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  • 學位論文

氧化還原控制新巨環矩形鐵硫核心{Cp2Fe2(μ-SEt)2}化合物的孔穴大小:自組裝與分段合成研究

Redox Control the Cavity of A New Rectangulr Macrocycle Base on Iron-Sulfur Core {Cp2Fe2(μ-SEt)2}: Stepwise Formation and Self-Assembly Study

指導教授 : 許智能

摘要


一個新型的四核矩形化合物[Cp4Fe4(μ-SEt)4(μ-1,4-CNC6H4NC)2] (BF4)4(54+)可以藉由[Cp2Fe2(μ-SEt)2(MeCN)2] (BF4)2 (22+)以及等當量的1,4-diisocyanobenzene配位基3自組裝形成;或是藉由先合成出化合物[Cp2Fe2(μ-SEt)2(μ-1,4-CNC6H4NC)2](BF4)2 (42+)再與化合物[Cp2Fe2(μ-SEt)2(MeCN)2] (BF4)2 (22+)一比一當量逐步形成。化合物54+的化學還原反應可以經由加入KC8實驗証實並且得到還原產物[Cp4Fe4(μ-SEt)4(μ-1,4-CNC6H4NC)2](BF4)2(52+),而此還原反應也可以藉由電化學來佐證。化合物42+、化合物54+與化合物52+的合成、光譜以及電化學方面的研究也已經完成。經由比較化合物54+與化合物52+的晶體結構的結果可以顯現其氧化還原控制四核矩形化合物的中央孔穴大小改變。

關鍵字

自組裝 超分子 分段合成

並列摘要


A new rectangular tetranuclear iron-sulfur complex [Cp4Fe4(μ-SEt)4(μ-1,4-CNC6H4NC)2](BF4)4 (54+) has been synthesized by the self-assembly reaction between [Cp2Fe2(μ-SEt)2(MeCN)2](BF4)2 (22+) and equimolar amounts of 1,4-diisocyaobenzene, or by stepwise formation via mixing complex [Cp2Fe2(μ-SEt)2(MeCN)2](BF4)2 (22+) and [Cp2Fe2(μ-SEt)2(μ-1,4-CNC6H4NC)2](BF4)2 (42+) in 1:1 molar ratio. The chemical reduction of (54+) by KC8 was examined and afforded (52+) where existence can also be proved by electrochemical method. The syntheses spectroscopic, and electrochemical studies of iron-sulfur complexes, (42+), (54+) and (52+), were performed. The redox control on cavity change of rectangular tetranuclear iron-sulfur complex is revealed by the comparison of the X-ray crystallographic analysis of complexes (54+) and (52+).

參考文獻


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