淡江大學覺生紀念圖書館 (TKU Library)
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系統識別號 U0002-1807201315472700
中文論文名稱 草醯胺架構的鈷、鎳、銅、鋅金屬液晶之合成與性質
英文論文名稱 New Metallomesogens Based on Oxamide Scaffold with Co(II), Ni(II), Cu(II), and Zn(II) ion: Synthesis, Characterizations and Mesogenic Properties
校院名稱 淡江大學
系所名稱(中) 化學學系碩士班
系所名稱(英) Department of Chemistry
學年度 101
學期 2
出版年 102
研究生中文姓名 宋文德
研究生英文姓名 Wen-De Sung
學號 600160070
學位類別 碩士
語文別 中文
口試日期 2013-07-11
論文頁數 199頁
口試委員 指導教授-王文竹
委員-林志彪
委員-賴重光
中文關鍵字 金屬液晶  草醯胺 
英文關鍵字 metallomesogens  oxamide  Co(II),Ni(II),Cu(II),and Zn(II) complex 
學科別分類 學科別自然科學化學
中文摘要 以草醯胺為中心架構,與不同碳數、鏈數的柳醛行縮合反應,合成出具有席夫鹼 ( Schiff-bass ) 官能基的化合物,分別為1Cn-epnom、2Cn-epnom與3Cn-epnom,並與鈷、鎳、銅、鋅金屬離子配位形成錯合物[M2(mCn-epnom)]。利用氫譜、質譜、元素分析及單晶分析對結構及純度作初步的鑑定。
藉由偏光顯微鏡、示差掃描卡計及變溫粉末X-ray繞射光譜來瞭解化合物在不同溫度下的液晶性質。其實驗結果顯示於化合物2Cn-epnom ( n = 14, 16 )具有Colh液晶相,但其液晶相範圍只有3~5℃,而其他1Cn-epnom與3Cn-epnom均為固相或軟固體。錯合物[M2(1Cn-epnom)]、[M2(2Cn-epnom)]與[M2(3Cn-epnom)]均呈現不同的液晶相,[M2(1Cn-epnom)] ( M = Co, Ni, Cu, Zn )為Smectic X液晶相,[M2(2Cn-epnom)] ( M = Co, Ni, Cu )為Colh液晶相,但[Zn2(2Cn-epnom)]卻為Smectic X 液晶相, [M2(3Cn-epnom)] ( M = Co, Ni, Cu, Zn )均為lamellar 液晶相。最後,透過變溫磁化率量測得知雙核銅錯合物在0~75 K時為鐵磁性,而75~373K為反鐵磁性。
英文摘要 Three series of molecules with new scaffold, in which two salicylaldimine groups are linked by an oxamide core, were studied. The synthesis, characterizations and mesogenic properties of these Schiff-base compounds and their dinuclear Co(II), Ni(II), Cu(II), and Zn(II) complexes is reported. The elemental analysis and spectroscopic (NMR, Mass, Uv-vis, and FT-IR) have been employed to investigate these compounds.
The mesogenic behaviors of three series of oxamide-core ligands (1Cn-epnom = L1n, 2Cn-epnom = L2n, 3Cn-epnom = L3n) and their dinuclear Co(II), Ni(II), Cu(II), and Zn(II) complexes were explored by polarized optical microscope (POM), differential scanning calorimetry (DSC), and powder X-ray diffraction (PXRD) in variable temperature. Most of theses compounds in the series of 2Cn-epnom and [M2(2Cn-epnom)] displayed columnar hexagonal phase. The complexes [M2(3Cn-epnom)] exhibited lamellar phase, and the complexes [M2(1Cn-epnom)] exhibited smectic X phase.
Finally, variable temperature magnetic susceptibility measurements of dinuclear copper(II) complexes showed ferromagnetism in 0~75K range and anti-ferromagnetism in 75~273K range.
