Primary alcohol‐functionalized β‐diketones (bdks) are successfully synthesized via facile one‐step Claisen condensation between aromatic monoketones and ε‐caprolactone (ε‐CL). To demonstrate application potentials, these bdk alcohols are used to chelate with various Lewis acids, including Tb (III), Eu (III), and B (III). It is discovered that the resulting Tb (III) and Eu (III) diketonate complexes can serve as both catalysts and initiators for ring‐opening polymerization (ROP) under solvent‐free conditions, using lactide monomer as an example. The polylactides (PLAs) thus obtained exhibit luminescence properties characteristic of Tb (III) and Eu (III), respectively. On the other hand, boron‐chelated diketone can initiate ROP of lactide in the presence of Sn(oct)2, and affords a PLA material with dual‐emission, i.e., fluorescence and room temperature phosphorescence. The synthesis described here represents a shortcut for the preparation of bdk‐based macroligands and subsequent functional materials.
