Fluxional Behavior and Stability of the Cu2B8- Cluster: A Copper Borozene with a Freely Rotating Cu2 Dimer
Jing-Kai Xu1, Hui-Yu Zhang1, Zhong-Hua Cui1,2
1Institute of Atomic and Molecular Physics, Jilin University, Changchun 130023, China.
Abstract:
We demonstrate that Cu2B8- exhibits distinct fluxional behavior, akin to that of a functional stirrer, with the Cu2 dimer freely rotating on the B8 molecular wheel. This behavior is confirmed by Born-Oppenheimer molecular dynamics simulations. The initiation of this dynamic motion is facilitated by an ultrasoft vibrational mode (less than 10 cm-1), resulting in a negligible rotational barrier of 0.03 kcal/mol, as calculated at the single-point CCSD(T) level. The high stability of Cu2B8- arises from the strong interlayer electrostatic interaction between Cu2 and B8, due to charge transfer from Cu2 to B8, along with additional covalent interactions from the delocalized π electrons of the B8 wheel to the Cu2 dimer. Notably, the Cu2 dimer in Cu2B8- features a two-center one-electron Cu-Cu single bond, while the B82- moiety displays double aromaticity, characterized by the presence of six delocalized π electrons and six delocalized σ electrons.
More Related Videos
06:53Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
08:55Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
Published on: June 7, 2018
Related Concept Videos
02:58Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
03:02Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
02:42Valence Bond Theory
02:46Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
02:30Stability of Substituted Cyclohexanes
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
02:33Lattice Centering and Coordination Number
Types of Unit Cells
Imagine taking a large number of identical...