Synthesis and Structures of Multi-copper(II) Framework Containing N4O4-Multidentate Ligands

自然界中的金屬蛋白催化許多生物體中氧化還原反應，其主要的活性中心通常都為多金屬離子作為輔因子，而生物體中含量豐富的銅離子在許多生理功能上扮演非常重要的角色。研究金屬蛋白的化學反應機制，因受限於蛋白質結構的折疊及活性離子的不穩定性，使得生物無機化學家企圖以合成模型化合物的方式來探討其活性中心的結構與其反應機制。 本篇論文主要為合成含氨基-酚及雙胺-雙醇官能基的N4O4八牙之配位基(L-6/7-PhRX)並與銅離子形成多銅錯合物，藉以來了解探討其配位基與銅離子之間的配位模式和其衍生的物理化學性質。藉由反應物中銅離子當量數的調控，可以得到三銅或七銅錯合物，以紅外光共振光譜(IR) 、紫外光-可見光光譜(UV-Vis)、電噴灑質譜儀(ESI-MS)、導電度測量(conductivity measurement)、電子自旋共振光譜(EPR)、超導量子干涉磁化儀(SQUID)、循環伏安電儀(Cyclic voltammogram)與元素分析儀(elemental analysis)，了解其分子結構的組成並對於其物理性質加以探討。 不同幾何形狀的三銅、七銅晶體皆由 X光單晶繞射解析出來，藉由紫外光-可見光光譜和導電度測量，可以得知，七銅錯合物由多餘的銅離子連接兩個三銅錯合物在晶體堆疊時形成，而當其溶於液體時會自解離成三銅錯合物。由電子自旋共振光譜及超導量子干涉磁化儀結果顯示，此類藉由氧原子做為架橋的三銅錯合物具有明顯的反鐵磁現象(antiferromagnetic coupling)。最後，利用循環伏安法可以測得此八配子配位基具有氧化的能力，因此可以利用此新式八配子配位基來探討生物體中含銅金屬蛋白中心對於單電子氧化的情形。Metalloproteins containing multi-copper centers as catalytically active site are usually involved in several major biological oxidation-reduction reactions. Thus multinuclear copper complexes have motivated many inorganic chemists to attempt to develop the synthesis as well as investigate coordination chemistry of such species. In this work, new multinuclear network of CuII ions with octadentate N4O4-ligands, specifically containing the combination of amino-phenoxide and diamine-dialkoxide components (L-6/7-PhRX) have been successfully synthesized and structurally characterized. The ligands are mainly characterized by NMR techniques. Furthermore, the inorganic species are examined by conductivity measurements, ESI-Mass, UV-Vis, IR, EPR, and CV. A few examples were confirmed by X-ray diffractions. Single crystals of the tricopper complexes and the unusual dimeric compounds were obtained by modulating the number of copper equivalent. The latter heptacopper complexes were dimerized from two tricopper(II) species which were interacted with an extra CuII ions by our phenolate and two bridged hydroxylate oxygens