含苯-1,4-二甲醯胺配位基及其二價金屬化合物之 合成、結構與核磁共振之研究

Synthesis, Structures and NMR Studies of the Compounds Bearing Benzene-1,4-dicarboxamide Groups and Their Divalent Metal Complexes

許嘉儒(Chia-Ju Hsu)

中原大學/理學院/化學研究所/碩士(2011年)

https://doi.org/10.6840/CYCU.2011.00262

摘要

本論文主要討論含苯-1,4-二甲醯胺配位基及其二價金屬化合物之合成、結構與核磁共振之研究。使用核磁共振技術對含苯-1,4-二甲醯胺配位基N,N'-bis(2-pyridinyl)-1,4-benzenedicarboxamide (L1)、N,N'-bis(3-pyridinyl)-1,4-benzenedicarboxamide (L2)、N,N'-bis(4-pyridinyl)-1,4-benzenedicarboxamide (L3) 與
N,N'-bis(2-pyrimidinyl)-1,4-benzenedicarboxamide (L4)做有系統的分析，觀察配位基之官能基對-NH-的影響，並用單晶X-ray繞射儀量測結果對配位基做比較與探討。我們藉由NMR脈衝實驗可得到許多關於配位基分子在液態下呈現之結果，而在固態結果中cis-及trans-兩種形式皆有存在。
利用配位基L2分別與ZnI2和Co(NO3)2反應可分別得到[Zn(HBDC)(BDC)0.5(L2)0.5]．3DMF, 1和，[Co3(BDC)3(L2)] , 2，以上兩個化合物的結構均已利用單晶 X-ray 繞射儀鑑定。化合物1為雙金屬中心結構，利用Zn金屬與對苯二甲酸所形成的二維網狀結構，孔洞大小為17.078 × 10.936 Å2。化合物2為三金屬中心結構，Co金屬與對苯二甲酸形成三股螺旋(Triple Helix)結構，接著堆疊成二維結構，最後利用配位基L2在二維結構面與面之間的連結形成了三維結構。配位基 L2在兩化合物中皆以trans- 形式存在。

關鍵字

含苯-1，4-二甲醯胺配位基 ； 二價金屬化合物

並列摘要

This thesis discusses the synthesis, structures and NMR studies of the compounds bearing benzene-1,4-dicarboxamide groups and their divalent metal complexes. NMR studies on N,N'-bis(2-pyridinyl)-1,4-benzenedicarboxamide (L1)、
N,N'-bis(3-pyridinyl)-1,4-benzenedicarboxamide (L2)、N,N'-bis(4-pyridinyl)-1,4-benzenedicarboxamide (L3) and N,N'-bis(2-pyrimidinyl)-1,4-benzenedicarboxamide (L4) show some of the informations for these ligands, but not the precise conformations. In the solid state these ligands show both the cis- and trans-conformations, which were verified by X-ray crystallography.
Reactions of ZnI2 and Co(NO3)2 with N,N'-bis(3-pyridinyl)-1,4-benzenedicarboxamide(L2), afforded [Zn(HBDC)(BDC)0.5(L2)0.5]．3DMF, 1 and [Co3(BDC)3(L2)], 2. Both complexes have been structurally characterized by X-ray crystallography. Complex 1 consists of dinuclear metal centers, which are linked by the BDC－ and L2 ligands to form a 2D network, and the approximately accessible cavity is 17.078 × 10.936 Å2. Complex 2 consists of trinuclear metal centers, which are linked by the BDC－ and L2 ligands to form a 3D structure. All the L2 ligands in these two complexes show trans-conformation.

並列關鍵字

Benzene-1，4-dicarboxamide ； Divalent Metal Complexes

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