Effect of appended porphyrin in poly(fluorene-alt-benzothiadiazole): synthesis, characterization, physico-chemical and electrochemical studies

Poly(fluorene-alt-benzothiadiazole) having 5 and 10% equivalent meso-tetraphenylporphyrin (m-MTPCC) linked through oxyethylene spacer in carbazole (P2, P3) and the parent poly(9,9-di-hexylfluorene-alt-2,1,3-benzothiadiazole) (P1) were synthesized using Suzuki polymerization reaction. These polymers were characterized using FT-IR, H-1 NMR, TGA and gel permeation chromatography. The synthesized polymers are soluble in common organic solvents and are found to be thermally stable. Weight average molecular weights of the polymers were 51.895, 71.224 and 34.789 kDa for P1, P2 and P3, respectively. These copolymers (P2 and P3) shows absorption maxima at around 320, 422, 452 nm and emission maxima at 540 nm in solution, whereas in film state, these polymers (P2 and P3) shows absorption maxima at around 322, 422, 466 and 554 nm and emission at around 539, 654 and 718 nm. The photoluminescence emission at 648 and 720 nm when excited at 320 nm shows that energy transfer from polymer backbone to porphyrin. Surface morphology, optical absorption and emission properties of these polymers with PCBM were also studied. Electrochemical characterization of these polymers shows deep HOMO levels for P2 and P3 when compared with parent polymer and the details are reported.