Design and Functions of Semiconducting Fused Polycyclic Furans for Optoelectronic Applications

Conspectus The fused polycyclic furan structure is a ubiquitous motif in naturally occurring organic compounds. However, they had been rarely seen in the literature of organic electronic research until very recently, probably because of the lack of stability of simple furans under conditions that the compounds experience in the active layer of the device. Nonetheless, from the viewpoint of molecular structure, furans look to have potential merits as organic semiconductors such as thiophenes, which are more popular in the organic electronic area. For example, the small atomic radius and large electronegativity of oxygen will increase intermolecular molecular orbital (MO) overlap and hence facilitate charge transporting ability in the solid state. In this Account, we describe the molecular design and optoelectronic applications of fused polycyclic furans, such as benzodifurans (BDFs), naphthodifurans (NDFs), and anthradifurans (ADFs). The molecular design that was exploited in this study crucially depends on the synthetic flexibility of a “modular” synthetic strategy that we purposely developed and reviewed in a separate report. Our synthetic strategy comprises two steps carried out in situ: cyclization of an o -alkynylphenol into a zincio benzofuran and its electrophilic Negishi-type trapping to obtain a range of multisubstituted fused furan compounds. These compounds are found to possess electronic structures resembling those of fused polyaromatic hydrocarbons, such as acenes or phenacenes, rather than oxygen-bridged phenylenevinylene, along with unique characteristics: a wide HOMO–LUMO gap originating from the weak aromaticity of the furan rings, an intense photoluminescent character, and mechanofluorochromism. Semiconducting properties of fused furans are also excellent among organic materials: some BDF derivatives show high hole mobility on the order of 10 –3 cm 2 /(V s) in the amorphous state using time-of-flight (TOF) technique. The p -type BDFs exhibit high performance as hole-transporting material in heterojunction organic light-emitting diodes (OLEDs), while carbazole-substituted BDFs (CZBDFs) are ambipolar with well-balanced high carrier mobility for both hole and electron and serve as host materials for full-color electroluminescence in both hetero- and homojunction architectures. More π-expanded NDFs showed good crystallinity and are effective active materials for organic field-effect transistors (OFETs) with a high hole mobility of up to 3.6 cm 2 /(V s) using a solution process. These studies have illustrated the high potential of fused polycyclic furans in organic electronics research, which thus far have attracted much less attention than their thiophene congeners.