Theoretical study on conformation and electronic state of Hückel-aromatic multiply N-confused [26]hexaphyrins

Research output: Contribution to journalArticlepeer-review

23 Citations (Scopus)

Abstract

Conformations and electronic states of Hückel-aromatic regular, singly, doubly, and triply N-confused [26]hexaphyrins were investigated using density functional theory (DFT) calculations. A comparison of the molecular energies of 754 structures in all revealed that the most stable conformers depend on the degree of confusion, where ring strain and intramolecular hydrogen bonding would play a critical role. Consequently, regular and singly N-confused hexaphyrins prefer a dumbbell conformation, doubly N-confused hexaphyrin prefers a rectangular conformation, and triply N-confused hexaphyrin prefers a triangular conformation. Introduction of N-confused pyrrole rings into the hexaphyrin framework causes narrower HOMO-LUMO energy gaps, while it does not affect the NICS values or aromaticity significantly. The steric repulsion imposed by meso-aryl substituents largely affects the relative energies among the conformers.

Original languageEnglish
Pages (from-to)8213-8223
Number of pages11
JournalJournal of Organic Chemistry
Volume75
Issue number23
DOIs
Publication statusPublished - Dec 3 2010

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Fingerprint Dive into the research topics of 'Theoretical study on conformation and electronic state of Hückel-aromatic multiply N-confused [26]hexaphyrins'. Together they form a unique fingerprint.

Cite this