Epoxy Functional Composites Based on Lanthanide Metal–Organic Frameworks for Luminescent Polymer Materials

The integration of metal–organic frameworks (MOF) into organic polymers represents a direct and effective strategy for developing innovative composite materials that combine the exceptional properties of MOFs with the robustness of organic polymers. However, the preparation of MOF@polymer hybrid composites requires an efficient dispersion and interaction of MOF particles with polymer matrices, which remains a significant challenge. In this work, a new simple and direct approach was applied for the development of Ln-MOF@polymer materials. A series of Ln-MOF@TGIC composites {Ln-MOF = [Ln(μ3-BTC)(H2O)6]n (Ln-BTC), where Ln = Eu, Tb, Eu0.05Tb0.95; H3BTC = 1,3,5-benzenetricarboxylic acid; TGIC = triglycidyl isocyanurate} were successfully obtained by applying a grinding method via the chemical bonding between uncoordinated carboxylate groups in Ln-BTC and epoxy groups in TGIC. The Ln-BTC@TGIC materials possess significant fluorescence characteristics with superior emission lifetimes and quantum yields if compared to parent Ln-MOFs. Interestingly, under the UV irradiation, a considerable color change from yellow in Eu0.05Tb0.95-BTC to red in Eu0.05Tb0.95-BTC@TGIC was observed. The energy-transfer mechanism was also rationalized by the density functional theory (DFT) calculations. The developed Ln-BTC@TGIC composites were further applied as functional fluorescent coatings for the fabrication, via a simple spraying method, of the flexible polyimide (PI) films, Ln-BTC@TGIC@PI. Thus, the present work unveils a new methodology and expands its applicability for the design and assembly of stable, multicomponent, and soft polymer materials with remarkable fluorescence properties.