The high design flexibility of organic semiconductors should lead to diverse and complex electronic functions. However, currently available high-performance organic semiconductors are limited in variety; most of p-type materials are based on thienoacenes or related one-dimensionally (1D) extended π-conjugated systems. In an effort to expand the diversity of organic semiconductors, we are working on the development of tetrabenzoporphyrin (BP) derivatives as active-layer components of organic electronic devices. BP is characterized by its large, rigid two-dimensionally (2D) extended π-framework with high light absorptivity and therefore is promising as a core building unit of organic semiconductors for optoelectronic applications. Herein, we demonstrate that BP derivatives can afford field-effect hole mobilities of >4 cm2 V-1 s-1 upon careful tuning of substituents. Comparative analysis of a series of 5,15-bis(n-alkyldimethylsilylethynyl)tetrabenzoporphyrins reveals that linear alkyl substituents disrupt the π-π stacking of BP cores, unlike the widely observed "fastener effect" for 1D extended π-systems. The n-octyl and n-dodecyl groups have the best balance between high solution processability and minimal π-π stacking disruption, leading to superior hole mobilities in solution-processed thin films. The resulting thin films show high thermal stability wherein the field-effect hole mobility stays above 1 cm2 V-1 s-1 even after heating at 160 °C in air, reflecting the tight packing of large BP units. These findings will serve as a good basis for extracting the full potential of 2D extended π-frameworks and thus for increasing the structural or functional diversities of high-performance organic semiconductors.
Keywords: molecular packing; organic semiconductors; organic transistors; substituent engineering; tetrabenzoporphyrin.