Solution Processable Benzooxadiazole and Benzothiadiazole Based D‑A‑D Molecules with Chalcogenophene: Field Effect Transistor Study and Structure Property Relationship

Abstract

We present here the physicochemical characterization of a series of D-A-D type molecules which comprise benzooxadiazole (BDO) and benzothiadiazole (BDT) core symmetrically linked to two aromatic-heterols (furan (F), thiophene (T) and selenophene (Se)) at 4 and 7-positions. The molecular structures of four compounds <b>2</b> (T-BDO-T), <b>3</b> (Se-BDO-Se), <b>5</b> (T-BDT-T), and <b>6</b> (Se-BDT-Se) were determined by single-crystal X-ray diffraction. The combination of chalcogen atoms of benzochalcogenadiazole and chalcogenophene in D-A-D molecules has significant impact on their molecular packing in crystal structures. Structural analyses and theoretical calculations showed that all the molecules are nearly planar. Crystal structures of <b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b> showed significant short range interactions such as π···π, CH···π, S···π, Se···π, N···H, O···H, S···H, Se···H, S···O, and Se···N interactions, which influence crystal packing and orientation of the capped aromatic-heterol rings with respect to the central BDO or BDT unit. The π-stacking interactions have been observed via intermolecular overlap of the donor with acceptor units of the adjacent molecules which facilitate the charge transport process. Good thermal stability and solubility in common organic solvents make them good candidate for flexible electronics. Interestingly, the molecules <b>2</b>, <b>3</b>, and <b>6</b> have the propensity to form ordered crystallites when sheared during the drying process in the thin films. Devices based on these solution processable all organic FETs demonstrated hole mobility as high as 0.08 cm² V^–1 s^–1 and <i>I</i>_on/<i>I</i>_off ratio of 10⁴