| 摘要: | 本篇系列一中描述的是利用不對稱的含pyrazole結構的配位基與銅配位形成一個桿狀形液晶分子。藉由X-ray單晶繞射分析，含銅錯合物中心以共平面的方式配位。在含銅錯合物系列中藉由改變碳鏈長度，來探討其對液晶性質的影響，發現改變液晶分子的側鏈基碳數，會對液晶相的形成造成顯著的影響，結果顯示銅錯合物的碳數為8時具有N 相，碳數為10、12、14、16則具有SmC相。 系列二及系列三目標是合成具雙金屬中心的液晶分子，利用雙金屬的配位方式，改變分子構形，進而得到多樣的液晶性質。在此成功合成出含烷氧鏈的配位基2Rrs碳數8、10、12、14與16皆為SmC相，配位基Rrs碳數為8、12與16則具有SmC相。再利用配位基2Rrs與金屬Cu配位碳數8、10、12、14與16皆為Colh相，配位基2Rrs與金屬Zn配位只有碳數16為Colh相。另外，Rrs與金屬Zn配位後碳數8、12與16皆有SmA及SmC相。 以上利用POM、DSC、變溫XRD探討其液晶性質。結構及純度上分別利用NMR、單晶結構與元素分析等儀器來鑑定。 In this thesis three 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, preparation, characterization and mesomorphric properties of copper(II) complexes derived from 3-[(4-alkoxy)phenyl]-1H-pyrazoles (Rpc) were described. X-ray single crystal structural analysis showed that these complexes were square-planar coordinated. The formation of mesophases was found to be sensitive to the number of carbon length of the side chains. All derivatives with shorter alkoxy chains (n = 8) exhibited nematic phase, however, all other derivatives with longer alkoxy chains (n = 10, 12, 14, 16) formed smectic C phases. In Series II, bis[?[2-[3,4-alkoxy-2-hydroxphenyl]imino]ethylidene]- 4-alkoxybenzenemethanols (2Rrs) and their metal complexes (M = Cu, Zn, Pd) were synthesized, and their mesomorphic properties studied. All derivatives 2Rrs exhibited smectic C phases. All copper(II) complexes (2Rrc; n = 8, 10, 12, 14,16 ) and zinc(II) complexes (2Rrz; n = 16) exhibited columnar hexagonal phases (Colh) phases. On the other hand, palladium complexes (2Rrp; n = 16) formed an unknown mesophases. In Series III, bis[?[2-[4-alkoxy-2-hydroxphenyl]imino]ethylidene]- 4-alkoxybenzenemethanols (Rrs; n = 8, 12, 16) and their metal complexes (M = Cu, Pd, Zn) were prepared and their mesomorphic properties investigated. All ligand derivatives exhibited smectic X and smectic C phase. Zinc(II) complexes (Rrz; n = 8, 12, 16) exhitbited smectic A or smectic C phases. However, palladium complexes (Rrp; n = 16) formed smectic X phases. Copper complexes (Rrc; n = 16) was not mesogenic. |
