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研究生： 徐彥皇
Yen-Huang Hsu
論文名稱： 含單金屬桿狀無機液晶之設計與探討
The study of metallomesogen
指導教授： 賴重光
C.K. Lai
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學學系
Department of Chemistry
畢業學年度： 90
語文別： 中文
論文頁數： 95
中文關鍵詞： 液晶
外文關鍵詞： metallomesogen
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    • 摘 要
    本實驗主要是研究含金屬中心之無機液晶的設計與探討。藉由改變柔軟長碳鏈的長度，來觀察其液晶相的形成與否。本實驗所合成之化合物藉由1H-與13C-NMR光譜及元素分析（EA）來鑑定分子的結構與純度。液晶現象的觀察是藉由偏光顯微鏡(polarizing optical microscopy)來觀察其光學紋理圖，再以熱差式掃描卡計儀(differential scanning calorimetry)測定其相變化時之熱焓值變化，最後以變溫粉末X光繞射儀(temperature-dependent X-ray diffraction)鑑定其液晶相的結構。
    系列一成功的合成出一系列Schiff base形式的diimine配位基，此配位基再與Cu(II)進行配位，形成錯合物。實驗結果顯示配位基呈現了液晶相,其液晶相為SmC及N相。錯合物側鏈基alkoxy group碳數n為10、12、14、16時呈現了SmC及SmA相。而配位基液晶相的範圍比錯合物大了約100℃。
    系列二合成了一系列以pyrazole 分子為配位基與PdCl2 配位而形成無機盤狀液晶。實驗中我們發現當配位基之側鏈基數目越多時（即推電子基越多），較能利用pyrazole 分子氮上的lone pair 來和Pd 金屬配位，所以只有側鏈基總數為五的pyrazole 分子能得到較高產率的Pd錯合物，其中錯合物側鏈基alkoxy group碳數n為12時呈現了結晶相，n為14和16時呈現了Colho相。

    Abstract
    Transition metal complexes of Schiff bases derived from salicyladimines are among the best known of complexes that exhibited mesogenic properties in metallo mesogenic structures. A variety of transition metals, such as Fe, Rh, Ir, VO, Ni, Co, Cu, Pt, Pd etc. forms novel mesomorphism with salicyladimine Schiff bases. The overall molecular shapes of these complexes derived from salicyladimines were more likely of rod-like or brick-like shapes with two or four extended flexible sidechains, and these complexes all exhibited nematic or smectic phases predominantly, regardless of the metal center incorporated in such systems. Difference in the mesogenic properties of these Schiff base metal complexes was attributed to the various types of geometric coordination of the metal centers.
    In this work the synthesis and mesomorphic properties of a homologous series of N-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl phenylanilines and their copper(II) complexes are reported. These rod-like copper(II) complexes exhibited smectic and nematic phases, as predicted for rod-like molecules. Their mesomorphic properties were characterized by DSC thermal analysis, optical polarized microscopy and powder XRD diffraction. All salicyladiminato ligands and their copper(II) complexes exhibited enantiotropy phases. The compounds of ligands showed smectic C (SmC) and nematic (N) phase and copper(II) complexes formed SmC and smectic A (SmA) phases. The difference in formation of mesophases was due to the molecular shape variation. In addition, copper complex with two hexadecyloxy (n=C16) group as sidechains have a widest temperature range of the SmC mesophase. The mesomorphic properties of these copper(II) complexes were also compared with other similar metallomesogenic bis(salicyladiminato)- copper(II) complexes in terms of molecular structures.