論文目次 中文摘要......................................................................................................................I
英文摘要....................................................................................................................II

第一章 緒論
1-1 液晶的簡介………….……………..............………………………………1
1-2 液晶的基本架構…………………………………………......……..……....3
1-3 氫鍵液晶.............................……………...……………………....…………5
1-3-1 金屬液晶之特性…………………………………………………….....5
1-3-2金屬液晶之回顧………………………………………………………..5
1-4 金屬液晶.............................……………...……………………........……..10
1-5 實驗設計…………………………………………………………….......14

第二章 實驗
2-1 實驗材料………………. ……………………………………...…………17
2-2 儀器設備............................. ……...……………………………............…18
2-3 合成流程圖…………………………………...…………………………..21
2-4 化合物的合成...…......................... ……...……………………………… 23
2-4-1化合物Methyl 3,4,5-tris(alkyloxy)benzoate的合成…….……….…..23
2-4-2化合物Ethyl 3,4-bis(alkyloxy)benzoate的合成………….…...…..…..24
2-4-3化合物Methyl 4-(alkyloxy)benzoate的合成……….…………….…..25
2-4-4化合物3,4,5-tris(alkyloxy)benzoic acid的合成………...……………26
2-4-5化合物3,4-bis(alkyloxy)benzoic acid的合成…………….....................27
2-4-6化合物4-(alkyloxy)benzoic acid的合成…............................................ 29
2-4-7化合物4-formyl-3-hydroxyphenyl 3,4,5-tris(alkyloxy)benzoate
的合成……….....................................................................................…30
2-4-8化合物4-formyl-3-hydroxyphenyl 3,4-bis(alkyloxy)benzoate
的合成…............................................................................…………….32
2-4-9化合物4-formyl-3-hydroxyphenyl 4-(alkyloxy)benzoate
的合成.…........................................................................…..........…...34
2-4-10化合物N1,N2-bis(3-aminopropyl)oxalamide
的合成...…............................................................................................35
2-4-11化合物N1,N2-bis(3-(3,4-bis(alkyloxy)benzylideneamino)-
propyl)oxalamide的合成..................................................................…36
2-4-12化合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)bis(3-hydroxy-4,1-phenylene)bis(3,4,5-tris(alkyloxy)-
benzoate)的合成…...........................................................................…37
2-4-13化合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)bis(3-hydroxy-4,1-phenylene)bis(3,4-bis(alkyloxy)-
benzoate)的合成…...........................................................................…38
2-4-14化合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)bis(3-hydroxy-4,1-phenylene)bis(4-(alkyloxy)-
benzoate)的合成…...........................................................................…40
2-4-15錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-
1,13-diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(3,4,5-
tris(alkyloxy)benzoate)dicobalt(II)的合成......................................…41
2-4-16錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(3,4,5-tris(alkyloxy)-
benzoate)dinickel(II)的合成.........................................................…...42
2-4-17錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(3,4,5-tris(alkyloxy)-
benzoate)dicopper(II)的合成...........................................................…43
2-4-18錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(3,4,5-tris(alkyloxy)-
benzoate)dizinc(II)的合成...............................................................…44
2-4-19錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(3,4-bis(alkyloxy)-
benzoate)dicobalt(II)的合成............................................................…46
2-4-20錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(3,4-bis(alkyloxy)-
benzoate)dinickel(II)的合成.............................................................…47
2-4-21錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(3,4-bis(alkyloxy)-
benzoate)dicopper(II)的合成...........................................................…48
2-4-22錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(3,4-bis(alkyloxy)-
benzoate)dizinc(II)的合成....................................................................49
2-4-23錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(4-(alkyloxy)-
