N8O2多牙配基合成及其與後過度金屬配位化學之探討

Abstract

本篇論文研究成功的合成出具有N8O2 多牙配體配基，此配基具有多種與金屬配位之可能性。在酸性條件下可成功的合成具雙核銅金屬錯化合物，在鹼性條件下可以成功地得到三核銅金屬錯化合物。雙/三核錯化合物間存在著平衡關係，並且可利用酸鹼加以調控。在可見光光譜滴定實驗中，發現到此平衡中間存在著不穩定的中間體，此中間體可利用質譜儀(ESI-MS)，可見光光譜儀(UV-VIS)以及理論計算加以分析，推測其具有四核銅之特徵。 此外，空氣中二氧化碳可介入此平衡反應，並且被加以捕捉，進而得到八核銅金屬錯化合物。以上之錯化合物皆已使用高解析質譜儀，可見光光譜儀，以及紅外線光譜儀等技術完整鑑定。八合核一雙核銅錯化合物更進一步使用X 光繞射分析儀進行結構解析。 利用雙核銅錯化合物當作模板，再加入額外的異金屬，可成功的合成出混金屬錯化合物。儘管缺少了X 光繞射分析鑑定此混金屬錯化合物之結構，仍利用了可見光光譜儀以及TD-DFT 理論計算決定了此錯化合物之結構以及金屬所在位置。

In this work, new N8O2 multidentate ligands are successfully synthesized and characterized. Their major structures contain three potential binding sites for copper(II) ions and the numbers of metal that bearing multidentate ligand are controlled by pH value. The dinuclear copper(II) complex is successfully synthesized and isolated under acidic condition. When additional copper ions and appropriate base are utilized, the dinuclear complex can be turned to the trinuclear complex. Also, dicopper and tricopper compound can easily take up CO2 to form octanuclear carbonato complex under suitable pH condition. These complexes are fully characterized by UV-VIS, HR-ESI mass, and IR spectroscopy. In addition, the dicopper, and octacopper compound are also studied by single-crystal X-ray diffraction analysis. According to the information of the dicopper complex can be easily synthesized in acidic condition, it makes the possibility for the synthesis of mixed metal complex. The mixed metal complex have been successfully synthesized and characterized. Despite lack of crystal structure, these mixed metal complexes still can be determined their metal location and geometry by using EPR, UV-VIS and DFT calculation.