本篇文章主要探討以腙基聯吡啶為基本架構，側邊接上以醛基為官能基之不同碳鏈數目的衍生物，合成出具有配位能力的配位子分別為(L1-Cn~L3-Cn)，在加入鈷、鎳、銅、鋅等不同的金屬鹽類形成錯合物。
    利用核磁共振光譜(NMR)對結構做初步的鑑定，再以質譜(Mass)及元素分析(EA)來探討化合物的結構及純度，同時也得到具有五配位的[Zn(L1-C2)Cl2]單晶結構。液晶相探討部分，以偏光顯微鏡(POM)對不同相之溫度變化及液晶相種類做初步觀察，再以熱插式掃描分析儀(DSC)測量相變化溫度及熱焓值變化，最後以x-ray粉末繞射儀(XRD)來鑑定液晶相的排列，得知錯合物[Co(L2-Cn)Cl2]、[Ni(L2-Cn)Cl2]、[Zn(L2-Cn)Cl2]的系列屬於盤型(discotic)的液晶相。在電子吸收光譜中，配位子在波長340 nm有π-π*的電子躍遷，錯合物大約在波長400-420 nm間有CT band的表現；另外在[Zn(L1-Cn)Cl2]和[Zn(L1-Cn)Cl2]系列中，分別在波長530 nm及545 nm有放光的表現。

The synthesis of new metal complexes based on hydrazones derived from 6,6’-dihydrazine- 2,2’-bipyridine has been carried out, and use different lengths of alkyl chains to modify the ligands (L1-Cn~L3-Cn). The complexes were prepared by adding the metal salts included of cobalt, nickel, copper and zinc. 
  The molecular structure and purity of these novel compounds have been verified by NMR, ESI-Mass, elemental analysis, and the single crystal of [Zn(L1-C2)Cl2] were also obtained. The phase behavior and mesogenic properties of these compounds were determined by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and powder x-ray diffraction techniques. [Co(L2-Cn)Cl2]、[Ni(L2-Cn)Cl2]、[Zn(L2-Cn)Cl2] complexes exhibit discotic mesophase. The π-π* transition of these ligands occurred at 340 nm, and the charge  transfer band of complexes were observed at ca. 400-420 nm in the absorption spectra. The fluorescent properties of [Zn(L1-Cn)Cl2] and [Zn(L2-Cn)Cl2] series were examined at 530 nm and 545 nm.

中文摘要
英文摘要
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 金屬液晶………………………………………………4
1-4 螺旋結構金屬液晶………………………………12
1-5 實驗設計方向............................13

第二章	實驗部分
2-1 試劑…………………………………………………15
2-2 合成部份……………………… 16
2-2-1前驅物6,6’-dihydrazine-2,2’-bipyridine (DHzBpy)的合成……19
2-2-2長碳鏈4-(alkyloxy)benzaldehyde的合成………………20
2-2-3長碳鏈3,4-Bis(alkyloxy)benzaldehyde的合成…………21
2-2-4長碳鏈3,4,5-Tris-alkyloxy-benzoic acid的合成………23
2-2-5長碳鏈前驅物4-(3',4',5'-trialkoxybenzoyloxy)-benzaldehyde的合成…25
2-2-6配位子的合成……………………………………………27
 2-2-7錯合物的合成……………………………………………32
2-3 物理鑑定方法…………………………………………41

第三章	結果與討論
3-1 配位子的設計…..………………………………………… 44
3-1-1 配位子合成.........................................45
3-1-2 錯合物合成.......................45
3-2 核磁共振光譜 (NMR) ………………… 46
3-2-1前驅物DhzBpy之氫譜 .............................46
