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.
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