本篇論文以1,10-雙雜菲(1,10-phenanthroline) 為架構，合成出類紫質開環配位子bis(1,10-phananthrolin-2-yl)amine (HDPA)，並對其物理化學性質進行分析，亦藉由HDPA是否質子化，調控反應物對架橋亞胺基或雜環氮進行修飾，作合成上之探討。由X-ray單晶結構解析，不同pH值環境下，HDPA可具饒曲transoid 及平面syn兩種結構。經氫核磁共振光譜研究顯示，調整pH值，HDPA的構形可因一罕見的分子內 CH•••N氫鍵，產生構形改變。理論計算結果發現，transoid 及平面syn兩種結構之熱焓值，僅差0.5 kcal mol-1，說明氫核磁共振光譜中所見現象，HDPA於溶液態中可進行兩種結構互換。

HDPA 與鋅離子反應可得HDPA的鋅錯合物[Zn(HDPA)(OAc)]。經x-ray單晶結構解析，因強烈π－π作用力影響，[Zn(HDPA)(OAc)]以雙聚體方式呈現於單晶結構中。於晶體堆疊方面，除了π－π作用力外，為使電荷平衡，[Zn(HDPA)(OAc)]亦與大陰離子 [Zn7(μ4-O)2(OAc)12]2-形成共結晶，而此七核鋅簇 [Zn7(μ4-O)2(OAc)12]2-是文獻中未曾被報導過的特殊陰離子。於紫外光-可見光譜中，[Zn(HDPA)(OAc)]的最低能量吸收峰可延伸至400 nm至500 nm，為 的分子內電荷轉移吸收峰。發射光譜中，可以利用 385 nm 為激發波長，使[Zn(HDPA)(OAc)]在385 nm及580 nm產生雙發色光。其中，385 nm為配位子π－π*的螢光，385 nm為架橋亞胺基nimine至配位子π*的螢光。藉由以上光學特性，進而設計離子偵測實驗，發現 HDPA 對於鋅離子具專一偵測性，可作為良好的離子偵測器。

2,2-dipyridylamine 與不同碳數的溴烷反應,可得到一系列高純度具有離子液體特性的N,N’-dialkyl-2,2’-azapyridocyane (Cn-Dpya-X) 衍生物。由X-ray單晶結構分析可知，長碳鏈修飾在吡啶而非架橋亞胺基，並與BF4-共結晶，堆疊成為一層狀結構。以溴為陰離子的系列化合物中，短碳鏈的離子液體具有接近室溫的溶點，長碳鏈的化合物則具有熱致型離子液晶的特性；在偏光顯微鏡下可觀測到SmA的紋理圖。此系列離子液體在加入水後，可轉為層狀排列的濃致型離子液晶。

A family of acyclic aza-bridged bis-1,10-phenanthroline compounds has been synthesized in a convenient way. The resulting compounds 2 and 2•HCl were fully characterized and their solid-state structures and NMR spectroscopic properties were investigated to assess how the structural units affect the alkylation reactions. Solid state structure and NMR spectroscopic investigation reveal the transoid structure for 2. The broadening NMR peak in 2 is due to an unusual intramolecular CH…N hydrogen bond. The unique conformation provides an efficient and regioselective method to prepare the amino-substituted bis-2,2’-1,10-phenanthroline derivatives and 1,10-phenanthrolino-N-alkylated compounds.

An aza-bridged bis-1,10-phenanthroline ligand HDPA was synthesized and observed to display a tetradentate coordination mode to form [Zn(HDPA)(OAc)]. The x-ray crystallography revealed the structure of [Zn(HDPA)(OAc)]2[Zn7(μ4-O)2(OAc)12], and the anion unit [Zn7(μ4-O)2(OAc)12]2- is the first case of a related structure of heptanuclear Zn(II) clusters. The compound then showed its lowest-energy transition assigned to   ILCT band and displayed dual fluorescence with λmax = 385nm and 580 nm upon excitation at 325 nm. The emissions with λmax = 580 nm came from an intraligand 1(nimine-π*) excited state. The investigated fluorescence properties of HDPA associated with various metal ions indicated that the emission with λmax at 580 nm was more sensitive with Zn(II) than with other interfering cations.

