近年來，由於鋁為高豐度、低價格與低毒性之元素，加上具良好的路易斯酸性。因此，能有效活化酯類單體，故而成為開環聚合反應中常見的金屬催化劑之一；同時，聚酯類化合物因具備良好的可降解性，也逐漸成為研究與應用上的關注焦點。鋁金屬催化劑可藉由設計配位基上取代基並結合多核金屬催化劑系統，藉以影響金屬中心的活性、選擇性與聚合控制性。因此，本研究參考過去相關文獻，合成出一系列含吡唑配位基之多核鋁錯合物，並針對三核催化劑中的配位基及鋁試劑進行修飾，以探討其在環己內酯開環聚合反應中的催化行為。結果顯示，所有催化劑對單體皆為一級反應，且催化劑具不同核數、修飾位點與電子效應時展現出不同但具規則的催化活性及控制性。接著，亦針對不同起始劑劑量與單體量下的開環聚合反應進行探討，以評估此催化系統的活性與可控性。最後，則藉由一系列 1H NMR 監測實驗及 BnOD 實驗證實此系統反應機制。;In recent years, aluminum has attracted attention as a ring-opening polymerization (ROP) catalyst due to its high abundance, low cost, low toxicity, and strong Lewis acidity, enabling efficient activation of ester monomers. Meanwhile, biodegradable polyesters have become increasingly important in research and applications. The catalytic performance of aluminum complexes can be tuned by modifying substituents on the ligands and employing multinuclear systems to influence activity, selectivity, and polymerization control. In this study, inspired by previous reports, a series of multinuclear aluminum complexes with pyrazolyl ligands were synthesized. For trinuclear catalysts, both ligand and aluminum reagent modifications were explored to investigate their catalytic behavior in ε-caprolactone ROP. All catalysts exhibited first-order kinetics toward the monomer, with catalytic activity and control varying systematically with nuclearity, modification site, and electronic effects. The influence of initiator and monomer loading was examined, and 1H NMR monitoring together with BnOD experiments confirmed the proposed reaction mechanism.
