Chiral and Achiral Crystal Structures of Au25(PET)180 Reveal Effects of Ligand Rotational Isomerization on Optoelectronic Properties

• Published in: Chemistry : a European journal 2024-01, Vol.30 (2), p.n/a
• Main Authors: Kuda‐Singappulige, Gowri Udayangani, Window, Phillip S., Hosier, Christopher A., Anderson, Ian D., Aikens, Christine M., Ackerson, Christopher J.
• Format: Article
• Language: English
• Subjects: Absorption spectra; Biomolecules; Chemistry; Cluster analysis; Conformation; Crystal structure; Dihedral angle; Empirical analysis; experiment-theory; gold nanoclusters; isomerism; Isomerization; Isomers; Ligands; Low temperature; Nanoclusters; Optical properties; Optoelectronics; superatoms
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202202760

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. Analysis of all Au25(phenylethanethiol)18 crystal structures, including 2 novel clusters, reveals that ligand rotational angles are interdependent and constrained to a narrow range of values.