Fluorescence Analysis of Local Microenvironments in Polymer Films Using Solvatochromic Dyes

Polymer films and polymer blend films are widely used as functional materials; however, their photophysical behavior cannot be fully explained solely by bulk properties such as relative permittivity or glass transition temperature. In this study, we investigate how local polymer microenvironments regulate fluorescence responses by employing two strongly emissive solvatochromic dyes-FπPCM, a D-π-A-type π-conjugation-extended fluorene dye, and PK, a D-π-A-type pyrene dye-as molecular probes. The photophysical properties of these dyes were systematically examined in a series of transparent polymer matrices, including polystyrene, polycarbonate, poly(methyl methacrylate), poly(vinyl chloride), triacetylcellulose, poly(butyl methacrylate), and poly(2-ethyl-2-oxazoline). Polymer films containing the dyes were prepared by solution casting from homogeneous polymer-dye solutions onto quartz substrates followed by solvent evaporation. Both dyes exhibited polymer-dependent variations in fluorescence wavelength, quantum yield, and lifetime, reflecting not only differences in polymer polarity but also local chain packing and specific dye-polymer interactions. Fluorescence lifetime analysis of PS/POz blend films revealed microscopic heterogeneity even in miscible systems, quantitatively captured using averaged lifetime parameters. Temperature-dependent fluorescence measurements further demonstrated that thermal history and structural relaxation significantly influence local polymer environments. In particular, ratiometric fluorescence analysis of PMMA/PBMA blend films enabled reproducible temperature sensing over a wide range from 30 to 120 °C, despite an overall negative temperature response. These results establish solvatochromic dyes as versatile optical probes for evaluating local polymer microenvironments and highlight their potential for polymer-state monitoring and fluorescence-based temperature-sensing applications.