Abstract Statistical copolymers of indigo (1a) and N-acetylindigo (1b) building blocks with defined structures were studied. They belong to the class of polymeric colorants. The polymers consist of 5, 5′-connected indigo units with keto structure and N-acetylindigo units with uncommon tautomeric indoxyl/indolone (= 1H-indol-3-ol/3H-indol-3-one) structure (see 2a and 2b in Fig. 1). They formed amorphous salts of elongated monomer lengths as ...