Bridging Aromatic/Antiaromatic Units: Recent Advances in Aromaticity and Antiaromaticity in Main‐Group and Transition‐Metal Clusters from Bonding and Magnetic Analyses

Abstract

Synthetic exploration and theoretical characterization of metal clusters are actively developing branches of modern inorganic chemistry. Advances in these areas constantly expand the rich structural diversity of viable species, allowing a detailed study of the fundamental characteristics of bench‐stable compounds. In this minireview, we summarize recent achievements in synthesis and computational analyses of main‐group and heterometallic clusters containing multiple aromatic/antiaromatic units. These systems range from bare clusters to ligand‐decorated aggregates, providing a fundamental understanding of the aromaticity and antiaromaticity concepts in species exhibiting unprecedented shapes and composition. The review gives a comprehensive summary of bonding and magnetic response properties of such systems deciphered from the Adaptive Natural Density Partitioning (AdNDP) approach and induced magnetic field analyses.

Local and global aromaticity under rotation: analysis of two- and three-dimensional representative carbon nanostructures

“…This observation is in line with other spherical aromatic species. [81][82][83][84][85][86] From 01 to 901, the shielding cone characteristics remain similar owing to the At the C 60 12À charge state, a spherical antiaromatic cage is achieved, 87 which consequently denotes a central deshielding region complemented by a shielding contour. Analysis of the contribution from both p-electron and s + core kernels (Fig.…”

Spherical Aromaticity of Tetrahedral Pnictogens Through Off‐Nucleus Isotropic Magnetic Shielding

“…[29] The molecular magnetic responses allowed studying the spherical aromaticity of molecules like the main-group and heterometallic clusters. [30] For instance, the magnetic responses effectively uncovered the aromatic features of the first multilayered spherical aromatic example of the [Sn@Cu 12 @Sn 20 ] 12À cluster. [31] Moreover, the magnetic field of specified orientations evidenced the existence of shielding cones as an aromatic feature of spherical C 20 À C 60 aromatics.…”

“…The molecular magnetic responses allowed studying the spherical aromaticity of molecules like the main‐group and heterometallic clusters [30] . For instance, the magnetic responses effectively uncovered the aromatic features of the first multilayered spherical aromatic example of the [Sn@Cu 12 @Sn 20 ] 12− cluster [31] .…”

Switch from local to global aromatic character in Möbius carbon nanobelts upon dioxidation. Evaluation of magnetic behavior in neutral and charged species

“…36,54,63,64 For planar aromatic rings, the shielding cone property is enabled under a perpendicular external field as a long-ranged shielding region along the ring axis, 36,39–42,65 complemented by a deshielding region contained at the molecular contour, which is also extended to spherical aromatic species. 66…”

“…36,54,63,64 For planar aromatic rings, the shielding cone property is enabled under a perpendicular external field as a long-ranged shielding region along the ring axis, 36,[39][40][41][42]65 complemented by a deshielding region contained at the molecular contour, which is also extended to spherical aromatic species. 66 For a field oriented along the x-axis (B x ext ), a cumulative overlap is observed between consecutive shielding cones from perpendicular rings in relation to the x-axis. 63 Similar results are obtained for B y ext .…”