本論文主要合成釓金屬的普魯士藍錯合物，得到四個以CN為架橋基4f-3d雙金屬錯合物及其單晶結構，
[Gd(DMF)3(o-phen)(H2O)2Fe(CN)6]2•H2O(1) 
[Gd(DMF)3(bpy)(H2O)Fe(CN)6]2•2H2O(2) 
[Gd(DMF)2(o-phen)(H2O)2Fe(CN)6]n•3nH2O•0.5n(DMF) (3)
[Gd(H2O)2Fe(CN)6]•2H2O (4)
其中錯合物1, 2, 3和4分別為異雙核，四核，一維及三維結構。在溫度範圍(2 - 300 K)測得這些透過CN架橋連接釓金屬與鐵(Ⅲ)錯合物的變溫磁化率，錯合物1, 2和3皆為反鐵磁性偶合作用，錯合物4在低溫下存在相轉移(phase – transition)，並在T = 6 K和16 K下測量磁化強度(M) (H = 0 - 5 T)，T = 16 K之實驗曲線符合基態總自旋量子數S = 3之理論曲線，但是T = 6 K之實驗曲線卻發現有兩個總自旋量子數，在低磁場下，符合S = 4之理論曲線，在高磁場下則符合S = 3之理論曲線。

Four novel cyano-bridged 4f-3d-metal complexes,       
    [Gd(DMF)3(o-phen)(H2O)2Fe(CN)6]2•H2O (1),
    [Gd(DMF)3(bpy)(H2O)Fe(CN)6]2•2H2O(2),     
    [Gd(DMF)2(o-phen)(H2O)2Fe(CN)6]n•3nH2O•0.5n(DMF) (3),
    [Gd(H2O)2Fe(CN)6]•2H2O (4), 
have been prepared and X-ray structural characterization. There are found that complexes 1, 2, 3 and 4 are dinuclear, trteanuclear, 1-D nd 3-D network structures, respectively. The temperature ( 2 – 300 K ) dependence of magnetic susceptibility measurements of these Gd3+-NC-Fe3+ complexes shown that complexes 1, 2 and 3 are antiferromagnetic interactions,complexes 4 at low temperature exhibits phase-transition. The field dependence ( 0 - 5 T ) of the magnetization of 4 measured at 6 K and 16 K show saturation of the magnetization. At T = 16 K curve shown correspond to total spin of ground state ST = 3, however, at T = 6 K curve shown two total spin states, one correspond to ST = 4 at low field and the other correspond to ST = 3 at high field.

目錄..............................................І
圖索引...........................................Ⅲ
表索引...........................................Ⅶ

第一章  緒論......................................1
1-1.  前言...............................................1
1-2.  分子磁性材料.......................................3
1-3.  CN– 架橋基配位.....................................8
1-4.  [MIII(CN)6]3– 共振式...............................10
1-5.  光激發............................................12
1-6.  普魯士藍錯合物....................................14
1-7.  鑭系金屬[M(CN)6]3-錯合物...........................19
1-8.  研究動機及目的....................................42
第二章  實驗與數據分析...........................43
2-1.  合成..............................................43
2-1-1.  合成錯合物....................................43
2-1-2.  使用試劑......................................44
2-1-3.  雙金屬錯合物之合成方法........................45
2-2.  物質分析與物化性測定..............................47
2-2-1.  使用儀器......................................47
2-3.  原理與數據處理....................................48
2-3-1.  紅外線光譜....................................48
2-3-2.  元素分析數值..................................50
2-3-3.  晶體結構解析..................................51
2-3-4.  磁性..........................................52
第三章  結果與討論...............................55
3-1. 異雙核 [Gd(DMF)3(o-phen)(H2O)2Fe(CN)6]2•H2O(1)..55
3-2. 環狀四核 [Gd(DMF)3(bpy)(H2O)Fe(CN)6]2•2H2O(2)...64
3-3. 一維結構
     [Gd(DMF)3(o-phen)(H2O)Fe(CN)6]2•8H2O•(DMF)(3)..73
3-4. 三維結構 [Gd(H2O)2Fe(CN)6]•2H2O (4) ............83
第四章  結論.....................................98
參考文獻.........................................100
附錄A.  單晶結構原始資料表及鍵長(Å)與鍵角(°).....107
附錄B.  變溫磁性數據原始資料....................128
附錄C.  變磁場磁性數據原始資料..................135