benzoate)dicobalt(II)的合成.............................................................…50
2-4-24錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(4-(alkyloxy)-
benzoate)dinickel(II)的合成............................................................…51
2-4-25錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(4-(alkyloxy)-
benzoate)dicopper(II)的合成............................................................…52
2-4-26錯合物4,4'-((1Z,13Z)-7,8-dioxo-2,6,9,13-tetraazatetradeca-1,13-
diene-1,14-diyl)-bis(3-hydroxy-4,1-phenylene)bis(4-(alkyloxy)-
benzoate)dizinc(II)的合成................................................................…53

第三章 結果與討論
3-1化合物之結構鑑定………….……........………………..…....................… 55
3-1-1核磁共振光譜………………………………………………………......55
3-1-2質譜………………………………………………….......………….…..63
3-1-3元素分析……………………………………………….......…………..66
3-1-4單晶X-ray結構…………………………………………………..……68
3-2化合物2Cn-pnom ( n = 10, 12, 14, 16 ) 液晶性質探討………….….....… 72
3-2-1化合物光學紋理之探討……………………………………..…….......72
3-2-2化合物熱分析之探討……………………………………………….....73
3-2-3化合物變溫粉晶繞射之探討………………………………………….74
3-2-4化合物2Cn-epnom討論……………………………………………….75
3-3化合物3Cn-epnom ( n = 10, 12, 14, 16 ) 液晶性質探討………….……. 76
3-3-1化合物光學紋理之探討……………………………………..…....……76
3-3-2化合物熱分析之探討……………………..……………………........…77
3-3-3化合物變溫粉晶繞射之探討…………..………………………............79
3-3-4化合物3Cn-epnom討論…………..……………………….....................80
3-4化合物2Cn-epnom液晶性質探討………….……………...........................81
3-4-1化合物光學紋理之探討………………………………………..............81
3-4-2化合物熱分析之探討……………………..………………………......82
3-4-3化合物變溫粉晶繞射之探討…………..………………….……….....85
3-4-4化合物2Cn-epnom之堆疊模型的理論計算探討…....…………….91
3-4-5化合物2Cn-epnom討論…....………………………………………….93
3-5化合物1Cn-epnom ( n = 10, 12, 14, 16 ) 液晶性質探討………….…......95
3-5-1化合物光學紋理之探討…………………………………..……………95
3-5-2化合物1Cn-epnom討論……………………..………..…………..……95
3-6化合物mCn-epnom性質比較 ( m = 1, 2, 3 and n = 10, 12, 14, 16)………96
3-7錯合物Co2-3Cn-epnom液晶性質探討………….……................................98
3-7-1錯合物光學紋理之探討……………….....................……...…..………98
3-7-2化合物熱分析之探討………………...........……………...…..…..…100
3-7-3化合物變溫粉晶繞射之探討……………….....……….......……..…100
3-7-4錯合物Co2-3Cn-epnom討論……………….....………...……....…..…103
3-8錯合物Ni2-3Cn-epnom液晶性質探討………….……................…...........104
3-8-1錯合物光學紋理之探討……………….....................…...……..…..…104
3-8-2化合物熱分析之探討………………...........……………...…..…..…105
3-8-3化合物變溫粉晶繞射之探討……………….....……….......……..…106
3-8-4錯合物Ni2-3Cn-epnom討論……………….....……...………..….…109
3-9錯合物Cu2-3Cn-epnom液晶性質探討………….……..............................110
3-9-1錯合物光學紋理之探討……………….....................……….....…..…110
3-9-2化合物熱分析之探討………………...........……….………....…..…111
3-9-3化合物變溫粉晶繞射之探討……………….....………….....…..……113
3-9-4錯合物Cu2-3Cn-epnom討論……………….....………...………..……115
3-10錯合物Zn2-3Cn-epnom液晶性質探討………….……............................116
3-10-1錯合物光學紋理之探討……………….....................…………….…116
3-10-2化合物熱分析之探討………………...........……….…..………..…117
3-10-3化合物變溫粉晶繞射之探討……………….....……….......………119
3-10-4錯合物Zn2-3Cn-epnom討論……………….....………..………….…122
3-11錯合物M2-3Cn-epnom性質比較 ( M = Co, Ni, Cu, Zn, and
n = 10, 12, 14, 16)………………………………………………………124
3-12錯合物Co2-2Cn-epnom液晶性質探討………….……............................126
3-12-1錯合物光學紋理之探討……………….....................…………….…126
3-12-2化合物熱分析之探討………………...........…………..………..…126
3-12-3化合物變溫粉晶繞射之探討……………….....…………......…..…128
3-12-4錯合物Co2-2Cn-epnom討論……………….....……….......…………131
3-13錯合物Ni2-2Cn-epnom液晶性質探討………….…….............................134
3-13-1錯合物光學紋理之探討……………….....................…………….…134
3-13-2化合物熱分析之探討………………...........………….…..…………136
3-13-3化合物變溫粉晶繞射之探討……………….....……….......…..…..137
3-13-4化合物Ni2-2Cn-epnom之堆疊模型的理論計算探討……………..142
3-13-5錯合物Ni2-2Cn-epnom討論……………….....….......………..……144
3-14錯合物Cu2-2Cn-epnom液晶性質探討………….…….............…...........145
3-14-1錯合物光學紋理之探討……………….....................………...…..…145
3-14-2化合物熱分析之探討………………...........……….………..…..…147
3-14-3化合物變溫粉晶繞射之探討……………….....……….......………148
3-14-4化合物Cu2-2Cn-epnom之堆疊模型的理論計算探討………………153
3-14-5錯合物Cu2-2Cn-epnom討論……………….....…….......………..…..155
3-15錯合物Zn2-2Cn-epnom液晶性質探討………….……............................156
3-15-1錯合物光學紋理之探討……………….....................…………….…156
