A study on the aromatic conjugation pathways and the ring currents of bridged [18]annulenes

Abstract

In this article, the topological resonance energy (TRE) method was used to investigate the global aromaticity of a set of [18]annulene-derived compounds which were obtained by replacing either two, four, or all six of the inner hydrogen atoms of [18]annulene with bridges (oxygen, imino-, sulfur, or combinations of the three). Our TRE results show that all the mono-bridged, di-bridged, and tri-bridged [18]annulenes are globally aromatic systems with positive TREs and show relatively larger aromaticity in comparison with the [18]annulene. The aromaticity of each compound was explained using the topological charge stabilization (TCS) rule. The bond resonance energy (BRE) and circuit resonance energy (CRE) methods were used to evaluate local aromaticity. Our BRE and CRE results show that incorporation of five-membered heterocyclic rings changes the main conjugation pathway of the bridged [18]-annulenes. The local aromaticities arising from the five-membered heterocyclic rings (6π) contribute strongly to global aromaticity. However, the ring current (RC), which arises from the 18π annulene-like pathway structures, is the primary determinant of the magnetic properties of the molecule. Our RC results are in good agreement with available ¹H-NMR chemical shift data.