含可撓曲吡啶配子之過渡金屬錯合物之自組裝、結構分析與物性探討

Self-assembly, Structures, and Properties of Transition Metal Complexes Containing Flexible Pyridine Ligands

蘇雅涵(Ya-Han Su)

指導教授 ： 曾添文

共同指導教授 ： 呂光烈

國立臺北科技大學/工程學院/化學工程研究所/碩士(2014年)

摘要

本實驗採用具可撓曲性有機配子5,5′-bis[2-(4-pyridinyl)-1H-benzimidazole] (pyben)與金屬鹽類反應生成有機金屬配位聚合物 (1－3），另外一部份為pyben分別與具有羧酸根有機配子及金屬鹽類之合成 (4－6)，並從單晶X-ray繞射結果探討其結構，從螢光光譜圖及氣體吸附圖譜探討各結構物的物理性質。
本論文分為兩部分，如下所示:
第一部份: 5,5′-Bis[2-(4-pyridinyl)-1H-benzimidazole] (pyben)與金屬鹽類之合成
為利用可撓曲有機配子5,5′-bis[2-(4-pyridinyl)-1H-benzimidazole] (pyben) 與金屬鹽類反應形成化合物1－3。利用具有苯并咪唑官能基及吡啶末端機的有機配子pyben與Ni(CH3COO)24H2O以水浴法自組裝合成，反應後得到化合物{[Ni(pyben)(CH3COO)2(H2O)2]EtOH}n (1)；利用有機配子pyben與Co(NO3)26H2O以室溫方式自組裝合成，反應後得到化合物{[Co(pyben)(NO3)2(H2O)]2EtOH}n (2)；利用有機配子pyben與Ni(CH3COO)24H2O及有機配子anthraquinone-2,6-disulfonic acid (aqds)以水浴法自組裝合成，反應後得到化合物{[Ni(pyben)(H2O)4]aqdsEtOH}n (3)。經由單晶X-ray繞射解析顯示，化合物1為一維鏈狀(chain)結構；化合物2為一維雙螺旋狀(double-helical)結構；化合物3為一維鋸齒狀(zigzag)結構；化合物1及化合物3皆為鎳金屬的一維結構，但因化合物3加入有機配子aqds作為調控，使得結構中有機配子pyben中苯并咪唑的撓曲角度有別，由此可以看出有機配子pyben的撓曲特性；而化合物1其一維鏈狀堆疊成類三維結構，使得結構中具有一維孔道，具有氣體吸附之特性，置換化合物中陰離子後進一步進行有關氣體吸附性質之探討。

第二部份: 5,5′-Bis[2-(4-pyridinyl)-1H-benzimidazole] (pyben)分別與具有羧酸根有機配子及金屬鹽類之合成
化合物4－6為利用有機配子5,5′-bis[2-(4-pyridinyl)-1H-benzimidazole] (pyben)分別與具有羧酸根有機配子與金屬鹽類，以50 °C水浴法自組裝，形成三種不同維度的化合物；利用有機配子pyben及有機配子1,2,4,5-tetracarboxybenzene (H4btec)與鈷金屬Co(NO3)26H2O進行自組裝反應，反應中鈷金屬未參與配位，反應可得到化合物 [(H2pyben)0.5(H2btec)0.5] (4) ；利用有機配子pyben及有機配子terephthalic acid (1,4-H2bdc)與Zn(NO3)26H2O反應得化合物{[Zn2(pyben)2(1,4-bdc)2]DMF3H2O}n (5)；利用有機配子pyben及有機配子isophthalic acid (1,3- H2bdc) 與Zn(NO3)26H2O於50 °C水浴下反應後可得化合物{[Zn2(pyben)2(1,3-bdc)2]2DMF4H2O }n (6)。經由單晶X-ray繞射解析顯示，化合物4為有機配子pyben及H4btec的共結晶化合物，相較於金屬與配子的配位能力，可看出有機配子pyben具有強烈的氫鍵作用力，因此增強化合物的熱穩定性，由TGA顯示可熱穩定至300°C。化合物5及化合物6為利用同分異構物的二羧酸配子進行自組裝合成，而得到兩種不同維度的化合物:化合物5為三維的pcu網狀結構，其結構具有二次互穿特性，使結構具有兩種不同大小孔道，其大小分別為12.75 × 3.75 A2及3.78 × 2.10 A2；化合物6為二維磚牆狀(brick wall)結構，其為sql層狀結構，而結構中各層以ABAB排列形成三維結構。

關鍵字

自組裝合成 ； 有機金屬化合物 ； 氣體吸附

並列摘要

In the first part of this thesis, a series of new metal-organic coordination complexes, {[Ni(pyben)(CH3COO)2(H2O)2]EtOH}n (1, pyben = 5,5′-bis[2-(4-pyridinyl)-1H-benzimidazole]), [Co(pyben)(NO3)2(H2O)]2EtOH}n (2), {[Ni(pyben)(H2O)4]aqdsEtOH}n (3, aqds = anthraquinone-2,6-disulfonic acid), were prepared by the self-assembly of benzimidazole derivative with transition metal ions in the presence of pyridyl N-donor ligands. Single-crystal X-ray diffraction analyses of complexes 1-3 indicated that they adopted a one-dimensional structure. Complex 1 has a 1D chain structure; complex 2 adopts a 1-D double-helical structure; while complex 3 is composed of a 1D zigzag structure. Both complexes 1 and 3 were prepared using the same metal ion (Ni2+) and similar reaction conditions, except that the sulfonate was added in one case and not in the other. The benzimidazole rings in the pyben ligand have different twist angles, indicating the flexibility of the pyben ligand. Complex 1 is a three-dimensional framework, in which one-dimensional channels were observed with a window size of 14.75 × 6.99 A2, filled with guest ethanol molecules. After subjecting 1 to ion exchange procedures, the gas adsorption behaviors of the corresponding compounds were further investigated.

In the second part of this thesis, three independent coordination complexes, [(H2pyben)0.5(H2btec)0.5] (4, H2btec = 1,2,4,5-tetracarboxybenzene), {[Zn2(pyben)2(1,4-bdc)2]DMF3H2O}n (5, 1,4-bdc2- = terephthalate), {[Zn2(pyben)2(1,3-bdc)2]2DMF4H2O}n (6, 1,3-bdc2- = isophthalate), with different dimensions were prepared by the self-assembly of benzimidazole derivative with transition metal ions and carboxylate-containing ligands. Complex 4 is a cocrystal, produced as the result of the co-crystallization of pyben and H2btec ligands. The metal ion (Co2+) did not participate in the coordination with the ligands. Strong hydrogen-bonding interactions in complex 4 were observed. Complex 4 was found to be thermally stable at temperatures of up to 300 °C. Complexes 5 and 6 are isomeric structures, both of that contain carboxylate groups. Complex 5 adopted a three-dimensional framework with a pcu topology. Interesting, complex 5 contains one-dimensional porous channels and possesses a 2-fold interpenetrated network. Complex 6 is a two-dimensional framework with a sql topology, these 2D layers are packed on an ABAB manner, giving rise to a 3D structure.

並列關鍵字

Self-Assembly ； Metal–Organic Framework ； Gas Adsorption

參考文獻

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