圖 索 引
圖1-2-1. 	磁作用表現圖................................4
圖1-3-1. 	[BIII(CN)6]3– 形成雙金屬複錯合物之三維架構.....9
圖1-4-1. 	[Fe(CN)6]3- 共振穩定式.......................10
圖1-4-2. 	雙核磁軌域作用圖...........................10
圖1-4-3(a). t2g eg正交作用圖.............................11
圖1-4-3(b). t2g重疊作用圖...............................11
圖1-5-1. 	Co[Fe(CN)6]經照光改變spin方向圖............12
圖1-5-2. 	逆磁Fe(II)-Co(III)照光形成鐵磁性Fe(III)-Co(II)..13
圖1-5-3. 	Ni(II)[Fe(II)(CN)5NO]光激發產生磁自旋偶合.......13
圖1-6-1.	普魯士藍的單位晶格圖.......................14
圖1-6-2.	普魯士藍分子軌域作用圖.....................15
圖1-6-3.	[Nd(DMF)4(H2O)3(μ-CN)Fe(CN)5•H2O]磁性性質圖18
圖1-7-1.	[LaFe(CN)6∙5H2O]結構圖......................20
圖1-7-2.	[Sm Fe(CN)6]異雙核錯合物單晶結構及Sm(Ⅲ)離子配
          位圖                                      21
圖1-7-3.	[SmFe]單晶結構及磁性性質圖.................21
圖1-7-4.	[HoFe]單晶結構及磁性性質圖.................22
圖1-7-5.	Gd(Ⅲ)及[Cr(CN)6]3-四核及一維鍊狀結構圖......22
圖1-7-6.	[LnFe(CN)6]單晶結構及磁性性質圖[Ln = Sm、Gd、
          Dy] ......................................23
圖1-7-7.	Sm2Fe2單晶結構圖及構形.....................24
圖1-7-8.	Dy2Fe2單晶結構圖及構形.....................24
圖1-7-9.	Sm2Fe2磁性性質圖...........................25
圖1-7-10.	Dy2Fe2磁性性質圖...........................25
圖1-7-11.	[Ce3+ - Co3+]單晶結構及氫鍵作用示意圖.........26
圖1-7-12.	[Yb3+ - Fe3+]單晶結構及xy平面鏈狀堆疊圖......27
圖1-7-13.	[Gd3+ - Fe3+] yz平面堆疊及π-π作用示意圖......28
圖1-7-14.	[Sm3+ - Fe3+]磁性表現圖.......................28
圖1-7-15.	[Gd3+ - Fe3+]磁性表現圖.......................29
圖1-7-16.	[Nd3+ - Co3+]單晶結構及Nd(Ⅲ)離子配位圖.......30
圖1-7-17.	[Ln3+ - Co3+]磁性表現及分子間氫鍵示意圖.......30
圖1-7-18.	[Tb3+ - Fe2+]單晶結構及2-D結構圖..............31
圖1-7-19.	[Sm3+ - Fe2+]單晶結構及1-D結構圖.............32
圖1-7-20.	[Tb3+ - Fe2+]磁性表現圖........................32
圖1-7-21.	[Nd3+ - Fe3+]單晶結構圖.......................33
圖1-7-22.	[Nd3+ - Fe3+]氫鍵作用示意圖...................34
圖1-7-23.	[Sm3+ - Fe2+]π-π作用示意圖..................34
圖1-7-24.(a)[Nd3+ - Cr3+]單晶結構圖....................35
圖1-7-24. b)[Nd3+ - Cr3+] 1-D鏈狀結構圖.................35
圖1-7-25. a)[Nd’3+ - Cr3+]單晶結構圖...................36
圖1-7-25. b)[Nd’3+ - Cr3+] 1-D鏈狀結構圖...............36
圖1-7-26. (a) (b) (c)[La3+ - Cr3+]氫鍵作用示意圖........37
圖1-7-26. d)[La3+ - Cr3+]π-π作用示意圖.................37
圖1-7-27. (a) (b) (c) (b)[Ho3+ - Cr3+]氫鍵作用示意圖...38
圖1-7-28.	[Sm3+ - Fe3+]單晶結構及一維鏈狀結構圖.........40
圖1-7-29. [Nd’3+ - Cr3+]堆疊圖........................41
圖1-7-30.	[Sm3+ - Fe3+]磁性表現圖.......................41
圖3-1-1. 	Complex (1)單晶結構圖.......................54
圖3-1-2.	Complex (1) Gd金屬中心八配位圖..............58
圖3-1-3.	Complex (1)單位晶格堆積圖...................59
圖3-1-4.	Complex (1)沿a軸觀察分子間作用示意圖.......59
圖3-1-5.	Complex (1)分子內氫鍵作用示意圖.............60
圖3-1-6.	Complex (1)莫耳磁化率與溫度乘積(χMT)對溫度(T)
         作圖.......................................63
圖3-2-1.	Complex (2)單晶結構圖.......................66
圖3-2-2.	Complex (2) Gd金屬中心八配位圖..............67
圖3-2-3.	Complex (2)單位晶格堆積圖...................68 
圖3-2-4.	Complex (2)分子間作用示意圖.................68
圖3-2-5.	Complex (2)分子內氫鍵作用示意圖.............69
圖3-2-6.	Complex (2)莫耳磁化率與溫度乘積(χMT)對溫度(T)
         作圖.......................................72
圖3-3-1.	Complex (3)單晶結構圖.......................75
圖3-3-2.	Complex (3) Gd金屬中心八配位圖..............76
圖3-3-3.	Complex (3)單位晶格堆積圖...................77
圖3-3-4.	Complex (3)一維鏈狀結構圖...................77
圖3-3-5.	Complex (3)分子間作用示意圖.................78
圖3-3-6.	Complex (3)π-π堆疊作用示意圖..............79
圖3-3-7.	Complex (3)莫耳磁化率與溫度乘積(χMT)對溫度(T)
         作圖.......................................82
圖3-4-1.	Complex (4)單晶結構圖.......................85
圖3-4-2.	Complex (4) Gd3+及Fe3+配位環境結構圖.........86
圖3-4-3.	Complex (4) 3-D結構圖.......................87
圖3-4-4.	Complex (4) Gd3+金屬中心八配位圖.............87
圖3-4-5.	Complex (4)單位晶格堆積圖...................88
圖3-4-6.	Complex (4) 3-D結構氫鍵作用示意圖...........89
圖3-4-7.	Complex (4) H = 1 T莫耳磁化率與溫度乘積(χMT)對
         溫度(T)作圖......... .......................93
圖3-4-8.	complex(4)莫耳磁化率(χM)及(χM) -1對溫度( T )作圖
          ...........................................94
圖3-4-9.	Complex (4) H = 0.5 T莫耳磁化率與溫度乘積(χMT)
         對溫度(T)作圖...............................95
圖3-4-10.	Complex (4) T = 16 K磁化強度( M )對外加磁場(βH )
         作圖.......................................96
圖3-4-11.	Complex (4) T = 6 K磁化強度( M )對外加磁場(βH )
         作圖.......................................97

