Laterally π-Extended Tetraazaperylenes: Facile Synthesis, Tunable Optoelectronic Properties, and Organic Field-Effect Transistor Applications.

Tetraazaperylene (TAP)-based polycyclic aromatic hydrocarbons have attracted a considerable amount of interest recently, but the development of efficient synthetic approaches for bay functionalization and modulation of their optoelectronic properties remains a considerable challenge. Herein, by developing a straightforward one-pot strategy utilizing synergistic C-C cross-coupling and C-H activation, a series of novel TAP derivatives with progressively laterally extended π-conjugation were synthesized. With an increase in conjugation length, the compounds exhibit a gradual red-shift in absorption, an increase in molar extinction coefficients, and a reduction of the HOMO-LUMO energy gap. In addition, single-crystal organic field-effect transistors (OFETs) fabricated with TAP-Ph, TAC-DPh, and TAC-DPhe show p-type charge transport behavior, with TAC-DPh achieving a hole mobility of 8.49 × 10-2 cm2 V-1 s-1 due to its more ordered solid-state packing. Our work introduces an efficient synthetic approach toward π-extended TAP derivatives and provides a fundamental understanding of the electronic structures in these π-systems.