3-15-2化合物熱分析之探討………………...........…………….…..…..…156
3-15-3化合物變溫粉晶繞射之探討……………….....……….......…....…158
3-15-4錯合物Zn2-2Cn-epnom討論……………….....…….....………….…162
3-16錯合物M2-2Cn-epnom性質比較 ( M = Co, Ni, Cu, Zn,
and n = 10, 12, 14, 16)…………………………………..………….…..164
3-17錯合物Co2-1Cn-epnom液晶性質探討……….............…….……...........166
3-17-1錯合物光學紋理之探討………………..............……………..…..…166
3-17-2化合物熱分析之探討………………...........…………….…..…..…166
3-17-3化合物變溫粉晶繞射之探討……………….....……….........…..…167
3-17-4錯合物Co2-1Cn-epnom討論……………….....………...………....…171
3-18錯合物Ni2-1Cn-epnom液晶性質探討………….…….............................172
3-18-1錯合物光學紋理之探討……………….....................…………….…172
3-18-2化合物熱分析之探討………………...........……….…..………..…172
3-18-3化合物變溫粉晶繞射之探討……………….....………......…....…173
3-18-4錯合物Ni2-1Cn-epnom討論……………….....………..………….…177
3-19錯合物Cu2-1Cn-epnom液晶性質探討………….……............................178
3-19-1錯合物光學紋理之探討……………….....................………….....…178
3-19-2化合物熱分析之探討………………...........……….…..………..…178
3-19-3化合物變溫粉晶繞射之探討……………….....………......…....…179
3-19-4錯合物Cu2-1Cn-epnom討論……………….....………...………....…182
3-20錯合物Zn2-1Cn-epnom液晶性質探討………….……............................183
3-20-1錯合物光學紋理之探討……………….....................…………….…183
3-20-2化合物熱分析之探討………………...........……….…..………..…183
3-20-3化合物變溫粉晶繞射之探討……………….....……….......………184
3-20-4錯合物Zn2-1Cn-epnom討論……………….....……....………….…187
3-21錯合物M2-1Cn-epnom性質比較 ( M = Co, Ni, Cu, Zn,
and n = 10, 12, 14, 16)………….……....................................................188
3-22化合物之磁性探討………….…….............................……..……...........190
3-22-1 Cu2-2C16-epnom之磁性分析……………….....……............…..…193



第四章 結論……………………………..........………………............…………194

第五章 參考文獻……………………………….......………..............…………197

圖目錄
圖 1-1. 三相變化分子示意圖。....................................................................................1
圖 1-2. 向列相液晶分子排列示意圖。........................................................................2
圖 1-3. 向列相對掌性液晶分子排列示意圖(a) N*, cholesteric;
(b) Sc*, chiral smectic C。...............................................................................2
圖 1-4. 筒相液晶分子排列示意圖(a) ND, discotic nematic phase;
(b) Nc, columnar nemetic phase; (c) Colh, hexagonal columnar phase;
(d) Colr , rectangular columnar phase;
(e) Coltet, tetragonal columnar phase。…………………………………….....3
圖 1-5. 液晶分子基本架構示意圖。............................................................................4
圖 1-6. 氫鍵型分子排列示意圖。................................................................................5
圖 1-7. 含醯胺官能基氫鍵型液晶分子示意圖。........................................................6
圖 1-8. 利用甲酸官能基間的氫鍵所製作的氫鍵型液晶分子。................................6
圖 1-9. 藉由分子間氫鍵彼此相互連結的氫鍵型液晶分子。....................................7
圖1-10. (a) 含醯胺官能基液晶分子空間排列示意圖,分子彼此間藉由氫鍵
排列成為一層狀結構。(b) 醯胺官能基液晶分子結構示意圖。..................7
圖 1-11. 草醯聯胺分子示意圖。...................................................................................8
圖 1-12. ( a ) 含尿素官能基液晶分子空間排列示意圖。
(b) 含尿素官能基液晶分子結構示意圖。....................................................8
圖 1-13. Diarylmercurials 液晶分子。..........................................................................11
圖 1-14. β-diketonate 液晶分子。...............................................................................11
圖 1-15. Dithiolene 液晶分子。....................................................................................11
圖 1-16. Schiff-base 液晶分子結構圖。.....................................................................12
圖 1-17. Schiff-base 液晶分子結構圖。........................……………………………12
圖 1-18. 金屬液晶分子結構圖。...........................………………………………….13
圖 1-19. 范文蕙學姊論文中液晶分子結構圖。........................................................13
圖 1-20. 雙核金屬液晶分子結構圖。........................................................................14
圖1-21. 林志恭學長論文的氫鍵液晶分子結構圖。.................................................15
圖 1-22. ( a ) PEOH2分子結構圖( b ) PMOH2分子結構圖。...................................15
圖 1-23. 劉醇輝學長論文的無機液晶分子結構圖。................................................15
圖 1-24. 林珮君學姐論文中的無機液晶分子結構圖。............................................16
