含雙醯胺吡啶配位基與二價金屬配位高分子之拓樸學研究

Topological investigation on divalent coordination polymers containing diprridyl amide ligands

吳明昊(Ming-Hao Wu)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2013年)

https://doi.org/10.6840/cycu201300393

摘要

以中性雙醯胺吡啶配位基bis(N-pyrid-4-ylmethyl)adipoamide (Mp46)及bis (N-pyrid-3-ylmethyl)adipoamide (Mp36)與二價金屬反應，在室溫下利用合成養晶法可得到十個配位高分子化合物，分別為：{[Zn(Mp46)1.5(CH3OH)2](ClO4)2．0.5(C2H5O)．H2O}∞ (1)、{[Co(Mp46)1.5(CH3OH)2](ClO4)2．0.5(C2H5O)．H2O}∞ (2)、{[Cd(Mp46)(DMF)2](ClO4)2．2DMF}∞ (3) 、[Zn(NO3)2(Mp46) (CH3OH)2．2CH3OH]∞ (4)、[Co(NO3)2(Mp46) (CH3OH)2．2CH3OH]∞ (5)、[ZnBr2(Mp46)]∞ (6)、[ZnCl2(Mp46)]∞ (7)、[Cd(NO3)2(Mp46)．2DMF]∞ (8)、[Zn(NO3)2(Mp36)]∞ (9)、[ZnI2(Mp46)．2THF]∞ (10)。化合物1與2具有(4,62)2(42,68,83,102)(64,82)拓譜學的三維網狀結構，化合物3與8具有(4,62)2(42,62,82)拓譜學的二維網狀結構，化合物4與5為一維長鏈狀結構，化合物6與7為零維環狀結構，化合物9為一維雙螺旋結構，化合物10為一維Z字鏈結構。
　　上述中性雙醯胺吡啶配位基，搭配不同長度的有機羧酸配位基在水熱條件下與二價金屬反應，可得到七配位高分子化合物，分別為：[Co(Mp46)(OBA)．H2O]∞ [H2OBA = 4,4’-oxybis(benzoic acid)] (11)、[Co(Mp36)(OBA)．H2O]∞ (12)、[Co(Mp36)0.5(SDA)．2CH3OH]∞ (H2SDA = 4,4’-sulfonyldibenzoic acid) (13) 、[Co(Mp36)0.5(SDA)．2CH3OH．2H2O]∞ (14)、[Co(Mp36)0.5(SDA)．0.5CH3OH．H2O]∞ (15)、[Co3(Mp46)0.5(1,2-BDC)3(CH3OH)]∞ (1,2-H2BDC = 1,2-benzenedicarboxylic acid) (16)、[Co(Mp36)0.5(1,3-BDC) (H2O)3]∞ (1,3-H2BDC = 1,3-benzenedicarboxylic acid) (17) 。化合物11為一個具有(44,62)拓譜學的二維 → 三維之多聚連鎖三維網狀結構，化合物12為一個具有孔道的一維柱狀結構，化合物13為一個具有(42,54)(4)2(5)2的一維自我貫穿結構，化合物14與15為同時具有(42,68,8,104)(4)2拓譜學的二維交互貫穿及二維 → 三維之交互接合三維網狀結構，化合物16為一個具有(4,52)(4,53,72)拓樸學的二維網狀結構，化合物17為一維鏈狀結構。

化合物1 – 17皆以單晶X-ray繞射儀、粉末X-ray繞射儀、元素分析儀、紅外光光譜儀、紫外-可見光光譜儀和螢光光譜儀鑑定其特性。

關鍵字

雙醯胺吡啶配位基 ； 拓樸學

並列摘要

This thesis discusses the synthesis, structures and properties of seventeen new coordination compounds containing bis(N-pyrid-4-ylmethyl)adipoamide (Mp46) or bis (N-pyrid-3-ylmethyl)adipoamide (Mp36) ligands. The reactions of divalent metal salts with Mp46 and Mp36 at room temperature afforded {[Zn(Mp46)1.5(CH3OH)2](ClO4)2．0.5(C2H5O)．H2O}∞ (1)、{[Co(Mp46)1.5(CH3OH)2](ClO4)2．0.5(C2H5O)．H2O}∞ (2)、{[Cd(Mp46)(DMF)2](ClO4)2．2DMF}∞ (3) 、[Zn(NO3)2(Mp46) (CH3OH)2．2CH3OH]∞ (4)、[Co(NO3)2(Mp46) (CH3OH)2．2CH3OH]∞ (5)、[ZnBr2(Mp46)]∞ (6)、[ZnCl2(Mp46)]∞ (7)、[Cd(NO3)2(Mp46)．2DMF]∞ (8)、[Zn(NO3)2(Mp36)]∞ (9)、[ZnI2(Mp46)．2THF]∞ (10). Complexes 1 and 2 form 3D frameworks with the (4,62)2(42,68,83,102)(64,82) topology, complexes 3 and 8 form 2D layers with the (4,62)2(42,62,82) topology, complexes 4 and 5 display 1D chains, complexes 6 and 7 form 0D metallocycles, while complex 9 displays 1D double helical chains and complex 10 shows 1D zigzag chains.

The reactions of cobalt(II) salts with Mp46/Mp36 and polycarboxylic acids under hydrothermal conditions gave [Co(Mp46)(OBA)．H2O]∞ [H2OBA = 4,4’-oxybis(benzoic acid)] (11), [Co(Mp36)(OBA)．H2O]∞ (12), [Co(Mp36)0.5(SDA)．2CH3OH]∞ (H2SDA = 4,4’-sulfonyldibenzoic acid) (13), [Co(Mp36)0.5(SDA)．2CH3OH．2H2O]∞ (14), [Co(Mp36)0.5(SDA)．0.5CH3OH．H2O]∞ (15), [Co3(Mp46)0.5(1,2-BDC)3(CH3OH)]∞ (1,2-H2BDC = 1,2-benzenedicarboxylic acid) (16) and [Co(Mp36)0.5(1,3-BDC) (H2O)3]∞ (1,3-H2BDC = 1,3-benzenedicarboxylic acid) (17). Complex 11 displays a 2D → 3D polycatenated framework with the (44,62) topology, complex 12 forms 1D channels, complex 13 displays a 1D self-penetrated framework with the (42,54)(4)2(5)2 topology, whereas complexes 14 and 15 display 2-fold interpenetrated 2D layers with (44,62) topology, which are also interdigitated to each other, complex 16 form a 2D layer with a (4,52)(4,53,72) topology, and complex 17 form a 1D chain.

All the complexes have been characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR, UV-vis and fluorescence spectroscopy.

並列關鍵字

coordination polymer

參考文獻

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