臺灣博碩士論文加值系統

我們成功合成出新的有機配子6-hydroxymethyl-pyridine-2-carbaldehyde-oxime ( H2hpco )，並以此合成出新的錳金屬簇[Mn2(hpco)2(DMF)2Cl2] (1)，並對結構性質進行探討。
利用已知配子N-(2-Pyridylmethyl)imino diethanol( H2pmide )合成3d-4f的三核混金屬簇化合物[MnLn2](Ln=Dy、Gd)，結果不如預期，因此將Ln金屬置換成過渡金屬Cu，並以此合成出新的混過渡金屬簇[MnCu2(pmideH)2(OAc)4]‧3CH3OH (2)，並對結構進行探討。
另外，以文獻上已知的配子2,3,5,6-tetrakis(2-pyridinyl)pyrazine( tppz )、2,6-bis(hydroxymethyl)-4-Methylphenol ( L )，並合成出新的一維金屬串鏈雙核鈷金屬簇{[Co2(tppz)(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3)以及合成出新的混過渡金屬簇化合物[MnIII12CaII7(HL)
12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6](MeO)2 (4)，並對結構性質和磁性測量進行探討。化合物(3)在直流磁場變溫磁化率的測量中得知為反鐵磁性偶合，以及在交變磁化率的測量中也沒有任何訊號產生，表示不具有單分子磁鐵的特性。化合物(3)結構中含有被配位或自由溶劑客分子所佔據的一維孔道。化合物(4)雖然在直流磁場變溫磁化率的測量中得知為鐵磁性偶合，但是在交變磁化率的測量中也沒有任何訊號產生，表示不具有單分子磁鐵的特性。

We had successfully synthesized a new organic ligand 6-hydroxymethyl-pyridine-2-carbaldehyde-oxime ( H2hpco ), and to create new manganese metal cluster [Mn2(hpco)2(dmf)Cl2]2 (1), and the structure properties were discussed.
On the other hand, synthesis of 3d-4f trinuclear mixed-metal complexes [MnLn2] (Ln = Dy, Gd ) with using known N-(2-Pyridylmethyl)imino diethanol( H2pmide ) lignad, but results isn’t expected. Therefore we replaced metal Ln to transition metal Cu, and synthesized a new trinuclear compound [MnCu2(pmideH)2(OAc)4]‧3CH3OH (2), and the structure were discussed.
We also use the orgnaic lignad 2,3,5,6-tetrakis(2-pyridinyl)pyrazine( tppz )、2,6-bis(hydroxymethyl)-4-Methylphenol(L) to create new one dimensional chain dinuclear coordinate polymer{[Co2(tppz)(DMF)2(Cl)2](ClO4)2‧1DMF}n (3) as well as the synthesis of new mixed transition metal compounds [MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6](MeO)2 (4), and the structure properties and magneticmeasurement are discussed.
Compound (3) was antiferromagnetic coupling in the dc magnetic susceptibility. The ac magnetic susceptibility measurements of the compound (3) didn’t show anyout-of-phase signals, which was not a single molecule magnet.Compound (3) contains the coordinated ligand or free guest solvent molecules to form the one-dimensional channel.Compounds (4) which was ferromagnetic coupling in the dc magnetic field measurement susceptibility.The ac magnetic susceptibility measurements of the compound(4) didn’t show any out-of-phase signals,which was
not a single molecule magnet.

目錄
第一章‧前言 1
1-1簡介 1
1.2介紹 3
第二章‧實驗部分 6
2.1研究目標 6
2.2有機配子的選擇 7
2.3實驗步驟 9
2-2實驗藥品 13
2-3實驗儀器 14
第三章‧結果與討論 16
3-1單晶結構分析與討論 16
3-1-1[Mn2(hpco)2(DMF)2Cl2] (1) 16
3-2-1[MnCu2(pmideH)2(OAc)4]‧3CH3OH (2) 20
3-3-1{[CoII2(tppz)(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3) 24
3-4-1[MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6]‧2MeO (L=2,6-bis(hydroxyl-methyl)-4-methylphenol) (4) 33
3.2 直流磁場磁化率和約化磁化測量 40
3.2-1{[CoII2(pdm)4(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3) 40
3.2-2[MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2 (MeOH)6] (4) 44
3.3 交流磁化 46
3.3-1{[CoII2(pdm)4(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3) 46
3.3-2[MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6] (4) 47
第四章‧結論 48
第五章‧參考文獻 50
第六章‧附錄 53
第七章‧附表 59


