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The self-assembling of fluorescent guest molecules, with the δ nanoporous host crystalline phase of syndiotactic polystyrene (s-PS) films, reduces chromophore diffusivity. Moreover, the chromophore fluorescence can be largely perturbed by formation of suitable polymer co-crystals. In particular, by excitation at the absorbance maximum (≈265 nm), s-PS/1,3,5-trimethylbenzene clathrate co-crystals present a broad fluorescence band nearly centered at 300 nm, while the corresponding intercalate co-crystals present a red-shifted fluorescence band with maxima at 330, 340, and 355 nm. This red shifted fluorescence is possibly due to absorption of the primary fluorescence by ground state complexes, formed in the intercalate co-crystal. The enhanced and red-shifted fluorescence could be relevant for optical and optoelectronic applications.

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