Substituent effects on the electronic characteristics of pentacene derivatives for organic electronic devices: Dioxolane-substituted pentacene derivatives with triisopropylsilylethynyl functional groups

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

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The intramolecular electronic structures and intermolecular electronic interactions of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene), 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m] -pentacene (TP-5 pentacene), and 2,2,10,10-tetraethyl-6,14-bis- (triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5 pentacene) have been investigated by the combination of gas-phase and solid-phase photoelectron spectroscopy measurements. Further insight has been provided by electrochemical measurements in solution, and the principles that emerge are supported by electronic structure calculations. The measurements show that the energies of electron transfer such as the reorganization energies, ionization energies, charge-injection barriers, polarization energies, and HOMO-LUMO energy gaps are strongly dependent on the particular functionalization of the pentacene core. The ionization energy trends as a function of the substitution observed for molecules in the gas phase are not reproduced in measurements of the molecules in the condensed phase due to polarization effects in the solid. The electronic behavior of these materials is impacted less by the direct substituent electronic effects on the individual molecules than by the indirect consequences of substituent effects on the intermolecular interactions. The ionization energies as a function of film thickness give information on the relative electrical conductivity of the films, and all three molecules show different material behavior. The stronger intermolecular interactions in TP-5 pentacene films lead to better charge transfer properties versus those in TIPS pentacene films, and EtTP-5 pentacene films have very weak intermolecular interactions and the poorest charge transfer properties of these molecules.

Original languageEnglish (US)
Pages (from-to)14185-14194
Number of pages10
JournalJournal of the American Chemical Society
Volume134
Issue number34
DOIs
StatePublished - Aug 29 2012

Fingerprint

Functional groups
Ionization potential
Derivatives
Equipment and Supplies
Molecules
Thymopentin
Electronic structure
Charge transfer
Polarization
Gases
Charge injection
Photoelectron Spectroscopy
Photoelectron spectroscopy
Electric Conductivity
Energy Transfer
Film thickness
Energy gap
Substitution reactions
formal glycol
pentacene

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Substituent effects on the electronic characteristics of pentacene derivatives for organic electronic devices : Dioxolane-substituted pentacene derivatives with triisopropylsilylethynyl functional groups. / Griffith, Olga Lobanova; Anthony, John E.; Jones, Adolphus G.; Shu, Ying; Lichtenberger, Dennis L.

In: Journal of the American Chemical Society, Vol. 134, No. 34, 29.08.2012, p. 14185-14194.

Research output: Contribution to journalArticle

@article{fe18cbec031141fbb3e0f47d0dcc996c,
title = "Substituent effects on the electronic characteristics of pentacene derivatives for organic electronic devices: Dioxolane-substituted pentacene derivatives with triisopropylsilylethynyl functional groups",
abstract = "The intramolecular electronic structures and intermolecular electronic interactions of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene), 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m] -pentacene (TP-5 pentacene), and 2,2,10,10-tetraethyl-6,14-bis- (triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5 pentacene) have been investigated by the combination of gas-phase and solid-phase photoelectron spectroscopy measurements. Further insight has been provided by electrochemical measurements in solution, and the principles that emerge are supported by electronic structure calculations. The measurements show that the energies of electron transfer such as the reorganization energies, ionization energies, charge-injection barriers, polarization energies, and HOMO-LUMO energy gaps are strongly dependent on the particular functionalization of the pentacene core. The ionization energy trends as a function of the substitution observed for molecules in the gas phase are not reproduced in measurements of the molecules in the condensed phase due to polarization effects in the solid. The electronic behavior of these materials is impacted less by the direct substituent electronic effects on the individual molecules than by the indirect consequences of substituent effects on the intermolecular interactions. The ionization energies as a function of film thickness give information on the relative electrical conductivity of the films, and all three molecules show different material behavior. The stronger intermolecular interactions in TP-5 pentacene films lead to better charge transfer properties versus those in TIPS pentacene films, and EtTP-5 pentacene films have very weak intermolecular interactions and the poorest charge transfer properties of these molecules.",
author = "Griffith, {Olga Lobanova} and Anthony, {John E.} and Jones, {Adolphus G.} and Ying Shu and Lichtenberger, {Dennis L}",
year = "2012",
month = "8",
day = "29",
doi = "10.1021/ja3056672",
language = "English (US)",
volume = "134",
pages = "14185--14194",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "34",

