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  • 學位論文

羧酸環己烷過渡金屬配位聚合物之合成,結構分析與物性探討

Synthesis, Structures, and Properties of Coordination Polymers Assembled from Transition-metal Ions and Cyclohexane-multicarboxylates

指導教授 : 曾添文 呂光烈

摘要


本論文分兩部分 (一)水熱自組裝合成bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (btda)與鈷金屬鹽類之配位化合物1-2 利用有機配子btda與鈷金屬離子,分別加入有機配子4,4'-bipyridine與不加入4,4'-bipyridine兩組,分別進行水熱自組裝合成,於160 °C下得到配位聚合物1與2。以有機配子btda和4,4'-bipyridine與Co(NO3)2•6H2O反應,得到化合物{[Co2(hcc)2/3(H2O)2]•1.5H2O}n (1);以btda與Co(NO3)2•6H2O反應,得到化合物[Co3(hcc)(H2O)6]n (2),H6hcc = 1,2,3,4,5,6-cyclohexanehexacarboxylic acid,得到的化合物1-2皆為三維結構。於反應過程中,經由in-situ使其C=C斷裂生成有機配子hcc (cyclohexane hexacarboxylate),此反應過程於過渡金屬中為第一例,且此有機配子與金屬離子的配位模式至目前也尚未發現先例。有機配子4,4'-bipyridine在此扮演結構導向試劑(SDA,structure directing agent)的角色,可以誘導配位聚合物的結構產生變化,本身卻沒有參與配位。 (二)水熱自組裝合成cyclohexanedicarboxylic acid與過渡金屬鹽類之配位化合物3-5 利用有機配子cis-1,2-cyclohexanedicarboxylic acid (1,2-H2chdc)及1,4-cyclohexanedicarboxylic acid (1,4-H2chdc)分別與不同的含氮有機配子2,4,6-tris(2-pyridyl)-s-triazine(tptz)或2,2'-bipyridine以及錳金屬離子或銅金屬離子,進行水熱自組裝反應,可得到配位聚合物 3-5。以有機配子1,2-H2chdc和tptz與MnCl2•4H2O反應,在140 °C下得到化合物[Mn2(1,2-chdc)2(tptz)2(H2O)2] (3);以有機配子1,4-chdc和tptz與MnCl2•4H2O反應,在140 °C下反應得到化合物{[Mn2(1,4-chdc)2(tptz)2]•16H2O}n (4);以有機配子1,4-chdc和2,2'-bipyridine與Cu(NO3)2•3H2O反應,在140 °C下得到化合物{[Cu(1,4-chdc)(2,2 '-Bipy)]•1/3H2O}n (5)。 然而在化合物 3-5中,過渡金屬離子與tptz及2,2'-bipyridine配子反應,應實驗顯示當其皆採螯合方式參與配位,導致所形成之化合物可能成為單體或一維無限鏈狀的結構之化合物,化合物3為單體結構,另化合物 4和5則為一維結構。

並列摘要


(1)Synthesis of coordination polymers tuned by structure directing agent under hydrothermal conditions. The hydrothermal reaction of Co(NO3)2•6H2O with bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (btda) generates two unique 3D metal-organic framework (MOF) of {[Co2(hcc)2/3(H2O)2]•1.5H2O}n (1, H6hcc = 1,2,3,4,5,6-cyclohexanehexacarboxylic acid) and [Co3(hcc)(H2O)6]n (2) under hydrothermal conditions. Six carboxylato moieties of hcc ligand were generated in situ via the hydrolysis of two anhydride motifs and accompanied the opening-oxidation on the bridged double bound on the btda molecule. The hcc structure of 1 reveals two types of coordination modes coordinated to ten and six Co(II) atoms, respectively. While the hcc ligand of 2 coordinated only in one mode to nine Co(II) atoms. The local coordination environments of CoII centers of 1 and 2 are distinct, and have been tuned by the presence of a 4,4'-bipyridine molecule, which plays a vital role as a structure directing agent (SDA). (2)Synthesis of cyclohexanedicarboxylic acid with transition metal salts of coordination compounds under hydrothermal conditions. The use of cis-1,2-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid with different nitrogen-containing organic gametes 2,4,6-tris(2-pyridyl)-s-triazine or 2,2'-bipyridine and manganese metal ions or copper ions, affords three coordination polymers 3-5 under hydrothermal conditions. Mixing of 1,2-chdc, tptz and MnCl2•4H2O produced compound [Mn2(1,2-chdc)2(tptz)2(H2O)2] (3). A mixture of 1,4-chdc, tptz and MnCl2•4H2O reacted to form compound {[Mn2(1,4-chdc)2(tptz)2]•16H2O}n (4). While treatment of 1,4-chdc, 2,2'-bipyridine and Cu(NO3)2•3H2O led to the formaion of compound {[Cu(1,4-chdc)(2,2'-bipy)]•1/3H2O}n (5). Compounds 4 and 5 adopt 1D structure, and compound 3 exhibits a 0D structure. Both of ligands tptz and 2,2'-bipyridine in the compound 3-5 are coodinated to metal ions in a chelating coordination mode. It is formed as the result of the restricted crystal structures of compounds 4 and 5, and has an impact on their these ligands structure as 1D coodination polymers.

參考文獻


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