Dithienoindophenines: p‐Type Semiconductors Designed by Quinoid Stabilization for Solar‐Cell Applications

Compared with the dominant aromatic conjugated materials, photovoltaic applications of their quinoidal counterparts featuring rigid and planar molecular structures have long been unexplored despite their narrow optical bandgaps, large absorption coefficients, and excellent charge‐transport properties. The design and synthesis of dithienoindophenine derivatives (DTIPs) by stabilizing the quinoidal resonance of the parent indophenine framework is reported here. Compared with the ambipolar indophenine derivatives, DTIPs with the fixed molecular configuration are found to be p‐type semiconductors exhibiting excellent unipolar hole mobilities up to 0.22 cm² V^?1 s^?1, which is one order of magnitude higher than that of the parent IP‐O and is even comparable to that of QQT(CN)4‐based single‐crystal field‐effect transistors (FET). DTIPs exhibit better photovoltaic performance than their aromatic bithieno[3,4‐b]thiophene (BTT) counterparts with an optimal power‐conversion efficiency (PCE) of 4.07 %.