CONSPECTUS: There exists a special kind of perfectionin symmetry, simplicity, and stabilityattainable for structures generated from precisely 60 ligands (all of a single type) that protect 145 metal-atom sites. The symmetry in question is icosahedral (I h ), generally, and chiral icosahedral (I) in particular. A 60-fold equivalence of the ligands is the smallest number to allow this kind of perfection. Known cluster compounds that approximate this structural ideal include palladium-carbonyls, I h -Pd 145 (CO) 60 ; gold-thiolates, I-Au 144 (SR) 60 ; and gold-alkynyls, I-Au 144 (C 2 R) 60 . Many other variants are suspected. The Pd 145 compound established the basic achiral structure-type. However, the Au 144 -thiolate archetype is prominent, historically in its abundance and ease of preparation and handling, in its proliferation in many laboratories and application areas, and ultimately in the intrinsic chirality of its geometrical structure and organization of its bonding network or connectivity. As discovered by mass spectrometry (the "30-k anomaly") in 1995, it appeared as a broad single peak, as solitary and symmetrical as Mount Fuji, centered near 30 kDa (∼150 Au atoms), provoking these thoughts: Surely this phenomenon requires a unique explanation. It appears to be the Buckminsterfullerene (carbon-60) of gold-cluster chemistry. Herein we provide an elementary account of the unexpected discovery, in which the Pd 145 -structure played a critical role, that led to the identification and prediction, in 2008, of a fascinating new molecular structure-type, evidently the first one of chiral icosahedral symmetry. Rigorous confirmation of this prediction occurred in early spring 2018, when two single-crystal X-ray crystallography reports were submitted, each one distinguishing both enantiomeric structures and noting profound chirality for the surface (ligand) layer. The emphasis here is on the structure and bonding principles and how these have been elucidated. Our aim has been to present this story in simplest terms, consistent with the radical simplicity of the structure itself. Because it combines intrinsic profound chirality, at several levels, with the highest possible symmetry-type (icosahedral), the structure may attract broader interest also from educators, especially if studied in tandem with the analysis of hollow (shell) metallic systems that exhibit the same chirality and symmetry. Because the shortest (stiffest) bonds follow the chiral 3-way weave pattern of the traditional South-Asian reed football, this cultural artifact may be used to introduce chiral-icosahedral symmetry in a pleasant and memorable way. One may also appreciate easily the bonding and excitations in I-symmetry metallic nanostructures via the golden fullerenes, that is, the proposed hollow Au 60 , 72 spheres. Beyond any aesthetic or pedagogical value, we aim that our Account may provide a firm foundation upon which others may address open questions and the opportunities they present. This Account can scarcely hint at the prospects for...
Here we report on the identification and applications of an aqueous 29-atom silver cluster stabilized with 12 lipoate ligands, i.e. Ag 29 (R-α−LA) 12 or (29,12), wherein R-α− LA = R-α-lipoic acid, a natural dithiolate. Its uniformity is checked by HPLC-ESI-MS and analytical ultracentrifugation, which confirms its small dimension (∼3 nm hydrodynamic diameter). For the first time, this cluster has been detected intact via electrospray ionization mass spectrometry, allowing one to confirm its composition, its [3-] charge-state, and the 8-electron shell configuration of its metallic silver core. Its electronic structure and bonding, including T-symmetry and profound chirality in the outer shell, have been analyzed by DFT quantum-chemical calculations, starting from the known structure of a nonaqueous homologue. The cluster is effective against Methicillin-Resistant Staphylococcus aureus bacteria (MRSA) at a minimum inhibitory concentration (MIC) of 0.6 mg-Ag/mL. A preformed Candida albicans fungal biofilm, impermeable to other antifungal agents, was also inhibited by aqueous solutions of this cluster, in a dose−response manner, with a half-maximal inhibitory concentration (IC 50 ) of 0.94 mg-Ag/mL. Scanning electron micrographs showed the post-treatment ultrastructural changes on both MRSA and C. albicans that are characteristic of those displayed after treatment by larger silver nanoparticles.
The combination of profound chirality and high symmetry on the nm-scale is unusual and would open exciting avenues, both fundamental and applied. Here we show how the unique electronic structure and bonding of quasi-2D gold makes this possible. We report a chiral symmetry breaking, i.e., the spontaneous formation of a chiral-icosahedral shell (I−Au60) from achiral (Ih) precursor forms, accompanied by a contraction in the Au–Au bonding and hence the radius of this perfect golden sphere, in which all 60 sites are chemically equivalent. This structure, which resembles the most complex of semi-regular (Archimedean) polyhedra (34.5*), may be viewed as an optimal solution to the topological problem: how to close a 60-vertex 2D (triangular) net in 3D. The singular rigidity of the I−Au60 manifests in uniquely discrete structural, vibrational, electronic, and optical signatures, which we report herein as a guide to its experimental detection and ultimately its isolation in material forms.
Motivated by the recent theoretical discovery [Nat. Comm. 9, 3352 (2018)] of a surprisingly contracted sixty-atom hollow shell of chiral-icosahedral symmetry (I-Au 60 ) of remarkable rigidity and electronegativity, we have explored, via first-principles DFT calculations, its physico-chemical interactions with internal and external shells, enabling conclusions regarding its robustness as well as identifying composite forms in which an identifiable I-Au 60 may be realized as a product of natural or laboratory processes. The I-Au 60 dimensions and rigidity suggest a templating approach; e.g., an I h -C 60 fullerene fits nicely within its interior, as a nested cage. In this work, we have focused on its susceptibility, i.e. the extent to which the unique structural and electronic properties of I-Au 60 are modified by incorporation into selected multi-shell structures. Our results confirm that the I-Au 60 shell is robustly maintained and protected in various bilayer structures: I h -C
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