Intermolecular effects on the hole states of triisopropylsilylethynyl- substituted oligoacenes

Olga Lobanova Griffith, Adolphus G. Jones, John E. Anthony, Dennis L Lichtenberger

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

The effects of intermolecular interactions on the electronic properties of bis-triisopropylsilylethynyl-substituted (TIPS) anthracene, tetracene, and pentacene are obtained from comparison of the ionization energies measured by solid-phase ultraviolet photoelectron spectroscopy (UPS) with the ionization energies measured by gasphase UPS, and with the oxidation potentials measured electrochemically in solution. Additional insight is provided by electronic structure calculations at the density functional theory level. The results show that the solution-phase oxidation potentials correlate linearly with the gas-phase first ionization energies of TIPS oligoacenes, and both energies decrease with the increase in acene core size as expected for the increasing delocalization of the HOMO. However, the solid-phase ionization energies are independent of the acene core size, and thus do not follow the trend indicated by the molecular electronic structures and verified by the gas-phase and solution measurements. The solid-phase electronic properties such as charge injection barriers, ionization energies, and HOMO-LUMO energy gaps are greatly affected by the polarization effects of the surrounding molecules in the solid state, which dominate over the changes in molecular electronic properties caused by the change in acene core size.

Original languageEnglish (US)
Pages (from-to)13838-13845
Number of pages8
JournalJournal of Physical Chemistry C
Volume114
Issue number32
DOIs
StatePublished - Aug 19 2010

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Ionization potential
Electronic properties
Ultraviolet photoelectron spectroscopy
ionization
Molecular electronics
solid phases
molecular electronics
ultraviolet spectroscopy
Electronic structure
Gases
energy
Oxidation
Charge injection
photoelectron spectroscopy
vapor phases
Anthracene
electronic structure
oxidation
Molecular structure
Density functional theory

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Intermolecular effects on the hole states of triisopropylsilylethynyl- substituted oligoacenes. / Griffith, Olga Lobanova; Jones, Adolphus G.; Anthony, John E.; Lichtenberger, Dennis L.

In: Journal of Physical Chemistry C, Vol. 114, No. 32, 19.08.2010, p. 13838-13845.

Research output: Contribution to journalArticle

Griffith, Olga Lobanova ; Jones, Adolphus G. ; Anthony, John E. ; Lichtenberger, Dennis L. / Intermolecular effects on the hole states of triisopropylsilylethynyl- substituted oligoacenes. In: Journal of Physical Chemistry C. 2010 ; Vol. 114, No. 32. pp. 13838-13845.
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