3-2-2 醛基衍生物之氫譜...................................46
3-2-3 配位子之氫譜.................48
3-3 錯合物之鑑定………………………………… 49
3-3-1元素分析 (EA) ................................49
3-3-2質譜 (Mass) .......................................50
3-3-3晶體結構 (crystal structure) ................51
3-4 液晶性質的探討…...................................55
3-4-1熱分析數據 (DSC) ...................................55
3-4-2偏光紋理圖 (POM)............................64
3-4-3 x-ray粉末繞射儀 (powder x-ray)............67
3-5 電子吸收光譜 (UV/Vis spectra)……………… 75
3-6 發射光譜 (Emission spectra)………………………… 77

第四章	結論…………………………………81 
第五章	參考文獻 ……………………82

圖目錄
圖1-1.1 The phase transition of the thermotropic liquid crystals……..……………1
圖1-1.2 Calamitic mesophases of (a) N (nematic) ;(b) SmA and (c) SmC……...….1
圖1-1.3 The two chiral mesophases: (a) N*, chiral nematic (cholesteric);
(b) Sc*, chiral smectic C………………………………………………..…2
圖1-1.4 Four types of columnar phase:(a) Colh , hexagonal columnar phase;
(b) Colr , rectangular columnar phase; (c) ColDb, oblique column phase;
(d) ColL , lamellar columnar phase…………………………………….…2
圖1-1.5 Discotic mesophases: (a) ND , discotic nematic phase;(b) Ncol , nematic
columnar phase……………………………………………………………3
圖1-2 The basic section of the liquid crystals………………..………..………..…3
圖1-3.1 Diarylmercurials liquid crystals molecule…………………………………4
圖1-3.2 Nickel dithiolene complexes ………………………………….…...………5
圖1-3.3 Alkoxy-substituted beznonitriles and benzoisonitriles………….…………6
圖1-3.4 small two-ring complexes of d10 metals………………….………..………6
圖1-3.5 Stilbazole complexes of group 10 metals……………………………….…6
圖1-3.6 Different substitute of β-diketonato complexes…………..……..…………6
圖1-3.7 Mesomorphic β-diketonates.………………………………………….……7
圖1-3.8 Rod- and disk-like β-diketonate complexes.……………….…..………… 7
圖1-3.9 Nickel dithiolene complexes.…………………………………………...… 7
圖1-3.10 Basic structure of metal complexes of salicylaldimines…………….……8
圖1-3.11 Different substitute of enaminoketonato complexes.………………….….8
圖1-3.12 (a)Dinuclear complex [Cu(NO2)2CuL]; (b) Macrocyclic oxamide-copper
complex………………………………………………………………….8
圖1-3.13 Self-organization of 4,4'-disubstituted 2,2'-bipyridine metal complexes...9
圖1-3.14 Conformational changes (trans–trans →cis–cis) occurring upon
Complexation………………………………………………………….....9