    目 錄 謝誌……………………………………………………………………Ⅰ 摘要……………………………………………………………………Ⅱ 英文摘要………………………………………………………………Ⅲ 目錄……………………………………………………………………Ⅳ 圖目錄…………………………………………………………………Ⅶ 表目錄…………………………………………………………………Ⅸ 附圖目錄………………………………………………………………Ⅹ 第一章 緒論……………………………………………………………1 1-1 前言……………………………………………………………2 1-2 液晶之起源與簡介………………………………………………2 1-3 液晶分子結構之設計……………………………………………4 1-4 液晶的分類………………………………………………………5 1-5 液晶的性質……………………………………………………12 1-6 無機液晶的設計與分類…………………………………………13 1-7 無機液晶之特性………………………………………………14 1-8 研究動機………………………………………………………16 第二章 實驗部分……………………………………………………19 2-1 實驗藥品………………………………………………………20 2-2 儀器設備………………………………………………………21 2-3 實驗流程………………………………………………………29 2-4 實驗步驟………………………………………………………31 2-4-1-1 4-Alkoxy-2-hydroxybenzaldehydes 之合成………………31 2-4-1-2 4-Alkoxy-nitrobenzenes 之合成…………………………….32 2-4-1-3 4-Alkoxy-phenylamines 之合成……………………………34 2-4-1-4 4-[(4-Alkoxy-phenylimino)-methyl]-phenol 之合成………..35 2-4-1-5 4-[(2-Hydroxy-4-alkoxy-benzylidene)-amino]-benzoic acid 之 合成………………………………………………37 2-4-1-6 N-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenyl anilines之合成……………………………………39 2-4-1-7 Bis[n-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenylanilines]copper(Ⅱ) 之合成 ………………………40 2-4-2-1 1,2-Dialkoxybenzenes之合成………………………………43 2-4-2-2 3,4-Dialkoxyacetophenones之合成………………………44 2-4-2-3 Methyl-3,4,5-trialkoxybenzoates之合成………………….45 2-4-2-4 1-(3,4-Dialkoxy-phenyl)-3-(3,4,5-trialkoxy-phenyl)- propane-1,3-dione之合成…………………………………..46 2-4-2-5 3-(3,4-Dialkoxy-phenyl)-5-(3,4,5-trialkoxy-phenyl)- 4H-pyrazoles 之合成……………………………………….48 2-4-2-6 Bis[3-(3,4-dialkoxy-phenyl)-5-(3,4,5-trialkoxy-phenyl)- 4H-pyrazole ]palladium(Ⅱ) complexes 之合成…………...49 第三章 結果與討論…………………………………………………51 3-1 系列一之結果與討論…………………………………………53 3-1-1 化合物合成反應機制之探討…………………………………53 3-1-2 NMR 之鑑定…………………………………………………56 3-1-3 ESR 之鑑定…………………………………………………56 3-1-4 偏光顯微鏡之觀察 …………………………………………59 3-1-5 熱分析儀………………………………………………………62 3-1-6 powder X-ray 繞射儀………………………………………65 3-1-7 元素分析數據…………………………………………………67 3-1-8 系列一之結論…………………………………………………68 3-2 系列二之結果與討論…………………………………………70 3-2-1 化合物合成反應機制之探討………………………………70 3-2-2 化合物的鑑定………………………………………………72 3-2-3 實驗之探討…………………………………………………72 3-2-4 配位基之液晶相討論………………………………………..74 3-2-5 錯合物之液晶相討論………………………………………76 3-2-6 系列二之結論…………………………………………………79 參考文獻………………………………………………………………..80 圖 目 錄 圖1.形成液晶的條件……………………………………………………4 圖2.液相型液晶與熱相型液晶…………………………………………5 圖3.桿狀液晶的種類及排列方式………………………………………6 圖4.盤狀液晶形成之基本方式………………………………………8 圖5.盤狀液晶之堆疊方式………………………………………………9 圖6.Colh之二種排列…………………………………………………10 圖7.氫鍵液晶分子………………………………………………….11 圖8.常見之有機及無機液晶……………………………………….11 圖9.J.Chem.Soc.,Dalton Trans., 2000, 1437-1445之分子結構…….16 圖10. Inorg. Chem. 1990, 29, 1177之分子結構………………………16 圖11.系列一之結構……………………………………………………17 圖12. Pd錯合物之結構……………………………………………….18 圖13.