Alvaro Muñoz-Castro
Affiliation: Universidad San Sebastián
Country: Chile
Abstract
The seminal concept of chemical bond¹
dates back more than a century ago, being the central concept in the
formation of molecular structures from individual atoms. Interestingly, such
a notion of a chemical bond involves the interaction between orbitals of
separated nuclei with different origins at a fixed distance. Herein, we
discuss modern aspects of chemical bonding in inorganic systems, opening a
novel notion of the versatility of this concept by introducing the
Concentric Bond along the superatom approach², involving the interaction of
orbitals that remain coincident with a common origin. In addition, the role
of the bond variation at optically excited states as a key factor in
luminescent properties is discussed.
These non-classical features are discussed in ligand-protected gold clusters, which enables a further rationalization of their electronic structures and luminescent properties with successful predictions, which can be employed to envisage molecular materials based on individual building blocks. The intercluster bonding is discussed, involving 1S and 1P superatomic shells and 8- cluster electron centers, is discussed,³ showing single, double, and aromatic bonds, in addition to a hypothetical example for a triple bond and eclipsed- /staggered isomerism.⁴ ⁵ Moreover, bonding in 1D-shell based superatoms is discussed ⁶, featuring multiple 1D≡1D bonding in the Au22 (dppp) cluster⁷, and, analog to the classic Ni(CO)4 18-electron organometallic compound⁸.
In addition, the three-dimensional aggregation of superatoms reveals the possibility of extending the superatom approach to higher-order superatom structures,⁹ enabling further exploration of larger clusters.
Figure 1. Schematic representation of fused polyhedral.
References:
- D. M. P. Mingos, The Chemical Bond I, Springer International Publishing, Cham, 2016, vol. 169.
- T. Tsukuda and H. Häkkinen, Protected Metal Clusters: From Fundamentals to Applications, Elsevier, 2015.
- A. Muñoz-Castro, Chem. Commun., 2019, 55, 7307–7310. 4
- A. Muñoz-Castro, Chem. Sci., 2014, 5, 4749–4754.
- L. G. Perla, A. Muñoz-Castro and S. C. Sevov, J. Am. Chem. Soc., 2017, 139, 15176–15181.
- A. Muñoz-Castro, Phys. Chem. Chem. Phys., 2020, 22, 1422–1426.
- J. Chen, Q.-F. Zhang, T. A. Bonaccorso, P. G. Williard and L.-S. Wang, J. Am. Chem. Soc., 2014, 136, 92–95.
- A. Muñoz-Castro, Zeitschrift für Anorg. und Allg. Chemie, 2021, 647, 1819–1823.
- A. Muñoz-Castro, Dalt. Trans., 2023, 52, 17696–17700.
Bio
Dr. Alvaro Muñoz-Castro, chemist from
Pontificia Universidad Católica de Chile, received his Ph.D. degree in
Molecular Physical-Chemistry at Universidad Andres Bello, Chile, under the
direction of Ramiro Arratia-Pérez in relativistic computational chemistry of
inorganic species. Currently, he is a full-time professor at Universidad San
Sebastián, Chile. His research interests range from molecular clusters and
superatoms, endohedral metallofullerenes, host guest species, and carbon
nanostructures, involving the understanding of magnetic response, optical,
luminescent, electron- delocalization, and structural properties. He is part
of the international advisory editorial board from ChemPhysChem and part of
the LatinXChem initiative. His achievements have been recorded to date in
more than 290 publications and four book chapters, with four supervised
Ph.D. theses, being part of strong national and international
networks.
More info: http://www.amclab.cl