系統識別號 | U0002-1807201315472700 |
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DOI | 10.6846/TKU.2013.00678 |
論文名稱(中文) | 草醯胺架構的鈷、鎳、銅、鋅金屬液晶之合成與性質 |
論文名稱(英文) | New Metallomesogens Based on Oxamide Scaffold with Co(II), Ni(II), Cu(II), and Zn(II) ion: Synthesis, Characterizations and Mesogenic Properties |
第三語言論文名稱 | |
校院名稱 | 淡江大學 |
系所名稱(中文) | 化學學系碩士班 |
系所名稱(英文) | Department of Chemistry |
外國學位學校名稱 | |
外國學位學院名稱 | |
外國學位研究所名稱 | |
學年度 | 101 |
學期 | 2 |
出版年 | 102 |
研究生(中文) | 宋文德 |
研究生(英文) | Wen-De Sung |
學號 | 600160070 |
學位類別 | 碩士 |
語言別 | 繁體中文 |
第二語言別 | |
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 |
關鍵字(中) |
金屬液晶 草醯胺 |
關鍵字(英) |
metallomesogens oxamide Co(II),Ni(II),Cu(II),and Zn(II) complex |
第三語言關鍵字 | |
學科別分類 | |
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. |
第三語言摘要 | |
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 |
參考文獻 |
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