Substituent effect on inter-ring interaction in paracyclophanes

Mol Divers. 2020 Feb;24(1):11-20. doi: 10.1007/s11030-019-09926-7. Epub 2019 Feb 19.

Abstract

The theoretical calculations, namely multipole-derived charge analysis, quantum theory of atom in molecules, and non-bonding interaction (NCI), were performed for [2.2]paracyclophanes, [2.2]paracyclophane-7,9-dienes, and [3.3]paracyclophanes optimized at B3LYP/6-311++G** level, including dispersion correction. The substituent effect of the electron donor N(Me)2 and electron acceptor NO2 group and the influence of the length of bridges joining the aromatic ring on aromatic ring interaction energy (AIE) and strain energy were discussed. The local and electrostatic character of the substituent effect in paracyclophanes was shown. The presence of the weak orbital through-space C···C interaction between the [3.3]paracyclophane ring and weak CH···O hydrogen bonds between the substituents in the different rings was shown.

Keywords: AIE; NCI; SE; [2.2]Paracyclophane; [2.2]Paracyclophane-7,9-dienes; [3.3]Paracyclophanes QTAIM.

MeSH terms

  • Animals
  • Ethers, Cyclic / chemistry*
  • Models, Molecular*
  • Molecular Structure
  • Piperidines / chemistry*

Substances

  • Ethers, Cyclic
  • Piperidines