The attainment of the superatomic state offers a unifying framework for the periodic classification of atomic clusters. Metallic clusters attain the superatomic state via the confined nearly free electron gas model that leads to groupings of quantum states marked by radial and angular momentum quantum numbers. We examine ligated octahedral metal-chalcogenide clusters where the nearly free electron gas model is invalid; however, the high symmetry can also lead to the bunching of electronic states. For octahedral TMEL clusters (TM = transition metal; E = chalcogen; L = ligand), the electronic shells are filled for valence electron counts of 96, 100, and 114 electrons. These magic electron counts are marked by large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, high ionization energies, and low electron affinity─all classic signatures of the superatomic state. We also find that clusters with electron counts differing from the magic counts show periodic patterns reminiscent of those observed in the periodic table of elements.
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http://dx.doi.org/10.1021/acs.inorgchem.2c02361 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada.
N-heterocyclic carbene (NHC)-protected gold nanoclusters display high stability and high photoluminescence, making them well-suited for fluorescence imaging and photodynamic therapeutic applications. We report herein the synthesis of two bisNHC-protected Au nanoclusters with π-extended aromatic systems. Depending on the position of the π-extended aromatic system, changes to the structure of the ligand shell in the cluster are observed, with the ability to correlate increases in rigidity with increases in fluorescence quantum yield.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
School of Chemistry & Chemical Engineering, Anhui University, Hefei, Anhui 230601, PR China.
Superatoms are stable clusters that mimic the chemical behavior of individual atoms in the periodic table. Many endeavors have been devoted to the design and characterization of various superatoms, while engineering superatoms to mimic the chemistry of chalcogens remains a challenge. In this paper, we present a new superchalcogen by evaluating a hollow tetrahedral AlO cluster with theoretical calculations.
View Article and Find Full Text PDFSci Adv
January 2025
College of Energy Materials and Chemistry, Inner Mongolia University, Hohhot 010021, China.
Hydrides in metal complexes or nanoclusters are typically viewed as electron-withdrawing. Several recent reports have demonstrated the emergence of "electron-donating" hydrides in tailoring the structure, electronic structure, and reactivity of metal nanoclusters. However, the number of such hydrides included in each cluster kernel is limited to one or two.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Beijing National Laboratory for Molecular Science (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Inorg Chem
January 2025
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-Ku, Sendai 980-8578, Japan.
One of the goals in synthetic chemistry is to obtain compounds featuring unusual valence states that are stable under ambient conditions. At present, stabilizing unusual Pt(III) states is considered difficult, except through direct Pt-Pt bonding such as that in platinum-blues or organometallization using bulky ligands. Pt(III) stabilization is also very difficult in halogen-bridged metal complex chains (MX-Chains).
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