which potentially provides a way to distinguish between isomers at low temperature.
RESUMEN
Gold nanoclusters show distinctive magnetic properties and electronic structure. Nanoclusters of sufficiently small size restructure geometrically to stabilize electronically (e.g., a Jahn-Teller effect), whereas geometric distortion may not be possible in larger nanoclusters. In this work, the charge-state-dependent magnetism of the Au102(SPh)441-/0/1+/2+ nanocluster is investigated through Evans method NMR measurements. The 2+ charge state is shown as paramagnetic. This suggests that the nanocluster does not distort geometrically to pair electrons. Because the nanocluster lies within the transition range of molecule-like to bulk-like properties, this suggests that the geometric stabilization that becomes important in larger "magic number clusters" may be resistant to electronically driven distortions observed in smaller nanoclusters.