圖1-3.15 Mesomorphic porphyrins and phthalocyanines………………………......9
圖1-3.16 Mesomorphic Re(I) complexes of 2,2'-bipyridines…………………......10
圖1-3.17 Rare-earth complexes of imidazo[4,5-f]1,10-phenanthroline ligand
(Ln=Y, La, Nd, Sm, Eu, Er, Yb)................................................................10
圖1-3.18 Di- and Trinuclear Ni(II), Cu(II), and VO(II) cis-Enamonoketone
Complexes…...........................................................................................11
圖1-3.19 Ortho-metallated Pd(II) complexes of azobenzene and azine mesogens..11
圖1-3.20 Di- and trinuclear heteropolynuclear metallomesogens contain both
a transition metal ion and a trivalent lanthanide ion…………………....11
圖1-4.1 The various pyridino-functionalized Schiff-base ligands coordinated to a
tetrahedral copper(I) center assemble into columnar liquid-crystalline materials………………………………………………………………….12
圖1-4.2 The first thermotrpoic terpy-based metallomesogens of copper(I) cation complexe……………………………………………………………...….13
圖1-4.2 a).Schematic front and lateral view of the smectic layering b).Schematic representation of the terpy-based metallohelicate……………..…...….13
圖3-1-1 錯合物之流程及縮寫代號..……………………...…………………….45
圖3-2-1 前驅物DhzBpy之氫譜…………………………………..…………….46
圖3-2-2 前驅物Ald-1C16之氫譜……………………………………………….47
圖3-2-3 前驅物Ald-2C14之氫譜………………………………..……………..47
圖3-2-4 前驅物Ald-3C12之氫譜……………………………………………….47
圖3-2-5 配位子L1-C14之氫譜…………………………………………….…..48
圖3-2-6 配位子L2-C14之氫譜…………………………………….…………..48
圖3-2-7 配位子L3-C16之氫譜…………………………………….…………..49
圖3-3-1 錯合物[Ni(L2-C12)Cl2]之質譜圖………………………….…………..50
圖3-3-2 錯合物[Zn(L1-C2)Cl2] 之單晶結構圖…………………….…………..52
圖3-3-3 錯合物[Zn(L1-C2)Cl2] 之配位結構示意圖…………….……………..53
圖3-3-4 錯合物[Zn(L1-C2)Cl2]之分子排列結構圖…………….………………54
圖3-3-5 錯合物[Zn(L1-C2)Cl2]之分子排列結構圖……………….……………54
圖3-4-1 配位子L1-C14於135度下之固態紋理圖…………………………..…55
圖3-4-2 配位子L1-Cn之相變化範圍柱狀圖……………………………….….56
圖3-4-3 配位子L2-C14於124度下之固態紋理圖………………………….…57
圖3-4-4 配位子L2-Cn之相變化範圍柱狀圖…………………………………..57
圖3-4-5 配位子L3-Cn之相變化範圍柱狀圖…………………………………..58
圖3-4-6 錯合物[Zn(L1-Cn)Cl2]之相變化範圍柱狀圖……..……………….…..59
圖3-4-7 錯合物[Zn(L1-C12)Cl2]之熱重分析(TGA)圖………………………....59
圖3-4-8 錯合物[Zn(L2-Cn)Cl2]之液晶排列示意圖……………………………60
圖3-4-9 錯合物[Zn(L2-Cn)Cl2]之相變化範圍柱狀圖……..……………….…..61
圖3-4-10 錯合物[Co(L2-Cn)Cl2]之熱分析(DCS)圖譜……...…………..….…..62
圖3-4-11 錯合物[ Ni(L2-Cn)Cl2]之熱分析(DCS)圖譜…….……..……….…......63
