“…Although less π-extended C n –BTBTs exhibit good solubility in common organic solvents at room temperature, they possess relatively deep energy levels of the highest occupied molecular orbital (HOMO) as a p-type OSC, often resulting in large operating voltages in field-effect transistors (FETs) with gold and carbon electrodes. Recently, we also developed conceptually new oxygen- and sulfur-bridged V-shaped binaphthalene π-electron cores (π-cores), dinaphtho[2,3- b :2′,3′- d ]furan (DNF–V) and -thiophene (DNT–V) (Figure a). ,− Both V-shaped derivatives showed (1) high chemical stability under ambient conditions due to deep HOMO levels of <−5.0 eV to resist oxidation by ambient O 2 , (2) suitable solubility in common organic solvents owing to their intramolecular dipole moments (Figure b), (3) high thermal stability without any reactive chemical bonds, and (4) charge carrier mobility equal or superior to currently used amorphous silicon semiconductors (0.5–1.0 cm 2 V –1 s –1 ). Comprehensive studies of their decyl-substituted derivatives, 3,9-didecyldinaphtho[2,3- b :2′,3′- d ]furan (C 10 –DNF–VW) and -thiophene (C 10 –DNT–VW), suggested that the central bridging elements and the lateral alkyl side chains conclusively affect their molecular geometries, aggregated structures, and semiconducting properties. ,, Unlike the reported conventional chalcogen-bridged π-cores, V-shaped π-cores form unique bent molecular structures (bent angles between naphthalenes: 3.91–13.9°) in the solid state depending on the bridged elements and substituents (Figure c).…”