Mapping the modification of ring currents induced by cyclopentafusion on a naphthalene core

P. W. Fowler*, E. Steiner, A. Acocella, L. W. Jenneskens, R. W.A. Havenith

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

34 Citations (Scopus)

Abstract

An analysis of the σ-, π- and total current density maps, calculated using a distributed-origin coupled Hartree-Fock method, of the non-alternant cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAH) acenaphthylene (1), pyracylene (2), fluoranthene (3) and cyclopenta[cd]fluoranthene (4) shows that, whereas the presence of a single pentagon in 1 and 3 has only minor effects on the core naphthalene unit, the strong cooperative effect of the two pentagons connected by a formal double bond in 2 and 4 results in intense paratropic currents in the pentagons, and markedly reduced aromaticity according to conventional criteria. The accuracy of the all-electron maps is supported by calculation of 1H and 13C NMR chemical shifts in agreement with experiment and their interpretation is consistent with nucleus-independent chemical shifts (NICS values). It is shown that the pattern of paratropic contributions can be explained qualitatively within Hückel-London π-electron theory.

Original languageEnglish
Pages (from-to)1058-1065
Number of pages8
JournalJournal of the Chemical Society, Perkin Transactions 2
Volume2
Issue number7
DOIs
Publication statusPublished - 2001
Externally publishedYes

Fingerprint

Dive into the research topics of 'Mapping the modification of ring currents induced by cyclopentafusion on a naphthalene core'. Together they form a unique fingerprint.

Cite this