系列二之結構……………………………………………………18 圖14.X-ray之繞射原理………………………………………………26 圖15a. Colh排列與各晶面之俯視圖…………………………………27 圖15b. Colr排列與各晶面之俯視圖…………………………………28 圖15c.典型之XRD圖譜…………………………………………….28 圖16.系列一之實驗流程與反應條件…………………………………29 圖17.系列二之實驗流程與反應條件…………………………………30 圖18.配位基之ESR 圖譜(n=14)…………………………………….57 圖19.錯合物之ESR 圖譜(n=14)…………………………………….58 圖20. 雙金屬Cu 錯合物之ESR 圖譜…………………………………58 圖21.配位基(n=14)之光學紋理圖，SmC相（250℃,100X）……..60 圖 22.銅錯合物(n=14)之光學紋理圖，SmC相（265℃,100X）……..61 圖 23.配位基之DSC 柱狀圖……………………………………….63 圖 24.銅錯合物之DSC 柱狀圖…………………………………….64 圖 25.配位基及錯合物之比較示意圖……………………………….65 圖 26.銅錯合物之powder X-ray 繞射圖（265℃）………………….66 圖 27. Pd錯合物的種類……………………………………………….73 圖 28. 3,5-Bis (4’-tetradecyloxy-phenyl)pyrazole 的光學紋理圖，SmC，150℃……………………………………………………75 圖 29. Pd錯合物(n=12)之光學紋理圖，結晶相，125℃，100X……….76 圖 30. Pd錯合物(n=14)之光學紋理圖，Colh，125℃，100X……….77 圖 31.系列二Pd錯合物之DSC 柱狀圖……………………………78 表 目 錄 表1.桿狀液晶一般結構及常使用之官能基……………………………7 表2.實驗之化學藥品………………………………………………….20 表3.液晶相所具有之特殊光學紋理圖………………………………..59 表4.系列一配位基之DSC 數據………………………………………62 表5.系列一銅錯合物之DSC 數據………………………………..63 表6.銅錯合物之X-ray 繞射數據…………………………………66 表7.元素分析表………………………………………………………67 表8.pyrazole 分子之DSC 數據（n=14）…………………………75 表9.系列二Pd 錯合物之DSC 數據………………………………77 表10.Pd錯合物及其配位基之DSC 數據……………………………79 附 圖 目 錄 附圖1. 4-Alkoxy-2-hydroxybenzaldehydes 之1H NMR圖譜………1 附圖2. 4-Alkoxy-2-hydroxybenzaldehydes 之13C NMR圖譜………2 附圖3. 4-Alkoxy-nitrobenzenes之1H NMR圖譜……………………3 附圖4. 4-Alkoxy-nitrobenzenes之13C NMR圖譜……………………4 附圖5. 4-Alkoxy-phenylamines之1H NMR圖譜……………………5 附圖6. 4-[(2-Hydroxy-4-alkoxy-benzylidene)-amino]-benzoic acid 之1H NMR圖譜………………………………………………6 附圖7. 4-[(2-Hydroxy-4-alkoxy-benzylidene)-amino]-benzoic acid 之13C NMR圖譜………………………………………………7 附圖8. 4-[(4-Alkoxy-phenylimino)-methyl]-phenol之1H NMR圖譜...8 附圖9. 4-[(4-Alkoxy-phenylimino)-methyl]-phenol之13C NMR圖譜..9 附圖10. N-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenylanilines之DSC圖譜…………………………………10 附圖11. Bis[n-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenylanilines]copper(Ⅱ) 之DSC圖譜…………………...11 附圖12. N-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenylanilines之ESR圖譜…………………………………12 附圖13. Bis[n-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenylanilines]copper(Ⅱ) 之ESR圖譜…………………...13 附圖14. N-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenylanilines之IR圖譜…………………………………..14 附圖15. Bis[n-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenylanilines]copper(Ⅱ) 之IR圖譜……………………...15 附圖16. Bis[n-(2-hydroxy-4-n-alkoxylbenzylidene)-4-n-alkoxyl- phenylanilines]copper(Ⅱ) 之XRD圖譜…………………...16 附圖17. 1,2-Dialkoxybenzenes之1H NMR圖譜……………………17 附圖18. 1,2-Dialkoxybenzenes之13C NMR圖譜……………………18 附圖19. 3,4-Dialkoxyacetophenones之1H NMR圖譜………………19 附圖20. 