- 學位論文
含吡啶之錳配位聚合物的自組裝合成、結構與磁性探討
Self-Assembly, Structures and Magnetic Properties of Pyridine-Containing Manganese-Based Coordination Polymers
摘要
(一)水熱自組裝合成含 pyridine 與carboxylate之配位化合物(1-3) 利用兩種有機配子4'-(4-carboxyphenyl)-2,2':6',2'-terpyridine與thiophene-2,5-dicarboxylic acid (TDCA)，分別與鎘和錳金屬離子，進行水熱法自組裝合成，得到化合物1-3，皆為配位化合物。取4'-(4-carboxyphenyl)-2,2':6',2'-terpyridine與氯化鎘反應，得到配位化合物{[CdCl(C22H14N6O4)]•3H2O}n (1)；以TDCA配子與氯化鎘反應，得到配位化合物{[Cd2(C22H14N6O4)2(C6H2O4S)]•3H2O}n (2)；以TDCA配子與氯化錳反應，得到配位化合物{[Mn2(C22H14N6O4)2(C6H2O4S)]•3H2O}n (3)。化合物2及3為三維八次互穿結構空間群為Pca21，其特殊的晶體構造屬於拓樸學中較少見的ThSi2 (ths) 結構，且目前具有ths結構的文獻中，最高互穿的次數為九次，而化合物2及3為八次互穿模式，在ths互穿中，排名屬於第二高。 (二)室溫自組裝合成配位化合物(4-8) 利用2,2'-bipyrimidine (2bpm) 和五種不同羧酸配子與錳金屬離子，以室溫擴散方式進行自組裝合成，得到配位化合物4-8。以potassium malonate配子反應，得到{[Mn2(2bpm)(C3H2O4)2(H2O)2]•3H2O}n (4)；以potassium succinate配子反應，得到[Mn2(2bpm)(C4H4O4)2(H2O)2(CH3OH)2]n (5) ；以potassium fumarate配子反應，得到{[Mn3(2bpm)(C4H2O4)3(H2O)6]•2H2O}n (6) ；以potassium terephthalate配子反應，得到[Mn2(2bpm)(C8H2O4)2(H2O)4]n (7) ；以potassium-1,3,5-benzenetricarboxylate (1,3,5-btc) 配子反應，得到{[Mn3(2bpm)(C9H3O6)2(H2O)8]•6H2O}n (8)。在第二個部分中，共得到五個配位化合物，在結構上化合物4、6和8為二維結構，化合物5和7為一維結構；除討論配位聚合物之結構外，並針對混不同長度的羧酸配子所產生的磁性影響，進一步做磁性探討，在磁性分析結果顯示化合物4-8皆具有反鐵磁性的特性。
並列摘要
(A) Synthesis of coordination polymers under hydrothermal conditions. Treatment of CdCl2•2.5H2O and MnCl4•4H2O with 4'-(4-carboxyphenyl)-2,2':6',2'-terpyridine or thiophene-2,5-dicarboxylic acid (TDCA) in aqueous solution under hydrothermal conditions led to the formation of coordination polymers {[CdCl(C22H14N6O4)]•3H2O}n (1), {[Cd2(C22H14N6O4)2 (C6H2O4S)]•3H2O}n (2), {[Mn2(C22H14N6O4)2(C6H2O4S)]•3H2O}n (3). Compounds 2 and 3 adopt a 8-fold interpenetrating three dimensional (3D) structure with ThSi2 (ths) topology.(B) Self-assembly of magnetic coordination polymers under room temperature. Treatment of MnCl4•4H2O with 2,2'-bipyrimidine (2bpm) and mixed five types of ligands under room temperature obtained five coordination polymers 4-8. Mixing of 2bpm and potassium malonate, potassium succinate, potassium fumarate, potassium terephthalate, or potassium-1,3,5-benzenetricarboxylate (1,3,5-btc) led to the formation of {[Mn2(2bpm)(C3H2O4)2(H2O)2]•3H2O}n (4), [Mn2(2bpm)(C4H4O4)2(H2O)2(CH3OH)2]n (5), [Mn3(2bpm)(C4H2O4)3(H2O)6]•2H2O}n (6), [Mn2(2bpm)(C8H2O4)2(H2O)4]n (7), {[Mn3(2bpm)(C9H3O6)2(H2O)8]•6H2O}n (8), respectively.Compounds 4、6 and 8 are 2D structures. Compounds 5 and 7 are 1D structures.The magnetic properties of compounds 4-8 were examined. Compounds 4-8 all are antiferromagnetic interaction.