圖 1-25. M-mCn-epnom分子結構圖. .........................................................................16
圖 3-1-1. 1H NMR spectrum (300 MHz) of pnom in d-CDCl3. ..................................55
圖 3-1-2. 1H NMR spectrum (600 MHz) of 3C10-hyald in d-CDCl3. .........................56
圖 3-1-3. 1H NMR spectrum (300 MHz) of 3C14-epnom in d-CDCl3. .......................57
圖 3-1-4. 1H NMR spectrum (300 MHz) of 2C10-hyald in d-CDCl3. ........................58
圖 3-1-5. 1H NMR spectrum (600 MHz) of 2C14-epnom in d-CDCl3. .......................59
圖 3-1-6. 1H NMR spectrum (300 MHz) of 1C14-hyald in d-CDCl3. .........................60
圖 3-1-7. 1H NMR spectrum (600 MHz) of 1C14-epnom in d-CDCl3. .......................61
圖 3-1-8. 1H NMR spectrum (300 MHz) of Ni2-2C16-epnom in d-CDCl3...................62
圖 3-1-9. MADLE-Mass spectra of Co2-2C16-epnom in DCM. .................................63
圖 3-1-10. MADLE-Mass spectra of Ni2-2C16-epnom in DCM..................................64
圖 3-1-11. MADLE-Mass spectra of Cu2-2C16-epnom in DCM. ...............................64
圖 3-1-12. MADLE-Mass spectra of Zn2-2C16-epnom in DCM. ................................65
圖 3-1-13. ORTEP diagram of complex Cu2-2C16-epnom with atom labels and
numbering scheme; hydrogen atoms are omitted for clarity.....................68
圖 3-1-14. Molecular structure of complex Cu2-2C16-epnom. ....................................68
圖 3-1-15. Molecular structure of complex Cu2-2C16-epnom. ....................................69
圖 3-1-16. Molecular structure of complex Cu2-2C16-epnom. ....................................69
圖 3-1-17. View of the stacking along the columnar axis, with thestacking periodicity
,h, also representing the molecular thickness. ..........................................70
圖 3-1-18. View of the stacking along a axis. .............................................................70
圖 3-2-1. Polarized optical textures after the cooling process for
(a) 2C10-pnom at 75oC, (b) 2C12-pnom at 75oC, (c) 2C14-pnom at 80oC,
(d) 2C16-pnom at 80oC. ...............................................................................73
圖 3-2-2. DSC curve of 2C10-pnom at a scan rate of 10 oC/min. ..............................74
圖 3-2-3. DSC curve of 2C10-pnom at a scan rate of 10 oC/min. ................................74
圖 3-3-1. Polarized optical textures after the cooling process for 3C10-epnom at
(a) 130 oC, (b) 125 oC, (c) RT. ....................................................................77
圖 3-3-2. DSC curve of 3C10-epnom at a scan rate of 10 oC/min. ..............................78
圖 3-3-3. DSC curve of 3C10-epnom at a scan rate of 10 oC/min. ..............................78
圖 3-3-4. Powder X-ray diffraction patterns of 2C12-epnom. .....................................79
圖 3-3-5. Powder X-ray diffraction patterns of 2C12-epnom at 80 oC. .......................79
圖 3-4-1. Polarized optical textures after the cooling process for 2C14-epnom at
(a) 126 oC, (b) 100 oC, (c) 80 oC, (d) RT. ...................................................82
圖 3-4-2. DSC curve of 2C10-epnom at a scan rate of 10 oC/min. ..............................83
圖 3-4-3. DSC curve of 2C12-epnom at a scan rate of 10 oC/min. ..............................83
圖 3-4-4. DSC curve of 2C14-epnom at a scan rate of 10 oC/min. ..............................84
圖 3-4-5. DSC curve of 2C16-epnom at a scan rate of 10 oC/min. ..............................84
圖 3-4-6. Powder X-ray diffraction patterns of 2C12-epnom at 110 oC. ......................85
圖 3-4-7. Powder X-ray diffraction patterns of 2C14-epnom at 130 °C. .....................86
圖 3-4-8. Powder X-ray diffraction patterns of 2C14-epnom at 128 °C. .....................86
圖 3-4-9. Powder X-ray diffraction patterns of 2C16-epnom at 130 °C. .....................88
圖 3-4-10. Powder X-ray diffraction patterns of 2C16-epnom at 125 °C. ...................88
圖 3-4-11. Powder X-ray diffraction patterns of 2C16-epnom at 120 °C. ...................89
圖 3-4-12. Colh的單位截面積示意圖。.......................................................................92
