One-Step Sixfold Cyanation of Benzothiadiazole Acceptor Units for Air-Stable High-Performance n-Type Organic Field-Effect Transistors.

Reported here is a new high electron affinity acceptor end group for organic semiconductors, 2,1,3-benzothiadiazole-4,5,6-tricarbonitrile (TCNBT). An n-type organic semiconductor with an indacenodithiophene (IDT) core and TCNBT end groups was synthesized by a sixfold nucleophilic substitution with cyanide on a fluorinated precursor, itself prepared by a direct arylation approach. This one-step chemical modification significantly impacted the molecular properties: the fluorinated precursor, TFBT IDT, a poor ambipolar semiconductor, was converted into TCNBT IDT, a good n-type semiconductor. The electron-deficient end group TCNBT dramatically decreased the energy of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO) compared to the fluorinated analogue and improved the molecular orientation when utilized in n-type organic field-effect transistors (OFETs). Solution-processed OFETs based on TCNBT IDT exhibited a charge-carrier mobility of up to μe ≈0.15 cm2  V-1  s-1 with excellent ambient stability for 100 hours, highlighting the benefits of the cyanated end group and the synthetic approach.