圖3-4-12 錯合物[Cu(L2-Cn)Cl2]之熱分析(DCS)圖譜…….…..…..……...……..64
圖3-4-13 錯合物[Co(L2-C12)Cl2]於175oC下之液晶紋理圖………..……..……65
圖3-4-14 錯合物[Co(L2-C14)Cl2]於185oC下之液晶紋理圖……………………65
圖3-4-15 錯合物[Co(L2-C16)Cl2]於165oC下之液晶紋理圖……….....….…..…66
圖3-4-16 錯合物[ Ni(L2-C16)Cl2]於165oC下之液晶紋理圖…………..….……66
圖3-4-17 錯合物[Zn(L2-C16)Cl2]於175oC下之液晶紋理圖…………..……..…67
圖3-4-18 錯合物[Zn(L2-C14)Cl2]於165oC下之液晶紋理圖…………..……..…67
圖3-4-19 錯合物[Zn(L2-C16)Cl2]於160oC下之液晶紋理圖………..….………67
圖3-4-20 化合物[Co(L2-C14)Cl2]在固態之粉末繞射圖…….…………..………68
圖3-4-21 化合物[Co(L2-C14)Cl2]在190度下之粉末繞射圖……………………69
圖3-4-22 化合物[Co(L2-C14)Cl2]在液相之粉末繞射圖………………..…….…69
圖3-4-23 化合物[Ni(L2-C16)Cl2]在固態之粉末繞射圖…………….…..………70
圖3-4-24 化合物[Ni(L2-C16)Cl2]在180度下之粉末繞射圖…………..….……71
圖3-4-25 化合物[Zn(L2-C14)Cl2]在結晶相之粉末繞射圖………….…..………72
圖3-4-26 化合物[Zn(L2-C14)Cl2]在165度下之粉末繞射圖…………..….……72
圖3-4-27 化合物[Zn(L2-C14)Cl2]在150度之粉末繞射圖………………………73
圖3-4-28 化合物[Zn(L2-C14)Cl2]在40度之粉末繞射圖……………………….73
圖3-5-1 配位子一化合物之吸收光譜,溶於CH2Cl2……………………………75
圖3-5-2 配位子二化合物之吸收光譜,溶於CH2Cl2……………………………76
圖3-6-1 配位子L1-C12之吸收與放射光譜,溶於CH2Cl2……………………..78
圖3-6-2 配位子L2-C12之吸收與放射光譜,溶於CH2Cl2……………………..78
圖3-6-3 錯合物[Zn(L1-C12)Cl2]之吸收與放射光譜,溶於CH2Cl2….…………79
圖3-6-4 錯合物[Zn(L2-C12)Cl2]之吸收與放射光譜,溶於CH2Cl2…..…...……80
表目錄
表3-3-1 配位子一、二錯合物之元素分析………………………………………49
表3-3-2 配位子一、二錯合物之質譜分析數據..………………………….......…51
表3-3-3 Crystal data and structure refinement of [Zn(L2-C2)Cl2]........................ 52
表3-4-1 配位子L1-Cn之熱分析(DSC)數據.........................................................55
表3-4-2 配位子L2-Cn之熱分析(DSC)數據.........................................................56
表3-4-3 配位子L3-Cn之熱分析(DSC)數據.........................................................57
表3-4-4 錯合物[Zn(L2-Cn)Cl2]之熱分析(DSC)數據............................................60
表3-4-5 錯合物[Co(L2-Cn)Cl2]之熱分析(DSC)數據............................................61
表3-4-6 錯合物[Ni (L2-C14)Cl2]之熱分析(DSC)數據..........................................62
表3-4-7 化合物[Co(L2-Cn)Cl2]在液晶相時之XRD整理表................................69
表3-4-8 化合物[Ni(L2-Cn)Cl2]在液晶相時之XRD整理表.................................71
表3-4-9 化合物[Zn(L2-Cn)Cl2]在液晶相時之XRD整理表.................................74
表3-5-1 配位子一化合物之吸收波長及消光係數值……………………………76
表3-5-2 配位子二化合物之吸收波長及消光係數值……………………………77
附圖目錄
附圖1. 化合物DCBP之1HNMR光譜(CDCl3, 300Hz)……….….………….…86
附圖2. 化合物DhzBpy之1HNMR光譜(d6-DMSO, 300Hz)……..………….…87