圖 3-4-13. Molecule packing diagram of 2Cn-epnom. ................................................93
圖 3-5-1. Polarized optical textures after the cooling process for 1C10-epnom
at 210 oC. ....................................................................................................95
圖 3-7-1. Polarized optical textures after the cooling process for Co2-3C16-epnom at
(a) 150℃, (b) 180℃, (c) 180℃ and (d) 180℃. .........................................99
圖 3-7-2. TGA thermograms of Co2-3C16-epnom. ....................................................100
圖 3-7-4. Powder X-ray diffraction patterns of Co2-3C16-epnom. ............................101
圖 3-7-5. Powder X-ray diffraction patterns of Co2-3C16-epnom at 140 °C. ............101
圖 3-7-6. Molecule packing diagram of Co2-3Cn-epnom. ...................................102
圖 3-8-2. Polarized optical textures after the heating process for Ni2-3C16-epnom at
(a) 60℃ and (b) 75℃. ………………………………….........................105
圖 3-8-3. DSC curve of Ni2-3C16-epnom at a scan rate of 10 oC/min. ......................105
圖 3-8-3. TGA thermograms of Ni2-3C16-epnom. ....................................................106
圖 3-8-4. Powder X-ray diffraction patterns of Ni2-3C16-epnom. .............................107
圖 3-8-5. Powder X-ray diffraction patterns of Ni2-3C16-epnom at 30℃. ……........107
圖 3-8-7. Powder X-ray diffraction patterns of Ni2-3C16-epnom at 80℃. ...............108
圖 3-8-8. Molecule packing diagram of Ni2-3Cn-epnom. .........................................109
圖 3-9-4. Polarized optical textures after the Cuoling process for Cu2-3C16-epnom at
(a) 30℃, (b) 40℃, (c) 90℃ and (d) 110℃. .............................................111
圖 3-9-5. DSC curve of Cu2-3C16-epnom at a scan rate of 10 oC/min. .....................112
圖 3-9-3. TGA thermograms of Cu2-3C16-epnom. ....................................................112
圖 3-9-4. Powder X-ray diffraction patterns of Cu2-3C16-epnom. ............................113
圖 3-9-5. Powder X-ray diffraction patterns of Cu2-3C16-epnom at 90 °C. ..............114
圖 3-9-6. Molecule packing diagram of Cu2-3Cn-epnom. .........................................115
圖 3-10-6. Polarized optical textures (a), (b), (c) and (d) after the cooling process
for Zn2-3C16-epnom at 110℃. ................................................................117
圖 3-10-7. DSC curve of Zn2-3C16-epnom at a scan rate of 10 oC/min. ...................118
圖 3-10-3. TGA thermograms of Zn2-3C16-epnom. ..................................................118
圖 3-10-4. Powder X-ray diffraction patterns of Zn2-3C16-epnom. ..........................119
圖 3-10-5. Powder X-ray diffraction patterns of Zn2-3C16-epnom at 120 °C. ..........120
圖 3-10-6. Powder X-ray diffraction patterns of Zn2-3C16-epnom at 140 °C. ..........120
圖 3-10-7. Molecule packing diagram of Zn2-3Cn-epnom. ......................................122
圖 3-12-8. DSC curve of Co2-2C16-epnom at a scan rate of 10 oC/min. ...................127
圖 3-12-3. TGA thermograms of Co2-2C16-epnom. ..................................................127
圖 3-12-4. Powder X-ray diffraction patterns of Co2-2C16-epnom. ..........................128
圖 3-12-5. Powder X-ray diffraction patterns of Co2-2C16-epnom at 100℃. ...........129
圖 3-12-6. Powder X-ray diffraction patterns of Co2-2C16-epnom at 120℃. ...........129
圖 3-12-7. Molecule packing diagram of Co2-2Cn-epnom. ......................................132
圖 3-13-9. Polarized optical textures after the cooling process for Ni2-2C16-epnom at
(a) 220℃, (b) 175℃, (c) 85℃, (d) 30℃, and the heating process at
(e) 145℃, (f) 220℃. ..............................................................................135
圖 3-13-10. DSC curve of Ni2-2C16-epnom at a scan rate of 10 oC/min. ...............136
圖 3-13-3. TGA thermograms of Ni2-2C16-epnom. ..................................................137
圖 3-13-4. Powder X-ray diffraction patterns of Ni2-2C16-epnom. ...........................138
