Synthesis of poly(4-(N-carbazolyl)methyl styrene)s: Tailoring optical properties through stereoregularity

[Display omitted] •Synthesis and characterization of stereoregular poly(4-(N-carbazolyl)methyl styrene)s.•The bulky carbazole groups reduce the conformational freedom of polymer chains.•Polymer tacticity strongly influences the fluorescence emission.•Excimer formation depends on the stereoregularity of polymer chains. The synthesis and the microstructural characterization of highly isotactic poly(4-(N-carbazolyl)methyl styrene) (i-PSK) are reported for the first time. Chemical physic and optical properties of i-PSK and syndiotactic PSK (s-PSK) are compared. Wide-angle X-ray diffraction (WAXD) and thermal (DSC) analysis show that i-PSK is amorphous as well as s-PSK sample. Moreover, FTIR spectra of the achieved stereoisomers, i-PSK and s-PSK, present few differences in accessible conformation distributions of polymer backbone chain. This behavior is likely due to the presence of bulky carbazole groups that reduce the conformational freedom of polymer chains. Fluorescence measurements on i-PSK and s-PSK films indicate that the excimer formation is essentially driven by the polymer tacticity. In detail, i-PSK generates both “sandwich-like” and “partially overlapping” excimers, while s-PSK gives rise only to “partially overlapping” ones.