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標題: | 三吡啶二胺配基之四核異金屬(鈷/鎢及鎳/鉬)串錯合物的合成及研究 Synthesis and Characterization of a series of Tetranuclear Heterometallic (Co/W and Ni/Mo)String Complexes with Tripyridyldiamino Ligand |
作者: | I-An Chen 陳奕安 |
指導教授: | 彭旭明(Shie-Ming Peng) |
關鍵字: | 三?啶二胺,混金屬,異金屬,金屬串, Tripyridyldiamino Ligand,Heterometallic,Metal string, |
出版年 : | 2014 |
學位: | 碩士 |
摘要: | 本論文為利用三吡啶二胺為配基(Tripyridyldiamino ligand 簡稱H2tpda)與6B 以及9B ˴ 10B金屬在高溫萘燒法條件下進行反應,成功合成出不對稱四核混金屬串錯合物[CoWCo2(μ5-tpda)4(Cl)2](BF4) (1)、 [CoWCo2(μ5-tpda)4(Cl)2] (2)、[CoWCo2(μ5-tpda)4(NCS)2](PF6) (3)以及[Mo2Ni2(μ5-tpda)4(Cl)(O)](PF6) (4)。並對這類含八配位構型之金屬串錯合進行其結構、磁性及電化學進行探討。
由X-ray單晶繞射解析可知,所有產物皆是以四片tpda2- 配基以全順向式之模式螺旋纏繞在四個金屬離子外圍,中間的鉬˴鎢金屬離子是以四方反稜柱的配位模式與氮原子鍵結,其他的鈷˴鎳金屬離子則是平面四方以及四角的配位構型。中間的鉬、鎢與旁邊金屬的距離大於3.0 A,超過金屬單鍵的共價半徑,推斷其金屬間的作用力是非常弱的。 以超導量子干涉測量磁性,可知(1)、(3)在300K時的μeff為2.59及2.44 B.M ,推測(1) ˴(3)金屬電子自旋為 Co2+ (S = 1/2) ; W4+ (S = 0) ; Co25+ (S = 1/2),接近於純自旋理論μeff = 2.45 B.M。錯合物(2)的還原的電子應是位於雙核鈷的單元,因此推測其只有一個磁性中心Co2+ (S = 1/2),300 K時的μeff為2.01 B.M.,接近於純自旋理論的 1.73 B.M。錯合物(4)在300 K時的μeff為3.04 B.M ,推測其自旋組態為Mo4+(1) (S = 0) ; Mo4+ (2) (S = 0) ; Ni2+(1) (S = 0) ; Ni2+(2) (S = 1),接近於純自旋理論μeff = 2.83 B.M.。 A series of tetranuclear heterometallic string complexes, [CoWCo2 (μ5-tpda)4(Cl)2](BF4) (1) , [CoWCo2(μ5-tpda)4(Cl)2] (2) , [CoWCo2 (μ5-tpda)4(NCS)2](PF6) (3) and [Mo2Ni2(μ5-tpda)4(Cl)(O)](PF6) (4) (tpda = tripyridyldiamino anion) were synthesized and characterized. The X-ray structural studies showed that all of them are helically wrapped by four all syn type H2tpda ligand, and have one 6B metal ion with square anti-prismatic geometry chelated by one pyridine N atom and the amido N atom of each of tpda2-. Axial ligands Cl- and NCS- are bonded to two Co ions for (1), (2) and (3), Cl- and O2- are bonded to Ni and Mo for (4). The distance between the middle 6B and nearby metal is larger than 3.0 A , which is elongated beyond the single-bond covalent radii of the metal atoms. The magnetic susceptibility showed that the μeff values of (1), (2), (3) and (4) at 300K are 2.59 , 2.44 and 2.01 B.M. respectively. The spin state of (1), (3) are the same, with Co2+ (S = 1/2), W4+ (S = 0), Co25+ (S = 1/2) configuration, which is close to the spin-only value 2.45 B.M. (2) is Co2+ (S = 1/2), W4+ (S = 0), Co2+(2) = Co2+(3) (S = 0) ,which is close to (1.73 B.M.) of spin-only value. The μeff of (4) is 3.04 B.M. , corresponding to Mo4+(1) (S = 0) , Mo4+ (2) (S = 0) , Ni2+(1) (S = 0) ; Ni2+(2) (S = 1) spin state. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/57203 |
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顯示於系所單位: | 化學系 |
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