附圖3. 化合物Ald-1C12之1HNMR光譜(CDCl3, 300Hz)…………………..…88
附圖4. 化合物Ald-1C14之1HNMR光譜(CDCl3, 300Hz)………………….…..89
附圖5. 化合物Ald-1C16之1HNMR光譜(CDCl3, 300Hz)…………………..….90
附圖6. 化合物Ald-2C10之1HNMR光譜 (CDCl3, 300Hz)………….….…..….91
附圖7. 化合物Ald-2C12之1HNMR光譜 (CDCl3, 300Hz)…..……..…………..92
附圖8. 化合物Ald-2C14之1HNMR光譜 (CDCl3, 300Hz)…………….……….93
附圖9. 化合物Ald-2C16之1HNMR光譜 (CDCl3, 300Hz)……………...….…..94
附圖10. 化合物Ald-3C10之1HNMR光譜 (CDCl3, 300Hz)………………….….95
附圖11. 化合物Ald-3C12之1HNMR光譜 (CDCl3, 300Hz)………………….…96
附圖12. 化合物Ald-3C14之1HNMR光譜 (CDCl3, 300Hz)…………….…….…97
附圖13. 化合物L1-C12之1HNMR光譜 (CDCl3, 300Hz)……………….…….…98
附圖14. 化合物L1-C14之1HNMR光譜 (CDCl3, 300Hz)………………...……..99
附圖15. 化合物L1-C16之1HNMR光譜 (CDCl3, 300Hz)…………………..…100
附圖16. 化合物L2-C10之1HNMR光譜 (CDCl3, 300Hz)……………...…….…101
附圖17. 化合物L2-C12之1HNMR光譜 (CDCl3, 300Hz)………………...…….102
附圖18. 化合物L2-C14之1HNMR光譜 (CDCl3, 300Hz)……………….….…103
附圖19. 化合物L2-C16之1HNMR光譜 (CDCl3, 300Hz)………………..……104
附圖20. 化合物L3-C10之1HNMR光譜 (CDCl3, 300Hz)…………………..…105
附圖21. 化合物L3-C12之1HNMR光譜 (CDCl3, 300Hz)………….….………106
附圖22. 化合物L3-C14之1HNMR光譜 (CDCl3, 300Hz)……………..………107
附圖23. [Zn(L2-C12)Cl2]之FAB-Mass圖譜…………………….……………..…108
附圖24. [Zn(L2-C14)Cl2]之FAB-Mass圖譜……………………….………..……109
附圖25. [Zn(L2-C16)Cl2]之FAB-Mass圖譜……………………………...………110
附圖26. [Ni(L2-C14)Cl2]之ESI-Mass圖譜……………………………………….111
附圖27. [Ni(L2-C16)Cl2]之ESI-Mass圖譜……………………………….………112
附圖28. [Co(L2-C12)Cl2]之ESI-Mass圖譜………………………………….……113
附圖29. [Co(L2-C14)Cl2]之ESI-Mass圖譜………………………………………114
附圖30. [Co(L2-C16)Cl2]之ESI-Mass圖譜………………………….…….…..….115
附圖31. [Cu(L2-C12)Cl2]之FAB-Mass圖譜....................................................…...116
附圖32. [Cu(L2-C14)Cl2]之FAB-Mass圖譜……………………………..…….…117
附圖33. [Cu(L2-C16)Cl2]之FAB-Mass圖譜………………………….……….….118
附圖34. [Co(L1-C12)Cl2]之FAB-Mass圖譜...........................................................119
附圖35. [Co(L1-C14)Cl2]之FAB-Mass圖譜……………………….….………….120
附圖36. [Co(L1-C16)Cl2]之FAB-Mass圖譜……………………………..…….…121
附圖37. [Zn(L1-C12)Cl2]之FAB-Mass圖譜…………………..…….……………122
附圖38. [Zn(L1-C14)Cl2]之FAB-Mass圖譜………………………….….……… 123
附圖39. [Zn(L1-C16)Cl2]之FAB-Mass圖譜……………………………….….….124
附圖40. L1-C12之DSC圖譜……………………………..………….…...……125
附圖41. L1-C14之DSC圖譜……………………………………………..……126
附圖42. L1-C16之DSC圖譜…………………………………………………..127
附圖43. L2-C10之DSC圖譜……………………….………………………..…128
附圖44. L2-C12之DSC圖譜…………………………………….………….…129