}

TY - JOUR

T1 - Substituent effects on the electronic characteristics of pentacene derivatives for organic electronic devices

T2 - Dioxolane-substituted pentacene derivatives with triisopropylsilylethynyl functional groups

AU - Griffith, Olga Lobanova

AU - Anthony, John E.

AU - Jones, Adolphus G.

AU - Shu, Ying

AU - Lichtenberger, Dennis L

PY - 2012/8/29

Y1 - 2012/8/29

N2 - The intramolecular electronic structures and intermolecular electronic interactions of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene), 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m] -pentacene (TP-5 pentacene), and 2,2,10,10-tetraethyl-6,14-bis- (triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5 pentacene) have been investigated by the combination of gas-phase and solid-phase photoelectron spectroscopy measurements. Further insight has been provided by electrochemical measurements in solution, and the principles that emerge are supported by electronic structure calculations. The measurements show that the energies of electron transfer such as the reorganization energies, ionization energies, charge-injection barriers, polarization energies, and HOMO-LUMO energy gaps are strongly dependent on the particular functionalization of the pentacene core. The ionization energy trends as a function of the substitution observed for molecules in the gas phase are not reproduced in measurements of the molecules in the condensed phase due to polarization effects in the solid. The electronic behavior of these materials is impacted less by the direct substituent electronic effects on the individual molecules than by the indirect consequences of substituent effects on the intermolecular interactions. The ionization energies as a function of film thickness give information on the relative electrical conductivity of the films, and all three molecules show different material behavior. The stronger intermolecular interactions in TP-5 pentacene films lead to better charge transfer properties versus those in TIPS pentacene films, and EtTP-5 pentacene films have very weak intermolecular interactions and the poorest charge transfer properties of these molecules.

AB - The intramolecular electronic structures and intermolecular electronic interactions of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS pentacene), 6,14-bis-(triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m] -pentacene (TP-5 pentacene), and 2,2,10,10-tetraethyl-6,14-bis- (triisopropylsilylethynyl)-1,3,9,11-tetraoxa-dicyclopenta[b,m]pentacene (EtTP-5 pentacene) have been investigated by the combination of gas-phase and solid-phase photoelectron spectroscopy measurements. Further insight has been provided by electrochemical measurements in solution, and the principles that emerge are supported by electronic structure calculations. The measurements show that the energies of electron transfer such as the reorganization energies, ionization energies, charge-injection barriers, polarization energies, and HOMO-LUMO energy gaps are strongly dependent on the particular functionalization of the pentacene core. The ionization energy trends as a function of the substitution observed for molecules in the gas phase are not reproduced in measurements of the molecules in the condensed phase due to polarization effects in the solid. The electronic behavior of these materials is impacted less by the direct substituent electronic effects on the individual molecules than by the indirect consequences of substituent effects on the intermolecular interactions. The ionization energies as a function of film thickness give information on the relative electrical conductivity of the films, and all three molecules show different material behavior. The stronger intermolecular interactions in TP-5 pentacene films lead to better charge transfer properties versus those in TIPS pentacene films, and EtTP-5 pentacene films have very weak intermolecular interactions and the poorest charge transfer properties of these molecules.

UR - http://www.scopus.com/inward/record.url?scp=84865614116&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84865614116&partnerID=8YFLogxK

U2 - 10.1021/ja3056672

DO - 10.1021/ja3056672

M3 - Article

C2 - 22867002

AN - SCOPUS:84865614116

VL - 134

SP - 14185

EP - 14194

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 34

ER -