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  • 學位論文

含雙醯胺吡啶與V字型配位基之二價鈷、鎳配位高分子的合成、結構與性質研究

Synthesis, Structures and Properties of Cobalt(II) and Nickel(II) Coordination Polymers Containing Dipyridyl Amide and V-shaped Dicarboxylate Ligands

指導教授 : 陳志德

摘要


一系列含 N,N’-二-(4-吡啶)辛二醯二胺 (L)與V字型配位基的鈷鎳錯合物已藉由水熱反應合成: {[Co(L)(MBA)]2H2O}n (H2MBA = diphenylmethane-4,4’-dicarboxylic acid), 1, {[Ni(L)(MBA)]2H2O}n, 2, {[Co2(L)(MBA)2]2CH3OH}n, 3 , {[Co2(L)(MBA)2]}n , 4 ,{[Co2(L)(OBA)2]7CH3OH}n [H2OBA = 4,4’-oxybis(benzoic acid)], 5, {[Co(L)(H2hfipbb)]2H2O}n [H2hfipbb=4,4′-(hexafluoroisopropylidene)bis(benzoic acid)], 6, {[Co(L)(SDA)].H2O}n (H2SDA = 4,4’-sulfonyldibenzoic acid), 7, {[Co2(L)(MBA)2]2CH3OH}n , 3, {[Ni(L)(SDA)]2H2O}n, 8。 這些化合物藉由單晶X-ray繞射儀來鑑定其結構,更進一步利用元素分析儀、粉末X-ray繞射儀、熱種分析儀來研究化合物的特性。其中化合物5 對於二氧化碳的吸附較氫氣及氮氣來的出色。 化合物1和2是利用一維的螺旋鏈形成1D→2D多具連鎖的結構。化合物3為一個2-fold 交互貫穿的結構,每個單元具有(42688104)(4)2-2,6L1的拓樸學。化合物4為一個2D→3D多聚連鎖的結構,每個單元具有(42688104)(4)2-2,6L1的拓樸學。化合物5為一個3-fold交互貫穿的結構,每個單元具有(63)(698)-gra的拓樸學。化合物6到8為2 或 3 fold 交互貫穿的結構,每個單元都具有(64810)(6)的拓樸學。而每個交互貫穿的結構可以進一步和相鄰兩層鏈在一起形成少見的2D→3D多聚連鎖的結構。

並列摘要


A series of Co(II) and Ni(II) coordination polymers containing N,N-di(4-pyridyl)suberoamide (L) and V-shaped dicarboxylate ligands: {[Co(L)(MBA)]2H2O}n (L = N,N’-di(4-pyridyl)suberoamide; H2MBA = diphenylmethane-4,4’–dicarboxylic acid), 1, {[Ni(L)(MBA)]2H2O}n, 2, {[Co2(L)(MBA)2]2CH3OH}n , 3, {[Co2(L)(MBA)2]}n, 4, {[Co2(L)(OBA)2]7CH3OH}n [H2OBA = 4,4’–oxybis(benzoic acid)], 5, {[Co(L)(H2hfipbb)]2H2O}n [H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid)], 6, {[Co(L)(SDA)]H2O}n (H2SDA = 4,4’-sulfonyldibenzoic acid), 7, {[Ni(L)(SDA)]2H2O}n, 8, are reported, which were prepared by hydrothermal reactions. Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, powder X-ray diffraction and thermal gravimetric analysis. The CO2 capture is preferable to N2 and H2 in the gas sorption for the desolvated product of 5. Complex 1 and 2 are 1D → 2D polycatenanes derived from the helical channels. Complex 3 shows the (42688104)(4)2-2,6L1 topology with a 2-fold interpenetrating mode. Complex 4 shows 2D layers with the (42688104)(4)2 2,6L1 topology, which catenate to each other to form a 2D → 3D inclined polycatenation framework. Complex 5 shows (63)(698)-gra topology with a 3-fold interpenetrating mode. The unusual topological features of 6 - 8 consists of the 2- and 3-fold interpenetrated layers with the (64810)(6) topology, which are further catenated to the two adjacent such sheets in parallel fashion to give overall unique 2D → 3D polycatenated frameworks.

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