Polymer glasses have an irregular structure. Among the causes for such complexity are the chemically distinct chain end-groups that are the most abundant irregularities in any linear polymer. In this work we demonstrate that chain end induced defects allow polymer glasses to create confined environments capable of hosting small emissive molecules. Using environmentally sensitive luminescent complexes we show that the size of these confinements depends on molecular weight and can dramatically affect the photoluminescence of free or covalently bound emissive complexes. We confirm the impact of chain end confinement on the bulk glass transition in poly(methyl acrylate) and show that commonly observed Tg changes induced by the chain ends should have a structural origin. Finally, we demonstrate that size and placement of luminescent molecular probes in pMA can dramatically affect the probe luminescence and its temperature dependence suggesting that polymer glass is a highly irregular and complex environment marking its difference with conventional small molecule solvents. Considering the ubiquity of luminescent glassy materials, our work lays down a blueprint for designing them with structural considerations in mind, ones where packing density and chain end size are key factors.
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