Unraveling the Photophysical Characteristics, Aromaticity, and Stability of π–Extended Acene‐Quinodimethyl Thioamides†

Local pro-aromaticity in acene thioamides chromophores is conducive to triplet photochemistry. However, additional aromatic sextet(s) on the π-core of these chromophores would affect their photostability and photochemistry.

Abstract

Poly-aromatic systems that contain quinodimethyl (QDM) units are appealing for several photonic and spintronic applications owing to the unique electronic structure, aromaticity, and spin state(s) of the QDM ring. Herein, we report the synthesis and characterization of novel QDM-based chromophores 1–3, which exhibit unique photo-excited behavior and aromaticity. Extending the aromatic core with a biphenyl/phenanthryl- and a pyrrolo-fragment led to reducing the optoelectronic bandgap and modulating the photophysics QDM 1–3. Yet, QDM 2 and 3 suffer from “aromaticity imbalance” and become relatively unstable compared to the parent compound QDM 1. Further assessment of local aromaticity using computational tools revealed that the pseudo-quinoidal ring B is the main driving force allowing to easily populate the excited triplet state of these chromophores. The present study provides complementary guidelines for designing novel non-classical poly-aromatic systems.

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