Symmetry collapse due to the presence of multiple local aromaticity in Ge244−

Abstract

Understanding the structural changes taking place during the assembly of single atoms leading to the formation of atomic clusters and bulk materials remains challenging. The isolation and theoretical characterization of medium-sized clusters can shed light on the processes that occur during the transition to a solid-state structure. In this work, we synthesize and isolate a continuous 24-atom cluster Ge244−, which is characterized by X-ray diffraction analysis and Energy-dispersive X-ray spectroscopy, showing an elongated structural characteristic. Theoretical analysis reveals that electron delocalization plays a vital role in the formation and stabilization of the prolate cluster. In contrast with carbon atoms, 4 s orbitals of Ge-atoms do not easily hybridize with 4p orbitals and s-type lone-pairs can be localized with high occupancy. Thus, there are not enough electrons to form a stable symmetrical fullerene-like structure such as C24 fullerene. Three aromatic units with two [Ge9] and one [Ge6] species, connected by classical 2c-2e Ge-Ge σ-bonds, are aligned together forming three independent shielding cones and eventually causing a collapse of the global symmetry of the Ge244− cluster.

Unraveling the flexible aromaticity of C13H9+/0/−: a 2D superatomic-molecule theory

“…Generally, when referring to a polycyclic aromatic hydrocarbon, we first seek to clarify if it features aromaticity [11][12][13][14][15][16] because aromatic compounds usually take on specific chemical and structural stability. In fact, the aromaticity of the phenalenyl cation, neutral radical and anion has been studied extensively at different theoretical levels.…”

Tinning the carbon: hydrostannanes strike back

“…52 The Adaptive Natural Density Partitioning 53 (AdNDP) algorithm, as implemented in the AdNDP 2.0 code, 54 was used to analyse the chemical bonding pattern of the undissociated structures. The AdNDP is a powerful tool that is capable of deciphering the chemical bonding pattern not only for molecules, but also for highly charged Zintl clusters 55,56 and solidstate materials. [57][58][59] The density matrices in the natural atomic orbitals' basis set used for the AdNDP were obtained at the U-M06-2X/def2-TZVPP level of theory 19,32 using NBO 7.0 software.…”

Photoelectron Spectroscopy and Theoretical Studies of Ge6MnO– Cluster with a MnV≡O Unit Interacting with a Double Aromatic Ge64– Ligand

“…Ge 6 10– was discovered in Ba 4 Li 2 Ge 6 which contains 10 π electrons . A prolate Ge 24 4– cluster was characterized by X-ray spectroscopy and analyzed with theoretical methods . A central bowl-shaped aromatic Ge 6 fragment played an important role in connecting the two aromatic [Ge 9 ] units in Ge 24 4– .…”