Aromatic amines: A comparison of electron-donor strengths

Ohyun Kwon, Stephen Barlow, Susan A. Odom, Luca Beverina, Natalie J. Thompson, Egbert Zojer, Jean-Luc Bredas, Seth R. Marder*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

110 Scopus citations

Abstract

The electron-donor abilities of ten aminophenyl systems and an additional aminothienyl system are compared using density functional theory calculations. The systems studied here include those with amine nitrogen atoms bearing alkyl or aryl groups and those with amine nitrogen atoms as part of a heterocycle. Their abilities to act as donors in electron-transfer processes are assessed from calculated vertical ionization potentials for the aminobenzenes, which are in good agreement with available experimental data. Their abilities to act as intramolecular π-electron donors in conjugated systems are inferred from the bond lengths and charge densities calculated for the corresponding 4-aminobenzaldehydes and 4-aminobenzonitriles. The computed 13C NMR chemical shifts for the 4-aminobenzaldehydes and 4-aminobenzonitriles are in good agreement with published and new experimental data. The chemical shifts correlate well with the computed charge densities and can, to some extent, be used as an experimental probe of π-donor strength. We find that the electron-transferdonor strengths do not correlate well with π-donor strengths: these differences can largely be attributed to steric effects.

Original languageEnglish (US)
Pages (from-to)9346-9352
Number of pages7
JournalJournal of Physical Chemistry A
Volume109
Issue number41
DOIs
StatePublished - Oct 20 2005

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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