Modulation of π-stacking modes and photophysical properties of an organic semiconductor through isosteric cocrystallization

Gonzalo Campillo-Alvarado; Michael Bernhardt; Daniel W Davies; Julio A N T Soares; Toby J Woods; Ying Diao

doi:10.1063/5.0059770

Modulation of π-stacking modes and photophysical properties of an organic semiconductor through isosteric cocrystallization

J Chem Phys. 2021 Aug 21;155(7):071102. doi: 10.1063/5.0059770.

Authors

Gonzalo Campillo-Alvarado¹, Michael Bernhardt¹, Daniel W Davies¹, Julio A N T Soares², Toby J Woods³, Ying Diao¹

Affiliations

¹ Department of Chemical and Biomolecular Engineering, University of Illinois Urbana-Champaign, 600 S. Mathews Avenue, Urbana, Illinois 61801, USA.
² Frederick Seitz Materials Research Laboratories Central Facilities, University of Illinois Urbana-Champaign, 104 South Goodwin Avenue, Urbana, Illinois 61801, USA.
³ School of Chemical Sciences, University of Illinois Urbana-Champaign, 505 S. Mathews Avenue, Urbana, Illinois 61801, USA.

PMID: 34418924
DOI: 10.1063/5.0059770

Abstract

We report on the control of π-stacking modes (herringbone vs slipped-stack) and photophysical properties of 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene (BP4VA), an anthracene-based organic semiconductor (OSC), by isosteric cocrystallization (i.e., the replacement of one functional group in a coformer with another of "similar" electronic structure) with 2,4,6-trihalophenols (3X-ph-OH, where X = Cl, Br, and I). Specifically, BP4VA organizes as slipped-stacks when cocrystallized with 3Cl-ph-OH and 3Br-ph-OH, while cocrystallization with 3I-ph-OH results in a herringbone mode. The photoluminescence and molecular frontier orbital energy levels of BP4VA were effectively modulated by the presence of 3X-ph-OH through cocrystallization. We envisage that the cocrystallization of OSCs with minimal changes in cocrystal formers can provide access to convenient structural and property diversification for advanced single-crystal electronics.