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標題: | 硫酮萘啶配基的三核鎳金屬串錯合物之合成、結構與磁性研究 Synthetic, Structural, and Magnetic Studies of Trinickel String Complexes Supported by Thione-naphthyridine Ligands |
作者: | Chien-Hung Cheng 鄭健鴻 |
指導教授: | 彭旭明 |
關鍵字: | 金屬串分子,三核鎳金屬串,硫酮?啶配基,反鐵磁作用,配位化學, Metal string,Trinickel metal string,Thione-naphthyridine ligand,Antiferromagnetism,Coordination chemistry, |
出版年 : | 2018 |
學位: | 碩士 |
摘要: | 本實驗室張惟程博士曾發表不對稱型萘啶酮配基Hnpo (Hnpo = 1,8-naphthyridin-2(1H)-one)的金屬串錯合物,與過去實驗室金屬串多氮配基不同的是此系列的金屬串錯合物是由配基上的氮、氮、氧原子與金屬進行配位。
在本篇研究中,將1,8-naphthyridin-2(1H)-one上萘啶的氧替換成硫,合成出氮、氮、硫系統的硫酮萘啶配基Hnpt (Hnpt = 1,8-naphthyridine-2(1H)-thione),之後將Ni(OAc)2與Hnpt進行高溫萘燒反應,加入LiCl及NaNCS做為軸向配基,可分別得到三核鎳金屬串錯合物[Ni3(npt)4(Cl)] (1)及[Ni3(npt)4(NCS)] (3)。3使用不同的養晶條件可得到不同的晶體結構3A及3B,由循環伏安法可知3有一組可逆的氧化還原對,位於E1/2 = 0.301 V。將1與3分別和[FeCp2](PF6)在CH2Cl2下反應,可以得到氧化一個電子後的產物[Ni3(npt)4(Cl)](PF6) (2)及[Ni3(npt)4(NCS)](PF6) (4),之後再將4和過量的NaNCS進一步反應,可以得到中性的雙邊軸向取代基錯合物[Ni3(npt)4(NCS)2] (5)。 經由超導量子干涉儀進行磁性量測及單晶繞射解析量測可知,在3中具有一個低自旋的Ni2+離子及一組高自旋(S = 3/2)的[Ni2]3+混價單元,在300 K時的有效磁矩為3.78 B.M.;在4中由三個Ni2+離子組成[Ni3]6+骨架,分別為兩個四配位低自旋與一個五配位高自旋電子組態 (S = 1) ,在300 K時的有效磁矩為2.91 B.M。而錯合物5的中心金屬骨架也是[Ni3]6+,兩端Ni2+離子為五配位高自旋電子組態 (S = 1),中間則是四配位低自旋電子組態的Ni2+離子,為一個反鐵磁性物質(J = -171.15 cm-1)。 Recently, it has been shown that the introduction of a planar NNO based ligand scaffold in metal string complexes plays a pivot role in boosting the single molecule conductance. Inspired by this study, herein we report the preliminary investigation on the novel trinickel string complexes [Ni3(npt)4(Cl)] (1) and [Ni3(npt)4(NCS)] (3) supported by NNS type ligand. The cyclic voltammetry of complex 3 exhibits only one-electron redox processes at E1/2 = 0.301 V. The one-electron oxidation species [Ni3(npt)4(Cl)](PF6) (2) and [Ni3(npt)4(NCS)](PF6) (4) can be synthesized by reacting 1 and 3 with one equivalent of [FeCp2](PF6) in CH2Cl2. The further reaction of 4 with NaNCS afford [Ni3(npt)4(NCS)2] (5). Base on X-ray studies and magnetic susceptibility measurements, 3 has a mixed-valent, high spin (S = 3/2) [Ni2]3+ unit within the metal framework. The magnetic measurements show that 3 is likely paramagnetic compound, and μeff = 3.78 B.M. at 300 K. The metal framework of 4 has a [Ni3]6+ core, is likely paramagnetic compound and μeff = 2.91 B.M., we assign that the terminal nickel ion which coordinate to the thiocyanate is high spin state (S = 1). Complex 5 likely antiferromagnetically coupled (J = -171.15 cm-1) with two terminal high spin Ni2+ (S = 1) ions and one diamagnetic low spin Ni2+ ion in the central position. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/69231 |
DOI: | 10.6342/NTU201801583 |
全文授權: | 有償授權 |
顯示於系所單位: | 化學系 |
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