 
圖目錄
圖 1[Mn2(hpco)2(DMF)2Cl2] (1) (a)有機配子的連接模式 (b)氯配位和μ-O橋接模式 (c)氧原子配位，紅色為O、淡藍色為N、綠色為Cl、紫色為Mn。 16
圖 2[Mn2(hpco)2(DMF)2Cl2] (1)的ORTEP晶體結構圖 17
圖 3[MnCu2(pmideH)2(OAc)4]‧3CH3OH (2) (a)有機配子的連接模式 (b)μ-O橋接模式 (c)氧原子配位，紅色為O、淡藍色為N、紫色為Mn、橘色為Cu。 20
圖 4[MnCu2(pmideH)2(OAc)4]‧3CH3OH (2)的ORTEP晶體結構圖 21
圖 5 [CoII2(tppz)(DMF)2(Cl)2]‧2ClO4‧1DMF(3)單晶ORTEP晶體結構圖 24
圖 6 {[CoII2(tppz)(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3)ORTEP晶體結構圖 25
圖 7 (3)粉末單晶繞射圖譜 25
圖 8 tppz有機配子配位模式 26
圖 9 tppz有機配子平面夾角 27
圖 10 化合物3 一維長鏈結構示意圖 28
圖 11 金屬串鏈與DMF的配位關係 28
圖 12 二維平面示意圖(a軸) 29
圖 13 三維結構示意圖 29
圖 14 三維結構一維孔道差異圖 30
圖 15 Co1、Co2配位模式示意圖 30
圖 16 [MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6]‧2MeO (L=2,6-bis(hydroxyl-methyl)-4-methylphenol) (4)的結構圖，深紫色為MnIII、藍綠色為CaII、紅色為O、灰色為C、綠色為Cl。 33
圖 17 [MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6]‧2MeO (L=2,6-bis(hydroxyl-methyl)-4-methylphenol) (4)的ORTEP晶體結構圖 34
圖 18 化合物4 a)金屬鈣配位模式b)金屬錳配位模式，藍綠色為鈣、淡紫色為錳、綠色為氯、紅色為氧 35
圖 19 [MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6]‧2MeO(4) 36
圖 20 中心金屬橋接O(1)、O(4)示意圖 38
圖 21 {[CoII2(pdm)4(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3)直流磁場變溫磁化率測量在5K~300K以及固定頻率1000Hz下 40
圖 22 化合物3 縱軸為磁化率倒數、橫軸為溫度作圖，紅色實線為Curie-Weiss law best fit、虛線圖案為實驗值 41
圖 23 {[CoII2(pdm)4(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3)直流磁場變溫磁化率測量 42
圖 24 {[CoII2(pdm)4(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3)約化磁化圖譜 43
圖 25[MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2 (MeOH)6] (4)直流磁場磁化率測量 44
圖 26 [MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6] (4) 約化磁化圖譜 45
圖 27 {[CoII2(pdm)4(DMF)2(Cl)2]‧2ClO4‧1DMF}n (3)交流磁化率測量 46
圖 28[MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6] (4)交流磁化率測量 47




表目錄
表 1錳金屬離子與周邊原子鍵長(Ǻ)與鍵角(°) 18
表 2 BVS公式中ri文獻上的參數 19
表 3 BVS鑑定化合物[Mn2(hpco)2(DMF)2Cl2] (1)金屬氧化態 19
表 4銅錳金屬離子與周邊原子鍵長(Ǻ)與鍵角(°) 22
表 5 BVS公式中ri文獻上的參數 23
表 6 BVS鑑定化合物[MnCu2(pmideH)2(OAc)4]‧3CH3OH (2)金屬氧化態 23
表 7鈷金屬離子與周邊原子鍵長(Ǻ)與鍵角(°) 31
表 8 BVS公式中ri文獻上的參數 32
表 9 BVS鑑定[CoII2(tppz)(DMF)2(Cl)2]‧2ClO4‧1DMF (3)金屬氧化態 32
表 10 BVS公式中ri文獻上的參數 37
表 11 BVS鑑定化合物[MnIII12CaII7(HL)12(µ4-O)8(µ3-Cl)6(µ3-MeO)2(MeOH)6]‧2MeO (4)金屬氧化態 37
表 12化合物(1)~(7)橋接O(1)與O(4)時鍵長(Ǻ)與鍵角(°)關係 39

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