Fluorene–Carbazole-Based Porous Polymers by Photoinduced Electron Transfer Reactions

A new photoinitiating system for the metal-free preparation of conjugated microporous polymers (CMPs) is reported. In this approach, irradiation of solutions containing an electroactive monomer, possessing both carbazole and fluorene units, 9,9′-(9,9-dihexyl-9H-fluorene-2,7-diyl)bis-9H-carbazole (CFD), and the iodonium salt (Ph2I+PF6–) as the oxidizing agent resulted in the formation of CMPs. Photoinduced step-growth polymerization proceeded through the successive electron transfer between the excited CFD and iodonium salt, proton release, and coupling reactions. The polymers formed were characterized by FT-IR and 1H NMR analyses. The electrochemical and optical properties of CMPs before and after the dedoping process were evaluated by cyclic voltammetry, differential pulse voltammetry, and UV–vis absorption and photoluminescence techniques. The porous structure of the obtained polymers was confirmed by atomic force microscopy and scanning electron microscopy studies.