含可撓曲四芽配子之金屬有機錯合物之自組裝合成，結構分析與物性探討

Self-assembly, Structures, and Properties of Metal Complexes Containing a Flexible Tetradentate Ligand

陳春億(Chun-Yi Chen)

指導教授 ： 曾添文 ； 呂光烈

國立臺北科技大學/工程學院/化學工程研究所/碩士(2013年)

https://doi.org/10.6841/NTUT.2013.00617

摘要

本論文分兩部分
(一) 自組裝合成苯咪唑四芽配子與過渡金屬鹽類之配位化合物
以有機配子1,2,4,5-tetrakis(benzoimidazol-1-ylmethyl)-benzene (TBim)各別與過渡金屬中之金屬離子(Cu(II), Co(II), Zn(II))進行自組裝反應，得到化合物1-5。以配子TBim與氯化銅在水熱條件下(120 ℃或140 ℃)反應可分別得{[Cu(TBim)0.5Cl]∙ 0.5 (DMF)}n (1)及{[(CuCl4)(TBimdm)0.5]•(H2O)} (5); 當有機配子(TBim)與鈷及鋅的醋酸鹽類在室溫下反應，可得到{[M(TBim)2(CH3COO)2]•4H2O}n (2; M = Co, 3; M = Zn), 當配子TBim與硝酸鋅在水浴(80 ℃)下反應，可得到{[Zn(TBim)1.5(NO3)](NO3)}n (4)。在第一部分，共可得到四個配位聚合物，及一個有機金屬錯合物。產物1-5經由紅外線共振吸收、元素分析、X光單晶繞射解析等作成份及結構鑑定，在本論文亦會探討其熱穩定性及其發光性質。
(二) 錸金屬離子及有機配子(TBim)作自組裝合成
利用有機配子TBim混合三種不同的醌類的配位基與含錸起始物Re2(CO)10進行水熱自組裝反應，可得到三種錸金屬錯合物6-8。以 1,5-diaminoanthraquinone (Daaq) 為配子時，得到{[Re4(CO)12(TBim)(Daaq)2]∙(toluene)} (6)；混以anthrarufin (Atrf) 配子可得到[Re4(CO)12(TBim)(Atrf)] (7)；以1,5-diamino-4,8-dihydroxy-
anthracene-9,10-dione (Dadh) 配子，得到[Re4(CO)12(TBim)(Dadh)] (8)。錯合物6-8之鑑定及結構解析，及經由紅外線共振吸收、核磁共振氫譜、質譜、元素分析及X光單晶繞射解析，其紫外-可見光吸收與其發光特性亦一併探討。

關鍵字

超分子 ； 自組裝 ； 過渡金屬 ； 錸金屬錯合物 ； 配位聚合物

並列摘要

This thesis is mainly focused on the self-assembly, structure, and properties of metal complexes containing a flexible tetradentate ligand.
(1) self-assembled coordination compounds using tetradentate ligand and transition metal salts.
Treatment of the organic tetradentate ligand TBim with divalent copper (II) ions under hydrothermal conditions at 120 ℃ and 140 ℃ afforded compounds {[Cu(TBim)0.5Cl]∙0.5(DMF)}n (1) and {[(CuCl4)(TBimdm)0.5]∙(H2O)} (5), respectively. Compounds {[Co(TBim)0.5(CH3COO)2]•H2O}n (2) was prepared by the reaction of TBim with cobalt acetate at room temperature. Compound {[Zn(TBim)1.5(NO3)](NO3)}n (4) was synthesized using TBim and Zinc nitrate at 80 ℃. In the first part, the synthetic procedures used for the preparation of compound 1-5 under different temperatures are discussed. These compounds were analyzed by FT-IR and EA techniques and their structures are confirmed by a single X-ray diffraction analyses. The thermal stabilities, and emission properties of 1-5 were examined and the findings are discussed in detail.
(2) Self-assembled rhenium complexes 6-8
Using three types of quinone-containing ligand (1,5-diaminoanthraquinone, anthrarufin, 1,5-diamino-4,8-dihydroxyanthracene-9,10-dione) with a rhenium precursor under solvothermal reaction, it is possible to produce the rhenium complexes ({[Re4(CO)12(TBim)(Daaq)2]∙(toluene)} (6), [Re4(CO)12(TBim)(Atrf)] (7), [Re4(CO)12(TBim)(Dadh)] (8)). These compounds were characterized by FT-IR, EA and their structures were confirmed by a single-crystal X-ray diffraction analysis. The UV-vis absorption, and emission properties of compounds 6-8 were also examined and the results are discussed in detail.

並列關鍵字

Coordination polymer ； Rhenium complexes ； Self-assembly ； Supramolecule ； Transition metal

參考文獻

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