3,4-Dialkoxyacetophenones之13C NMR圖譜……………..20 附圖21. Methyl-3,4,5-trialkoxybenzoates之1H NMR圖譜…………21 附圖22. Methyl-3,4,5-trialkoxybenzoates之13C NMR圖譜………..22 附圖23. 1-(3,4-Dialkoxy-phenyl)-3-(3,4,5-trialkoxy-phenyl)- propane-1,3-dione之1H NMR圖譜………………………...23 附圖24. 1-(3,4-Dialkoxy-phenyl)-3-(3,4,5-trialkoxy-phenyl)- propane-1,3-dione之13C NMR圖譜………………………..24 附圖25. 3-(3,4-Dialkoxy-phenyl)-5-(3,4,5-trialkoxy-phenyl)- 4H-pyrazoles之1H NMR圖譜……………………………..25 附圖26. 3-(3,4-Dialkoxy-phenyl)-5-(3,4,5-trialkoxy-phenyl)- 4H-pyrazoles之13C NMR圖譜……………………………..26 附圖27. Bis[3-(3,4-dialkoxy-phenyl)-5-(3,4,5-trialkoxy-phenyl)- 4H-pyrazole ]palladium(Ⅱ) complexes之IR圖譜…………27 附圖28. 3,5-Bis(4’-tetradecyloxy-phenyl)pyrazole之DSC圖譜……28 附圖29. 3,5-Bis(3,4-ditetradecyloxy-phenyl)pyrazole之DSC圖譜…29 附圖30. 3-(3,4-Dialkoxy-phenyl)-5-(3,4,5-trialkoxy-phenyl)- 4H-pyrazoles之DSC圖譜………………………………….30 附圖31. Bis[3-(3,4-didodecyloxy-phenyl)-5-(3,4,5-tridodecyloxy- phenyl)-4H-pyrazole ]palladium(Ⅱ)之DSC圖譜…………31 附圖32. Bis[3-(3,4-ditetradecyloxy-phenyl)-5-(3,4,5-tritetradecyloxy- phenyl)-4H-pyrazole ]palladium(Ⅱ)之DSC圖譜…………32

    參考文獻
    1. S. M. Malinak, D. Coucouvanis, Inorg. Chem. 1996, 35, 4810.
    2. B. K. Sadashiva, A. Ghode, Liq. Cryst. 1994, 16, 33.
    3. Kazuchika Ohta, Mol. Cryst. Liq. Cryst. 1991, 208, 21-32.
    4. M. J. Heeg, J. L. Mack, M. D. Glick, and R. L. Lintvedt, Inorg.
    Chem. 1981, 20, 833.
    5. W. Baker, J. Chem. Soc. 1933, 1381.；K. Venkataraman, etc., J.
    Chem. Soc. 1934, 1767 .
    6. V. Prasad, B. K. Sadashiva, Mol. Cryst. Liq. Cryst. 1993, 225, 303.
    7. S. C. Shaw, etc., J. Indian. Chem. Soc. 67, 1990, 684.
    8. S. A. Mudson, P. M. Maitlis, Chem. Rev. 1993, 93, 861.
    9. K. Miyajima and Y. Matsunaga, Mol. Cryst. Liq. Cryst. 1995, 260, 499.
    10. W. Beck and K. Raab, Inorg. Synth. 1990, 28, 15.
    11. V. N. Kalinin, V. I. Zdanovich, P. V. Petrovskii, A. S. Batsanov and Yu. T. Struchkov. Metalloorg. Khim. 1990, 3, 662.
    12. S. T. Trzaska, T. M. Swager, Chem. Mater. 1998, 10, 438.
    13.J. Barbera, C. Cativiela, J. L. Serrano, M. M. Zurbano, Liq. Cryst. 1992, 11, 881.
    14.A. Jakli, A. Saupe, G. Scherowsky, X. H. Chen, Liq. Cryst. 1997, 22, 309.
    15.B. Xu, T. M. Swager, J. Am. Chem. Soc. 1995, 117, 5011.
    16.H. Zheng, C. K. Lai, T. M. Swager, Chem. Mater. 1995, 7, 2067.
    17.A. Chakravorty, Inorg. Chem. 1981, 20, 660.
    18.W. Mazurek, B. J. Kennedy, Inorg. Chem. 1985, 24, 3258.
    19.D. L. Davies, A. J. Grist, Inorg. Chim. Acta. 1995, 89.
    20.J. C. Fanning, X. Wang, Inorg. Chim. Acta. 1995, 199.
    21.J. E. Davies, B. M. Gatehouse, J. Chem. Soc., Dalton Trans. 1973, 25.

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