Citation: Quan Zhou, Xiao-Min Chen, Xujie Qin, Zhe-Ning Chen, Jun Chen, Wei Zhuang. The counterintuitive aromaticity of bent metallabenzenes: A theoretical exploration[J]. Chinese Chemical Letters, ;2025, 36(4): 109770. doi: 10.1016/j.cclet.2024.109770 shu

The counterintuitive aromaticity of bent metallabenzenes: A theoretical exploration

Quan Zhou ^{a, b} ,
Xiao-Min Chen ^{a, c} ,
Xujie Qin ^{a, b} ,
Zhe-Ning Chen ^{a, b, d, *,} ,
Jun Chen ^{a, b, d, *,} ,
Wei Zhuang ^{a, b, d, *,}

a.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
College of Chemistry, Fuzhou University, Fuzhou 350108, China
d.
Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen 361005, China

znchen@fjirsm.ac.cn

chenjun@fjirsm.ac.cn

wzhuang@fjirsm.ac.cn

Received Date: 31 December 2023
Revised Date: 18 February 2024
Accepted Date: 14 March 2024
Available Online: 15 March 2024

Figures(6)

Metallabenzenes, a type of aromatic compound that includes metal atoms, have opened up new avenues for creating materials with unique properties. A distinctive feature of metallabenzenes is the significant deviation of their metal atoms from the planar configuration of the C5 ring, a phenomenon that paradoxically enhances their aromatic character. In this investigation, we propose that this counterintuitive increase in aromaticity upon geometric distortion is governed by the interactions of frontier orbitals in the σ-space. This insight not only corroborates the previously suggested role of σ-space orbitals in inducing geometric non-planarity in metallabenzenes but also underscores their pivotal contribution to the compounds' enhanced aromaticity. As a result, this work broadens the scope of the σ-control mechanism, highlighting its usefulness for the rational design of functional metalla-aromatic materials.
- Metallabenzenes,
- Metalla-aromaticity,
- σ-Control,
- NICS,
- Functional materials
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