| 摘要: | 系列一以benzohydrozone及phenolacrylaldehyde進行Schiff base反應後合成出配位基2a、2b分別與Cu(OAc)2及Zn(OAc)2進行反應得到單金屬Cu及Zn錯合物，分別為1a及1b。 配位基2a、2b及Cu錯合物1a及1b在碳數為8, 10, 12, 14, 16皆具有Colh相，Zn錯合物1b，碳數為12, 14, 16具有Colh相，顯示在改變側鏈基碳數，會對液晶相的形成造成顯著的影響。 並透過理論計算、模擬分子結構推測配位基及Cu與Zn錯合物盤狀堆疊的情形，並利用IR、EPR等證實金屬錯合物為單金屬配位。 系列二是以1,3,4-oxadiazole雜環作為設計的主幹，利用改變側鏈基數目合成出配位基4a、4b，其中配位基4b與Cu(OAc)2及Pd(OAc)2配位而得到Cu及Pd錯合物3b。 在配位基4a (n = 16)具有SmA相，顯示較長且較少支數碳鏈有利於桿狀型液晶生成；配位基4b (n = 8, 12, 16)皆為結晶相，與金屬配位後Cu錯合物3b 碳數為8, 12，具有Colh相，Pd錯合物3b 碳數為8, 12, 16皆具有Colh，在結構較對稱且碳鏈數較多之情況下較易形成盤狀型液晶分子。 上述兩系列皆利用POM、DSC及變溫XRD探討其液晶性質。結構及純度上分別利用NMR與元素分析等儀器來鑑定。 In this these two series of new compounds were prepared and their mesomorphic properties investigated. All organic derivatives were characterized by 1H-NMR and 13C-NMR spectroscopes, whereas all metal complexes were characterized by IR spectroscopy and elemental analysis. Their physical properties were characterized by polarized optical microscopy (POM), differential scanning calorimetry (DSC), and temperature-dependent powder X-ray diffraction (XRD) measurements. In series I, The Cu(II) complexes 1a, 1b and ligands 2a, 2b are both column-like liquid crystals.The Zn(II) complexes 2b are also column-like liquid crystals with longer alkoxy chains (n = 12, 14,16) The mesophase was identified as hexagonal columnar mesophase (Colh) phase by XRD. In series II, ligands 4a (n = 16) exhibited smectic A phases. Ligands 4b (n = 8, 12, 16) exhibited crystal phases, but their metal complexes (M = Cu, Pd) form liquid crystal pahes. The Cu(II) complexes 3b (n = 12, 16) and the Pd(II) complexes 3b (n =8, 12, 16) are both column-like liquid crystals. The mesophase was identified as hexagonal columnar mesophase (Colh) phase by XRD. |