圖 3-13-5. Powder X-ray diffraction patterns of Ni2-2C16-epnom at 200 °C. ..........138
圖 3-13-6. Powder X-ray diffraction patterns of Ni2-2C16-epnom at 100 °C. ..........139
圖 3-13-7. Powder X-ray diffraction patterns of Ni2-2C16-epnom at 25 °C. ............139
圖 3-13-8. Powder X-ray diffraction patterns of Ni2-2C16-epnom.............................140
圖 3-13-9. Powder X-ray diffraction patterns of Ni2-2Cn-epnom
(n = 10, 12, 14, 16) at 180 °C............................................................ .....140
圖 3-13-10. Molecule packing diagram of Ni2-2Cn-epnom. .....................................143
圖 3-13-11. Two discotic packing diagram of Ni2-2Cn-epnom..................................144
圖 3-14-11. Polarized optical textures after the cooling process for Cu2-2C16-epnom at
(a) 220℃, (b) 200℃, (c) 30℃, and the heating process at (d) 110℃,
(e) 150℃, (f) 200℃............................................................................. 146
圖 3-14-12. DSC curve of Cu2-2C16-epnom at a scan rate of 10 oC/min..............147
圖 3-14-3. TGA thermograms of Cu2-2C16-epnom. ..................................................148
圖 3-14-4. Powder X-ray diffraction patterns of Cu2-2C16-epnom at 190 °C. ..........149
圖 3-14-5. Powder X-ray diffraction patterns of Cu2-2C16-epnom at 110 °C. ..........149
圖 3-14-6. Powder X-ray diffraction patterns of Cu2-2C16-epnom at 50 °C. ............150
圖 3-14-7. Powder X-ray diffraction patterns of Cu2-2C16-epnom at 25 °C. ............150
圖 3-14-8. Powder X-ray diffraction patterns of Cu2-2C16-epnom. ..........................151
圖 3-14-9. powder X-ray diffraction patterns of Cu2-2Cn-epnom
( n = 10, 12, 14, 16 ) at 180 °C. ..............................................................151
圖 3-14-10. Molecule packing diagram of Cu2-2Cn-epnom. ....................................154
圖 3-14-11. Two discotic packing diagram of Cu2-2Cn-epnom. ...............................155
圖 3-15-13. DSC curve of Zn2-2C16-epnom at a scan rate of 10 oC/min...................157
圖 3-15-3. TGA thermograms of Zn2-2C16-epnom....................................................157
圖 3-15-4. Powder X-ray diffraction patterns of Zn2-2C16-epnom. ..........................158
圖 3-15-14. Powder X-ray diffraction patterns of Zn2-2C16-epnom at 25 °C. ........159
圖 3-15-15. Powder X-ray diffraction patterns of Zn2-2C16-epnom at 100 °C. .......159
圖 3-15-6. Molecule packing diagram of Zn2-2Cn-epnom. .......................................162
圖 3-17-1. TGA thermograms of Co2-1C16-epnom. ..................................................167
圖 3-17-2. Powder X-ray diffraction patterns of Co2-1C16-epnom. ..........................168
圖 3-17-16. Powder X-ray diffraction patterns of Co2-1C16-epnom at 230℃. ........168
圖 3-17-4. Powder X-ray diffraction patterns of Co2-1C16-epnom at 230℃. ...........169
圖 3-17-5. Molecule packing diagram of Co2-1Cn-epnom. ......................................171
圖 3-18-1. TGA thermograms of Ni2-1C16-epnom. ..................................................173
圖 3-18-2. Powder X-ray diffraction patterns of Ni2-1C16-epnom. ...........................174
圖 3-18-17. Powder X-ray diffraction patterns of Ni2-1C16-epnom at 230℃. .........174
圖 3-18-74. Powder X-ray diffraction patterns of Ni2-1C16-epnom at 250℃. ..........175
圖 3-18-5. Molecule packing diagram of Ni2-1Cn-epnom. .......................................177
圖 3-19-1. TGA thermograms of Co2-1C16-epnom. ..................................................180
圖 3-19-2. Powder X-ray diffraction patterns of Co2-1C16-epnom. ..........................181
圖 3-19-18. Powder X-ray diffraction patterns of Cu2-1C14-epnom at 230 ℃. .......181
圖 3-19-4. Molecule packing diagram of Cu2-1Cn-epnom. ......................................183
圖 3-20-1. TGA thermograms of Zn2-1C16-epnom. ..................................................184
圖 3-20-2. Powder X-ray diffraction patterns of Zn2-1C16-epnom. ..........................185
圖 3-20-19. Powder X-ray diffraction patterns of Zn2-1C16-epnom at 230℃. ........185