The synthesis and characterization of N,N’-dialkyl-2,2’-azapyridocyane (Cn-Dpya-X, n = 4, 8, 10, 12, 14, 16 and 18 for X = Br-, ClO4-, BF4-, NO3-) of ionic liquid series are reported. The x-ray crystallography revealed the structure of [C14-Dpya-BF4] and identified the lamellar packing. The short alkyl chains compounds (n = 4,8 and 10) exhibit liquid properties at room temperature. The ionic liquid crystalline behavior of Cn-Dpya-Br (n = 12,14,16,18) was investigated by means of differential scanning calorimetry, polarizing light optical microscopy and X-ray diffractometry. All these four compounds exhibit SmA mesophases when cooling from isotropic liquid. Addition of water to Cn-Dpya-Br (n = 14,16 and 18) is shown to result the lyotropic liquid crystal behaviors.

Contents
中文摘要	i
Abstract	ii
Chapter I.	
Aza-bridged Bis-1,10-phenanthroline Acyclic Derivatives: Synthesis, Structure and Regioselective Alkylation	
Introduction	2
Results and Disscusion 2
Summary 14
Chapter II.	
An Intraligand Charge-Transfer Fluorescent Sensor of Bis-diphenanthrolinylamine for Zn(II)	
Introduction 16
Experimental 22
Results and  DIscussion 24
Summary 47
Chapter III.	
Thermotropic and Lyotropic Liquid Crystals of Dipyridylamine Salts	
Introduction 49
Experimental 53
Results and Discussion 60
Summary 80
Conclusion 82
Reference 84
Supporting Information 90


List of Figures

Figure 1-1	1H-NMR spectra of (a) [H2DPA]Cl, (b)HDPA, (c)MeDPA ,(d)N-MeDPA in DMSO-d6 solution at 300 K. 5
Figure 1-2	1H-NMR spectra of MeDPA in DMOS-d6 solution in various temperature. 9
Figure 1-3	ORTEP representations of the X-ray crystal structures of the HDPA and [H2DPA]Cl. 11
Figure 2-1	Cartoon representation of Cys2His2 zinc finger motif. 17
Figure 2-2	Classification of zinc fluorescence probes. 19
Figure 2-3	Principle of cation recognition by fluorescent PET sensors. 19
Figure 2-4	Spectral displacements of PCT sensors. 20
Figure 2-5	ORTEP diagram of [Zn(HDPA)(OAc)]2[Zn7(μ4-O)2(OAc)12]. 26
Figure 2-6	Packing diagram of [Zn(HDPA)(OAc)]2[Zn7(μ4-O)2(OAc)12]. 27
Figure 2-7	Molecular diagram of [Zn(HDPA)(OAc)]+. 27
Figure 2-8	Molecular diagram of [Zn7(μ4-O)2(OAc)12]2-. 28
Figure 2-9	UV/Vis spectra of 2.68 × 10-5 M HDPA in CH3CN, addition of Zn(OAc)2 MeOH solution. 31
Figure 2-10	UV/Vis spectra of 2.68 × 10-5 M HDPA in CH3CN, addition of Zn(OAc)2 MeOH solution. 32
Figure 2-11	UV/Vis spectra of 2.68 × 10-6 M HDPA CH3CN,addition of Zn(OAc)2 MeOH solution. 33
Figure 2-12	UV/Vis spectra of HDPA:Zn(OAc)2 = 1:1 mole ratio in 1% DMSO MeCN solution,various concentration. 34
Figure 2-13	Contour plots and orbital energies for Zn(HDPA)(OAc) at solid state obtained by DFT method. 36
Figure 2-14	UV/Vis spectrum of HDPA:Zn(OAc)2 =1:1 mole ratio CH3CN solution, addition of HCl MeOH solution. 37
Figure 2-15	Tunable ILCT process of Zn(HDPA)(OAc). 37
Figure 2-16	UV/Vis spectra of HDPA:Zn(OAc)2 = 1:7 mole ratio CH3CN solution, addition of ethylenediamine MeOH solution. 38
Figure 2-17	UV/Vis spectrum of HDPA: Zn(OAc)2 = 1:7 mole ratio CH3CN solution addition of ethylenediamine MeOH solution.	39
Figure 2-18	The absorption, emission and excitation spectrum of 2.68 × 10-5 M Zn(DPA)(OAc) CH3CN solution at room temperature, λex = 450 nm. 40
Figure 2-19	Single-exponential fluorescence decay of Zn(DPA)(OAc) in CH3CN solution. 41
Figure 2-20	The absorption and emission spectrum of 2.68 × 10-5 M Zn(DPA)(OAc) CH3CN solution at room temperature, λex = 325nm. 42
Figure 2-21	Emission spectra of 2.6 × 10-5 M HDPA CH3CN solution, addition of Zn(OAc)2 MeOH solution, λex = 325 nm and 450nm. 43
Figure 2-22	Fluorescence response of HDPA (1.32 × 10-6 M, CH3CN) to different ions (1.32 × 10-6 M, MeOH). 45
Figure 3-1	Common cations and anions of ionic liquid. 49
Figure 3-2	Schematic representation of solid, liquid crystal and liquid. 51
Figure 3-3	Schematic representation of the common mesophase. 52
Figure 3-4	ORTEP diagram of C14-Dpya-BF4. 60
Figure 3-5	Packing diagram of C14-Dpya-BF4. 62
Figure 3-6	DSC Curve of C12-Dpya-Br. 65
Figure 3-7	DSC Curve of C14-Dpya-Br. 67
Figure 3-8	DSC Curve of C16-Dpya-Br. 67
Figure 3-9	DSC Curve of C18-Dpya-Br. 68
Figure 3-10	Variation of phase transition temperatures of the Cn-Dpya-Br (n = 10,12,14,16,18. 70
Figure 3-11	The optical texture observed by C18-Dpya-Br. 70
Figure 3-12	Melting point temperature ranges of different ionic liquid crystals. 72
Figure 3-13	The optical texture observed by C14-Dpya-Br/H2O. 72
Figure 3-14	Powder XRD of C14-Dpya-Br at 65 ˚C,crystalline phase. 73
Figure 3-15	Powder XRD of C14-Dpya-Br at 80 ˚C,mesophase. 74
Figure 3-16	Powder XRD of C14-Dpya-Br at 110 ˚C, isotropic. 74
Figure 3-17	Powder XRD of C16-Dpya-Br at 70 ˚C,crystalline phase. 75
Figure 3-18	Powder XRD of C16-Dpya-Br at 97 ˚C, mesophase. 76
Figure 3-19	Powder XRD of C18-Dpya-Br at 118 ˚C, mesophase. 76
Figure 3-20	Powder XRD of C18-Dpya-Br at various temperature. 77
Figure 3-21	Schematic representation of different solid comformations. 78


