Molecular packing-dependent exciton dynamics in functionalized anthradithiophene derivatives: From solutions to crystals

J. D.B. Van Schenck, G. Mayonado, J. E. Anthony, M. W. Graham, O. Ostroverkhova

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


Understanding the impact of inter-molecular orientation on the optical properties of organic semiconductors is important for designing next-generation organic (opto)electronic and photonic devices. However, fundamental aspects of how various features of molecular packing in crystalline systems determine the nature and dynamics of excitons have been a subject of debate. Toward this end, we present a systematic study of how various molecular crystal packing motifs affect the optical properties of a class of high-performance organic semiconductors: functionalized derivatives of fluorinated anthradithiophene. The absorptive and emissive species present in three such derivatives (exhibiting "brickwork,""twisted-columnar,"and "sandwich-herringbone"motifs, controlled by the side group R) were analyzed both in solution and in single crystals, using various modalities of optical and photoluminescence spectroscopy, revealing the nature of these excited states. In solution, in the emission band, two states were identified: A Franck-Condon state present at all concentrations and an excimer that emerged at higher concentrations. In single crystal systems, together with ab initio calculations, it was found in the absorptive band that Frenkel and Charge Transfer (CT) excitons mixed due to nonvanishing CT integrals in all derivatives, but the amount of admixture and exciton delocalization depended on the packing, with the "sandwich-herringbone"packing motif least conducive to delocalization. Three emissive species in the crystal phase were also identified: Frenkel excitons, entangled triplet pairs 1(TT) (which are precursors to forming free triplet states via singlet fission), and self-Trapped excitons (STEs, similar in origin to excimers present in concentrated solution). The "twisted-columnar"packing motif was most conducive to the formation of Frenkel excitons delocalized over 4-7 molecules depending on the temperature. These delocalized Frenkel states were dominant across the full temperature range (78 K-293 K), though at lower temperatures, the entangled triplet states and STEs were present. In the derivative with the "brickwork"packing, all three emissive species were observed across the full temperature range and, most notably, the 1(TT) state was present at room temperature. Finally, the derivative with the "sandwich-herringbone"packing exhibited localized Frenkel excitons and had a strong propensity for self-Trapped exciton formation even at higher temperatures. In this derivative, no formation of the 1(TT) state was observed. The temperature-dependent dynamics of these emissive states are reported, as well as their origin in fundamental inter-molecular interactions.

Original languageEnglish
Article number164715
JournalJournal of Chemical Physics
Issue number16
StatePublished - Oct 28 2020

Bibliographical note

Funding Information:
We thank Professor B. Gibbons, Dr. S. Parkin, and Dr. L. Zakharov for the access to the XRD facilities and single-crystal XRD structure determination. This work was supported by the National Science Foundation (Grant Nos. DMR-1808258 and DMREF-1627428).

Publisher Copyright:
© 2020 Author(s).

ASJC Scopus subject areas

  • Physics and Astronomy (all)
  • Physical and Theoretical Chemistry


Dive into the research topics of 'Molecular packing-dependent exciton dynamics in functionalized anthradithiophene derivatives: From solutions to crystals'. Together they form a unique fingerprint.

Cite this