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  • 學位論文

新型四氮配基及其混配基之直線型四核金屬串錯合物之合成與研究

Syntheses and Studies of Novel Tetradentate Nitrogen Ligands (Hnyqa) and Their Mixed Ligand Linear Tetranuclear Metal String Complexes

指導教授 : 彭旭明

摘要


本論文研究內容為奈啶奎林胺(Hnyqa)與修飾官能基的二吡啶二胺(H2npdpda,H2andpda)配基之三核鎳金屬簇錯合物、單核錯合物、和混配基四核鎳金屬串錯合物之合成、結構分析、磁性及其電子吸收光譜之探討。 利用鈀錯合物當催化劑,合成出三個新型的非對稱性配基,經由1H NMR與快速原子撞擊質譜(FAB-MS)確認配基的組成。 在高溫萘燒反應條件下,Hnyqa配基與鎳金屬離子會形成三核鎳金屬簇錯合物[Ni3(nyqa)4Cl2];同樣地在高溫萘燒反應條件下,Hnyqa配基和H2npdpda配基(或H2andpda配基)也可成功得到混配基四核鎳金屬串錯合物[Ni4(μ4-npdpda)3(μ4-nyqa)(NCS)]和[Ni4(μ4-andpda)3(μ4-nyqa)(NCS)],由X-ray 單晶繞射解析可知,Hnyqa配基和H2npdpda配基(或H2andpda配基)以全順向式之配位模式與鎳離子鍵結。 磁性結果得知,三核鎳金屬簇錯合物為鐵磁性物質,三個鎳金屬皆為高自旋狀態(S = 1);經由公式的擬合,可以得到相鄰鎳離子與鎳離子之間的偶合常數(J)為+2.43 cm-1;混配基四核鎳金屬串錯合物的金屬串皆為順磁的分子,其具有軸向配基的鎳金屬為高自旋態(S = 1),其餘鎳金屬皆為低自旋態(S = 0)。 經由循環伏安法發現,混配基四核鎳金屬串錯合物皆有三組氧化峰,其氧化電位介於0.339-0.955 V。   我們成功利用混配基的組裝方式得到四核鎳金屬串錯合物,進行電化學及磁性的性質探討;此外,以Hnyqa配基與鎳金屬反應得到的三核鎳金屬簇錯合物為本實驗室系統中較少見的鐵磁性物質。

關鍵字

金屬串 萘啶 奎林

並列摘要


The aim of this thesis is to investigate the synthesis, structures and properties of the new trinickel cluster, mononuclears and the new linear tetranickel complexes with two kinds of ligands, where the ligands are the three unsymmetrical ligands, 2-1,8-naphthyridyl-2’-inolinylamine (Hnyqa),N-(2-naphthalenyl)diaminodipyridine (H2npdpda), and N-(anisyl)diaminodipyridine (H2andpda). The three unsymmetrical ligands were synthesized by the palladium-catalyzed crosscoupling reaction. The ligands were characterized on the base of 1H NMR spectroscopy and mass spectrometry. [H2nyqa(ClO4)] (1), [Cu(μ2Hnyqa)2(MeOH)2](ClO4)2 (2), [Co(μ2-Hnyqa)2](BF4)2 (3), the new trinickel cluster [Ni3(nyqa)4Cl2] (4), [Ni4(μ4-npdpda)3(μ4-nyqa)(NCS)] (5) and[Ni4(μ4-andpda)3(μ4-nyqa)(NCS)] (6) were synthesized and characterized by X-ray crystallography. The framework of both complexes 5 and 6 are supported by two kinds of ligands. The magnetic susceptibility shows that complex 4 is ferromagnetic and the coupling constant is + 2.43 cm-1 and complexes 5 and 6 are paramagnetic. Cyclic voltammetrical data show that complexes 5 and 6 exhibits three quasireversible oxidation waves between 0.339-0.955 V. The complexes 1-6 were synthesized and characterized by X-ray crystallography, SQUID experiment and cyclic ammetrical method. The complex 4 is weak ferromagnetic; Complexes 5 and 6 can be easily oxidized. The oxidation potential (Eox) in complex 5 shifts to higher potential as compared with complex 6, because complex 6 have stronger electron donating function group than complex 5 .

並列關鍵字

metal string pyridine quinoline

參考文獻


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