List of Tables

Table 1-1	Reaction conditions of CP and HDPA.	4
Table 1-2	Chemical shifts and coupling constants for selected compounds. 5
Table 1-3	Crystal data and structure refinement for [H2DPA]Cl. 12
Table 1-4	Crystal data and structure refinement for HDPA. 13
Table 2-1	Crystal data and structure refinement for [Zn(HDPA)(OAc)][Zn7(μ4-O)2(OAc)12]. 29
Table 2-2	Selected bond lengths (Å) and angles (º) for [Zn(HDPA)(OAc)][Zn7(μ4-O)2(OAc)12]. 30
Table 2-3	Fluorescent properties of zinc complexes. 44
Table 2-4	Relative absorbance of 1.34 × 10-6 M HDPA CH3CN solution to 1 equiv of metal ions MeOH solution. 45
Table 3-1	Elemental Analysis data of Cn-Dpya-Br. 59
Table 3-2	Crystal data and structure refinement for C14-DPYA-BF4. 63
Table 3-3	The phase transition and temperatures(oC) of C10-Dpya-Br. 64
Table 3-4	The phase transition and temperatures (oC) of C12-Dpya-Br. 65
Table 3-5	The phase transition and temperatures(oC) of C14-Dpya-Br. 66
Table 3-6	The phase transition and temperatures (oC)of C16-Dpya-Br. 68
Table 3-7	The phase transition and temperatures (oC) of C18-Dpya-Br. 69
Table 3-8	d-spacing list of Cn-Dpya-Br at crystal phase. 77
Table 3-9	Relationship between alkyl chain and d-spacing of Cn-Dpya-Br 
at mesophase. 79
Table 3-10	Porperties of some common ILCs. 80

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