Ayer, Mathieu A. Simon, Yoan C. Weder, Christoph 2016 Molecules comprising aliphatic azo moieties are widely used as radical polymerization initiators, but only a few studies have explored their usefulness as stimuli-responsive motifs in macromolecular constructs. The controlled degradation of azo-containing polymers has indeed remained largely unexplored. Here we present the syntheses of linear azo-containing polyamides and polyurethanes and report on their thermally and optically induced responses in solution and the solid state. We show that the stimuli- induced degradation behavior depends strongly on the nature of the polymer backbone, the state of matter, and in solution, on the nature of the solvent. The stimuli-responsive solid-state properties of the azo-containing materials may be particularly useful. In the case of the polyurethanes studied here, temperature- or light-induced cleavage of the azo motifs led to a controllable decrease in the molecular weight, which, in turn, caused a reduction of the elongation at break, modulus, and strength. The controlled degradation of the polymer in well-defined areas can be readily achieved via photopatterning, and this approach was shown to be useful to produce solid structures with graded mechanical properties. application/pdf https://folia.unifr.ch/global/documents/305643 https://folia.unifr.ch/documents/305643/files/Weder2016Macromolecules.pdf https://folia.unifr.ch/documents/305643/files/Weder2016Macromolecules_SI.pdf eng info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.macromol.6b00418 info:eu-repo/semantics/openAccess License undefined Macromolecules. - 2016, vol. 49, p. 2917–2927 info:eu-repo/classification/udc/54 Azo-Containing Polymers with Degradation On-Demand Feature http://purl.org/coar/resource_type/c_6501