A Solution‐Processable <i>meso</i>‐Phenyl‐BODIPY‐Based <i>n</i>‐Channel Semiconductor with Enhanced Fluorescence Emission

Abstract

The molecular design, synthesis, and characterization of an acceptor-donor-acceptor (A-D-A) semiconductor BDY-Ph-2T-Ph-BDY comprising a central phenyl-bithiophene-phenyl π-donor and BODIPY π-acceptor end-units is reported. The semiconductor shows an optical band gap of 2.32 eV with a highly stabilized HOMO/LUMO (-5.74 eV/-3.42 eV). Single-crystal X-ray diffraction (XRD) reveals D-A dihedral angle of ca. 66° and strong intermolecular "C-H ⋅⋅⋅ π (3.31 Å)" interactions. Reduced π-donor strength, increased D-A dihedral angle, and restricted intramolecular D-A rotations allows for both good fluorescence efficiency (Φ_F =0.30) and n-channel OFET transport (μ_e =0.005 cm² /V ⋅ s; I_on /I_off =10⁴ -10⁵ ). This indicates a much improved (6-fold) fluorescence quantum yield compared to the meso-thienyl BODIPY semiconductor BDY-4T-BDY. Photophysical studies reveal important transitions between locally excited (LE) and twisted intramolecular charge-transfer (TICT) states in solution and the solid state, which could be controlled by solvent polarity and nano-aggregation. This is the first report of such high emissive characteristics for a BODIPY-based n-channel semiconductor.