Ternary CBe4Au4 cluster: a 16-electron system with quasi-planar tetracoordinate carbon

• Published in: Physical chemistry chemical physics : PCCP Vol. 20; no. 9; pp. 6299 - 6306
• Main Authors: Guo, Jin-Chang, Feng, Lin-Yan, Zhai, Hua-Jin
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 2018
• Subjects: Aromaticity; Carbon; Chemical bonds; Clusters; Electron affinity; Electrons; Isomers; Molecular orbitals
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/c7cp08420j

Planar hypercoordinate carbons as exotic chemical species are dominated by 18-electron counting. We report herein a 16-electron planar tetracoordinate carbon (ptC) cluster, CBe4Au4, which is quasi-planar to be exact, being composed of a C center, a square-planar Be4 ring, and four outer Au bridges. The quasi-ptC cluster is established as a global minimum via computer structural searches, located 14.6 kcal mol−1 below the nearest competitor at the CCSD(T) level. It shows thermodynamic and electronic robustness, with a low electron affinity (1.54 eV at B3LYP) and a large HOMO–LUMO gap (2.21 eV for excitation energy). Bonding analyses reveal 2π and 6σ double aromaticity, in addition to four three-center two-electron (3c-2e) Be–Au–Be σ bonds, confirming that 16-electron counting is perfect for the system. We believe that double (π and σ) aromaticity is a general concept that governs planar or quasi-planar carbons, which overrides the 18-electron rule. Competition between quasi-ptC and tetrahedral carbon (thC) isomers in the CBe4M4 (M = K, Au, H, Cl) series is also examined, which sheds crucial light on factors that govern the ptC clusters. The present findings offer opportunities for further planar and unconventional molecules.