Abstract: | The polycondensation of a dihydrazino‐pyrimidine ( 5 and 6 ) with a pyrimidine‐dicarbaldehyde ( 7 and 8b ) provides an efficent access to helical polymeric strands based on the formation of hydrazone connections between the pyrimidine groups. The folding into a helical structure is enforced by the helicity codon defined by the (hydrazone? pyrimidine) sequence. The polymers obtained have been characterized by mass spectrometry, indicating molecular weights up to ca. 12000 Da. Electronic spectra display specific absorption and emission features. These helical polymers present a core diameter of ca. 20 Å, a pitch of 3.5 Å, and, for a molecular weight around 9000 Da, a height of ca. 42 Å with 12 turns. The self‐assembled helical polymers obtained represent stable frameworks for the lateral attachment of functional residues in a helical disposition. Such entities may possess a range of novel chemical as well as biological properties. |