(B3CB3)N2 Monolayer Consisting of CO2‑Type Superatomic Molecules with Sandwich Hexacoordinate Carbons

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-12, Vol.128 (49), p.10579-10586
• Main Authors: Gui, Zaijun, Wang, Zhifang, Guo, Lijiao, Li, Dan, Yuan, Qinqin, Cheng, Longjiu
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c06831

Searching for a useful way to build stable hypercoordinate carbon species is a great way to enrich carbon-based chemical rules. Here, we extend the super valence bond model into superatom–atom superbonding to theoretically predict a two-dimensional (B3CB3)­N2 monolayer, which is the first design of a stable nonplanar hexacoordinate carbon containing material, featuring a sandwich B3CB3 configuration. Chemical bonding analyses indicate that its stability originates from the unique super CO2 structures, where each tricoordinate B3 unit has six delocalized electrons acting as a super oxygen (S2P4), and the B3CB3 unit mimics the bonding pattern of the CO2 molecule via the superatom–atom super double bond. Thus, the (B3CB3)­N2 monolayer can be visualized as an assembly of super CO2 units linked by N atoms. The calculated moderate direct band gap (∼1.71 eV) and high light absorption coefficient of the (B3CB3)­N2 monolayer make it a promising candidate for further applications in electronics and optoelectronics. This work provides a possible pathway to design hypercoordinate carbon materials via superatom–atom cluster assembly, which is expected to be applied across diverse fields.