附圖45. L2-C14之DSC圖譜……………………………….…………………..130
附圖46. L2-C16之DSC圖譜……………………………………………….…..131
附圖47. L3-C10之DSC圖譜……………………………..……………………..132
附圖48. L3-C12之DSC圖譜……………………….…………………….…..…133
附圖49. 49:L3-C14之DSC圖譜…………………………………………….…134
附圖50. [Co(L2-C12)Cl2]之DSC圖譜…………………….……………………135
附圖51. [Co(L2-C14)Cl2]之DSC圖譜…………………….……………………136
附圖52. [Co(L2-C16)Cl2]之DSC圖譜……………………………………….…137
附圖53. [Ni(L2-C12)Cl2]之DSC圖譜…………………………………………..138
附圖54. [Ni(L2-C14)Cl2]之DSC圖譜…………………………………………..139
附圖55. [Ni(L2-C16)Cl2]之DSC圖譜………………………………..…………140
附圖56. [Zn(L2-C12)Cl2]之DSC圖譜……………………………..……………141
附圖57. [Zn(L2-C14)Cl2]之DSC圖譜………………………………….…….…142
附圖58. [Zn(L2-C16)Cl2]之DSC圖譜………………………………………….143
附圖59. [Cu(L2-C12)Cl2]之DSC圖譜………………………………………….144
附圖60. [Cu(L2-C14)Cl2]之DSC圖譜…………...……………………………..145
附圖61. [Co(L2-C12)Cl2]之變溫粉末繞射圖……………………..……………146
附圖62. [Co(L2-C14)Cl2]之變溫粉末繞射圖……………...…………………...146
附圖63. [Co(L2-C16)Cl2]之變溫粉末繞射圖…………………………………..147
附圖64. [Ni(L2-C12)Cl2]之變溫粉末繞射圖………………………………..….147
附圖65. [Ni(L2-C14)Cl2]之變溫粉末繞射圖………………………………...…148
附圖66. [Ni(L2-C16)Cl2]之變溫粉末繞射圖…………………………………...148
附圖67. [Zn(L2-C12)Cl2]之變溫粉末繞射圖…………………………………..149
附圖68. [Zn(L2-C14)Cl2]之變溫粉末繞射圖…………………………………..149
附圖69. [Zn(L2-C16)Cl2]之變溫粉末繞射圖…………………………………..150
附圖70. L1-Cn之電子吸收光譜………………………………………………...151
附圖71. L2-Cn之電子吸收光譜………………………………………………...151
附圖72. L3-Cn之電子吸收光譜………………………………………………...152
附圖73. [Co(L1-Cn)Cl2]之電子吸收光譜……………………………...……….152
附圖74. [Zn(L1-Cn)Cl2]之電子吸收光譜………………………………...…….153
附圖75. [Co(L2-Cn)Cl2]之電子吸收光譜………………………………………153
附圖76. [Ni(L2-Cn)Cl2]之電子吸收光譜……………………………………….154
附圖77. [Cu(L2-Cn)Cl2]之電子吸收光譜…………………………………...….154
附圖78. [Zn(L2-Cn)Cl2]之電子吸收光譜………………………………………155
附圖79. [Co(L3-Cn)Cl2]之電子吸收光譜………………………………………155
附圖80. [Ni(L3-Cn)Cl2]之電子吸收光譜…………...…………………………..156
附圖81. [Zn(L3-Cn)Cl2]之電子吸收光譜…………………...………………….156
附圖82. L1-C14之發射光譜……………………………………………………157
附圖83. [Zn(L1-C14)Cl2]之發射光譜…………………………………………..157
附圖84. L1-C16之發射光譜……………………………………………………158
附圖85. [Zn(L1-C16)Cl2]之發射光譜…………………………………………..158
附圖86. L3-C10之發射光譜……………………………………………………159
附圖87. [Zn(L3-C10)(ClO4)2]之發射光譜………………………………………159
附圖88. L3-C12之發射光譜…………………………………………………….160
附圖89. [Zn(L3-C12)(ClO4)2]之發射光譜……………………………...……….160
附圖90. L3-C14之發射光譜…………………………………………………….161
附圖91. [Zn(L3-C14)(ClO4)2]之發射光譜………………………………………161

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