Chemical Stabilities of the Lowest Triplet State in Aryl Sulfones and Aryl Phosphine Oxides Relevant to OLED Applications

Huifang Li, Minki Hong, Annabelle Scarpaci, Xuyang He, Chad Risko, John S. Sears, Stephen Barlow, Paul Winget, Seth R. Marder*, Dongwook Kim, Jean Luc Brédas

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations


Aryl sulfones and phosphine oxides are widely used as molecular building blocks for host materials in the emissive layers of organic light-emitting diodes. In this context, the chemical stability of such molecules in the triplet state is of paramount concern to long-term device performance. Here, we explore the triplet excited-state (T 1 ) chemical stabilities of aryl sulfonyl and aryl phosphoryl molecules by means of UV absorption spectroscopy and density functional theory calculations. Both the sulfur-carbon bonds of the aryl sulfonyl molecules and the phosphorus-carbon bonds of aryl phosphoryl derivatives are significantly more vulnerable to dissociation in the T 1 state when compared to the ground (S 0 ) state. Although the vertical S 0 ? T 1 transitions correspond to nonbonding ? ?-orbital transitions, geometry relaxations in the T 1 state lead to σ-σ∗ character over the respective sulfur-carbon or phosphorus-carbon bond, a result of significant electronic state mixing, which facilitates bond dissociation. Both the activation energy for bond dissociation and the bond dissociation energy in the T 1 state are found to vary linearly with the adiabatic T 1 -state energy. Specifically, as T 1 becomes more energetically stable, the activation energy becomes larger, and dissociation becomes less likely, that is, more endothermic or less exothermic. While substitutions of electron-donating or -accepting units onto the aryl sulfones and aryl phosphine oxides have only marginal influence on the dissociation reactions, extension of the ?-conjugation of the aryl groups leads to a significant reduction in the triplet energy and a considerable enhancement in the T 1 -state chemical stabilities.

Original languageEnglish (US)
Pages (from-to)1507-1519
Number of pages13
JournalChemistry of Materials
Issue number5
StatePublished - Mar 12 2019

Bibliographical note

Publisher Copyright:
© 2019 American Chemical Society.

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry


Dive into the research topics of 'Chemical Stabilities of the Lowest Triplet State in Aryl Sulfones and Aryl Phosphine Oxides Relevant to OLED Applications'. Together they form a unique fingerprint.

Cite this