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With the aim of finding insights into the as‐yet unclear chemical structure of thianthrenic polymers, a detailed IR analysis on a sample previously prepared by us is reported. The IR spectrum is interpreted mainly by way of two correlated reference units: the unsubstituted thianthrene and the 1,2,4,5‐tetrahalosubstituted benzene. Since a full interpretation of the spectrum of the thianthrene molecule is still lacking, we have tried a first assignment, taking o‐dihalobenzenes as component models. The spectrum of the polymer is found to correlate well with spectra of the reference moieties. Other units, taken into account to get the most reliable picture of the polymeric structure, seem to be present at appreciable concentrations. Our results lead us to propose the existence of regular, fully intramolecularly cyclized thianthrenic segments limited by defective units, mainly 1,2,4‐trithiosubstituted benzene. A narrow peak at 886 cm−1 can be interpreted as a regularity band, supporting the existence of chain segments where the repeat units are correlated by translational symmetry.

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Ladder oligophenothiazines were synthesized by direct catalyzed insertion of elemental sulfur in anilino‐substituted phenothiazines and para‐oligoanilines. The starting 3‐ and 3,7‐anilino derivatives of phenothiazine were prepared with improved selectivities and yields by new syntheses. The oxidability of the oligomers is discussed.