Bonding Character, Electron Delocalization, and Aromaticity of Cyclo[18]Carbon (C ₁₈ ) Precursors, C ₁₈ ‐(CO) _<i>n</i> ( <i>n</i> =6, 4, and 2): Focusing on the Effect of Carbonyl (‐CO) Groups**

Abstract

Abstract The bonding character, electron delocalization, and aromaticity of the cyclo[18]carbon (C 18 ) precursors, C 18 ‐(CO) n ( n =6, 4, and 2), have been studied by combining quantum chemical calculations and various electronic wavefunction analyses with different physical bases. It was found that C 18 ‐(CO) n ( n =6, 4, and 2) molecules exhibit alternating long and short C−C bonds, and have out‐of‐plane and in‐plane dual π systems (π out and π in ) perpendicular to each other, which are consistent with the relevant characteristics of C 18 . However, the presence of carbonyl (‐CO) groups significantly reduced the global electron conjugation of C 18 ‐(CO) n ( n =6, 4, and 2) compared to C 18 . Specifically, the ‐CO group largely breaks the extensive delocalization of π in system, and the π out system is also affected by it but to a much lesser extent; as a consequence, C 18 ‐(CO) n ( n =6, 4, and 2) with larger n shows weaker overall aromaticity. Mostly because of the decreased but still apparent π out electron delocalization in the C 18 ‐(CO) n ( n =6, 4, and 2), a notable diatropic induced ring current under the action of external magnetic field is observed, demonstrating the clear aromatic characteristic in the molecules. The correlation between C 18 ‐(CO) n ( n =6, 4, and 2) and C 18 in terms of the gradual elimination of ‐CO from the precursors showed that the direct elimination of two CO molecules in C 18 ‐(CO) n ( n =6, 4, and 2) has a synergistic mechanism, but it is kinetically infeasible under normal conditions due to the high energy barrier.