Low-Band-Gap BODIPY Conjugated Copolymers for Sensing Volatile Organic Compounds.

Conjugated polymers with strong photophysical properties are used in many applications. A homopolymer (P1) and five new low band gap copolymers based on 4,4'-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) and acceptors 3,6-dithienyldiketopyrrolopyrrole (P2), phthalimide (P3), benzotriazole (P4), 4,7-dithienyl[1,2,3]triazolo[4,5g]quinoxaline (P5), and 2,5-dithienylthieno[3,4-b]pyrazine (P6) were prepared by means of Sonogashira polymerization. The characterization of polymers by using (1) H NMR, absorption, and emission spectroscopy is discussed. All polymers with high molecular weights (Mn ) of 16 000 to 89 000 g mol(-1) showed absorption maxima in the deep-red region (λ=630-760 nm) in solution and exhibited significant redshifts (up to 70 nm) in thin films. Polymers P2, P5, and P6 showed narrow optical band gaps of 1.38, 1.35, and 1.38 eV, respectively, which are significantly lower than that of P1 (1.63 eV). The HOMO and LUMO energy levels of the polymers were calculated by using cyclic voltammetry measurements. The LUMO energy levels of BODIPY-based alternating copolymers were independent of the acceptors; this suggests that the major factor that tunes the LUMO energy levels of the polymers could be the BODIPY core. All polymers showed selective and reproducible detection of volatile organic solvents, such as toluene and benzene, which could be used for developing sensors.