CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, 230026, China.
Macromol Rapid Commun. 2014 Mar;35(5):566-73. doi: 10.1002/marc.201300834. Epub 2013 Dec 19.
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.
通过芳香单酮和ε-己内酯（ε-CL）之间的简便一步克莱森缩合，成功合成了伯醇官能化的β-二酮（bdks）。为了展示应用潜力，这些 bdk 醇被用于与各种路易斯酸（包括 Tb（III）、Eu（III）和 B（III））螯合。结果发现，所得的 Tb（III）和 Eu（III）二酮配合物可以在无溶剂条件下作为开环聚合（ROP）的催化剂和引发剂，以丙交酯单体为例。由此获得的聚丙交酯（PLA）分别表现出 Tb（III）和 Eu（III）的发光特性。另一方面，硼螯合二酮可以在 Sn(oct)2 的存在下引发丙交酯的 ROP，并提供具有双发射的 PLA 材料，即荧光和室温磷光。这里描述的合成代表了制备基于 bdk 的大环配体和随后的功能材料的捷径。
