"設計與合成含1,10-鄰二氮菲配基之金屬籠狀化合物及其在克腦文蓋爾縮合反應的催化應用"

Abstract

在近代化學中，超分子化學引起了許多化學家的興趣，在這個領域之中研究者致力於研究分子間的作用力。在這個研究基礎上，我們可以系統化地去設計以金屬與配體所建構的金屬籠狀化合物，在本研究之中，我們合成了一系列以1,10-鄰二氮菲為建構單元的配基，在不同幾何形狀配基的錯合實驗之中，我們發現到以1,1′-聯-2-奈酚為建構單元的配基具有可調整的骨架，在混入不同的金屬離子後，可以成功地形成雙金屬的籠狀化合物，並利用核磁共振儀與質譜分析鑑定其結構，另外，具有光學活性的1,1′-聯-2-奈酚的配基在混入金屬離子後可以產生光學選擇性的金屬籠狀化合物，我們也混合金屬與不同聯結位置的1,10-鄰二氮菲為建構單元的配基，預期結果可產生自排序的選擇性錯合. 超分子化學也被視為可以了解與生物系統的工具，為了仿造生物體中酵素的功能，我們合成了具有內修飾的金屬籠狀化合物去測試催化反應，在一系列的實驗之後，我們發現在[Zn2{(S)-L11}3]催化之下，苯甲醛衍生物與丙二腈可以在非鹼性的溫合條件下進行克腦文蓋爾縮合反應，此外，這個金屬籠狀化合物的催化劑還具有可回收性以及對反應物有尺寸的選擇性。

Supramolecular chemistry dealing with noncovalent interactions between molecules is an attractive topic in the modern chemistry. On the basis of design principles for coordination-driven self-assembly of metallocages, a series of phenanthroline-based ligands were prepared. Through a systematic study on ligand geometry, the ligand with a rotatable BINOL core was found to afford matallocages upon coordination to Zn(II), Cd(II) and Fe(II), which were characterized by NMR spectroscopy and ESI-MS spectrometry. Besides, chiral BINOL-based ligands complexed with metal ions resulted in chiral self-sorting. Moreover, the narcissistic self-sorting process of metallocages was observed with ligands differing in the substitution positions of phenanthroline. Supramolecular metallocages could be considered as a good platform for mimicking biological systems. To this end, endo-functionalized metallocages were introduced to catalytic reactions. In the results of Knoevenagel condensation reactions, [Zn2{(S)-L11}3] showed catalytic activity for a series of benzaldehyde substrates with malononitrile under mild conditions as well as reusability and molecular-size selectivity.