Photoinduced step-growth polymerizations of thiophene-carbazole based covalent organic polymer

A novel metal-free photochemical method for the synthesis of porous conjugated polymers was used to inves-tigate the effects of introducing thiophene co-monomer to the carbazole-based polymer, 4,4 '-bis(3,6-di(thiophen-2-yl)-9H-carbazol-9-yl)-1,1 '-biphenyl (CBP-Th), in terms of its structural, optical, electrochemical and morphological properties. Irradiation of a CBP-Th monomer solution led to the formation of a dark-colored polymer, PCBP-Th, and the role of thiophene on polymerization was investigated, involving electron transfer between CBP-Th and the iodonium ion in the exciplex produced by proton release and radical coupling reactions. The UV-Vis spectra broadened and redshifted due to the elongation of conjugation and solid-state pi-pi in-teractions by extra thiophene additive after the polymerization process. The addition of thiophene co-monomer also resulted in decreasing the onset potentials and thus slightly raised HOMO positions determined by the DPV technique. In theoretical calculations, it has been observed that the charge distribution of PCBP-Th at HOMO is over the entire conjugated structure and it has localization in thiophene-thiophene bridges at LUMO. Since the thiophene co-monomer changes the intermolecular distance, the thermal stability of PCBP-Th polymers de-creases and accordingly increases the amorphous characters. According to AFM, TEM and SEM images, intro-ducing the thiophene co-monomer led to the formation of larger clusters, resulting in a more pronounced surface texture on both the powders and thin films.