Poly(3‐docosoxy‐4‐methylthiophene) (PDMT) was synthesized and investigated. PDMT can form a mesophase by rapid quenching from the isotropic melt. Variable‐ temperature reflection and fluorescence spectroscopy of thin films and differential scanning calorimetry were used to study the thermal behavior of PDMT. PDMT shows a two‐ step thermochromic transition from the mesophase, and endotherms in the thermograms could be assigned to melting of each phase. A comparison to with related poly(3‐alkylthiophene)s suggests that the mechanism of the thermochromic transition is very similar.
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