Advanced functional polymeric materials based on spiropyrans (SPs) feature multi-stimuli responsive characteristics, such as a change in color with exposure to light (photochromism) or acids (halochromism). The inclusion of stimuli-responsive molecules in general – and SPs in particular – as main-chain repeating units is a scarcely explored macromolecular architecture compared to side chain responsive polymers. Herein, we establish the effects of substitution patterns on SPs within a homopolymer main-chain synthesized via head-to-tail Acyclic Diene METathesis (ADMET) polymerization. We unambiguously demonstrate that varying the location of the ester group (–OCOR) on the chromophore, which is essential to incorporate the SPs in the polymer backbone, determines the photo- and halochromism of the resulting polymers. While one polymer shows effective photochromism and resistance towards acids, the opposite – weak photochromism and effective response to acid – is observed for an isomeric polymer, simply by changing the position of the ester-linker relative to the benzopyran oxygen on the chromene unit. Our strategy represents a simple approach to manipulate the stimuli-response of main-chain SP bearing polymers and highlights the critical importance of isomeric molecular constitution on main-chain stimuli-sensitive polymers as emerging materials