表 索 引
表1-6-1.	普魯士藍的錯合物的發展.......................16
表1-7-1.	Ln3+ - Fe3+間磁性作用..........................27
表1-7-2.	Ln3+ - Cr3+間磁性作用..........................39
表2-3-1-1.	IR光譜吸收特性........................49
表2-3-2-1.	元素分析數值...........................50
表2-3-4-1.	巴斯卡常數表..........................53
表2-3-4-2.	理論XMT值相關數值...................54
表3-1-1.	Complex (1)的單晶基本資料....................58
表3-1-2.	Complex (1)主要鍵長(Å)與鍵角(°).....61
表3-1-3.	Complex (1)分子間作用鍵長(Å) ................61
表3-2-1.	Complex (2)單晶基本資料......................67
表3-2-2.	Complex (2)主要鍵長(Å)與鍵角(°).....70
表3-2-3.	Complex (2)分子間作用鍵長(Å) ................70
表3-3-1.	Complex (3)單晶基本資料......................76
表3-3-2.	Complex (3)主要鍵長(Å)與鍵角(°).....80
表3-3-3.	Complex (3)分子間作用鍵長(Å) ................80
表3-4-1.	Complex (4)單晶基本資料......................90
表3-4-2.	Complex (4)主要鍵長(A)與鍵角(°).....91

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