圖 3-20-4. Molecule packing diagram of Zn2-1Cn-epnom. ......................................187
圖 3-22-1 Magnetic behavior (χM as a function of temperature T and χMT as
a function of temperature T) in the range 5-373K for compound
Cu-2C16-epnom........................................................................................193

表目錄
表 3-1-1. Element analysis……........................................................................……......…….66
表 3-4-1. Powder X-ray diffraction Data of 2C14-epnom during the cooling cycle.....87
表 3-4- 2 Powder X-ray diffraction Data of 2C14-epnom during the cooling cycle.....89
表 3-4-3. Powder X-ray diffraction Data of 2Cn-epnom during the cooling cycle…..90
表 3-4-4. Molecule packing is calculated by Powder X-ray diffraction data………..93
表 3-6-1. The transition temperature and enthalpies of complexes 2Cn-pnom………96
表 3-6-2. The transition temperature and enthalpies of complexes 3Cn-epnom…......97
表 3-6-3. The transition temperature and enthalpies of complexes 2Cn-epnom……..97
表 3-7-1. Powder X-ray diffraction Data of Co2-3Cn-epnom (n = 10, 12, 14, 16)
at 140 °C………………………………………………………………....102
表 3-8-2. Powder X-ray diffraction Data of Ni2-3Cn-epnom (n = 10, 12, 14, 16)
at 30 °C………………………………………………………….……..108
表 3-9-1. Powder X-ray diffraction Data of Cu2-3Cn-epnom (n = 10, 12, 14, 16)
at 90 °C…………………………………………………………………..114
表 3-10-1. Powder X-ray diffraction Data of Zn2-3Cn-epnom (n = 10, 12, 14, 16)
at 120 °C………………………………………………………………..121
表 3-11-1. The transition temperature and enthalpies of complexes
M2-3C16-epnom………………………………………………………124
表 3-11-2. Powder XRD diffraction data of M2-3C16-epnom compounds……….…125
表 3-12-3. Powder X-ray diffraction Data of Co2-2C16-epnom
during the heating cycle………………………………………………..130
表 3-12-2. Powder X-ray diffraction Data of Co2-2Cn-epnom
(n = 10, 12, 14, 16) at 100 °C………………………………..…………131
表 3-12-3. Molecule packing is calculated by Powder X-ray diffraction data……..131
表 3-13-1. Powder X-ray diffraction Data of Ni2-2C16-epnom
during the cooling cycle……………………………………………………..141
表 3-13-2. Powder X-ray diffraction Data of Ni2-2Cn-epnom
(n = 10, 12, 14, 16) at 180 °C………………………………………….142
表 3-13-3. Molecule packing is calculated by Powder X-ray diffraction data…….143
表 3-14-4. Powder X-ray diffraction Data of Cu2-2C16-epnom
during the cooling cycle………………………………………………152
表 3-14-2. Powder X-ray diffraction Data of Cu2-2Cn-epnom
(n = 10, 12, 14, 16) at 180 °C……………………………………..……153
表 3-13-3. Molecule packing is calculated by Powder X-ray diffraction data…….154
表 3-15-5. Powder X-ray diffraction Data of Zn2-2C16-epnom
during the heating cycle……………………………………………….160
表 3-15-2. Powder X-ray diffraction Data of Zn2-2Cn-epnom
(n = 10, 12, 14, 16) at 180 °C………………………………….....…….161
表 3-16-1. The transition temperature and enthalpies of complexes
M2-2C16-epnom………………………………………………………165
表 3-16-2. Powder XRD diffraction data of M2-2C16-epnom compounds ……….165
表 3-17-6. Powder X-ray diffraction Data of Co2-1C16-epnom
during the heating cycle……………………………………………….169
表 3-17-2. Powder X-ray diffraction Data of Co2-1C16-epnom
during the Cooling cycle…………………………………………..….170
表 3-17-3. Powder X-ray diffraction Data of Co2-1Cn-epnom
(n = 10, 12, 14, 16) at 230 °C………………………………………..…170
表 3-18-7. Powder X-ray diffraction Data of Ni2-1C16-epnom
during the heating cycle…………………………………………………..….175
表 3-18-2. Powder X-ray diffraction Data of Ni2-1Cn-epnom
(n = 10, 12, 14, 16) at 230 °C………………………………………….176
表 3-19-1. Powder X-ray diffraction Data of Cu2-1Cn-epnom
(n = 10, 12, 14, 16) at 230 °C…………………………………………182
表 3-20-1. Powder X-ray diffraction Data of Zn2-1Cn-epnom
(n = 10, 12, 14, 16) at 230 °C…………………………………………186
表 3-21-1. The transition temperature and enthalpies of complexes
M2-1C16-epnom………………………………………………………...188
表 3-21-2. Powder XRD diffraction data of M2-3C16-epnom compounds…………189
Scheme
Scheme I. Synthesis of 2Cn-pnom…………………………………...........…………21
Scheme II. Synthesis of M2-2Cn-epnom…………………………………...………22
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