微調具光學活性聯二萘酚和其二甲亞碸包合物的光激發光性質

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研究生：	彭鎮帆 Jen Fan Peng
論文名稱：	微調具光學活性聯二萘酚和其二甲亞碸包合物的光激發光性質 Fine Tuning of Photoluminescence Properties of Optically Active 2,2''-Dihydroxy-1,1''-dinaphthyl and Its Dimethyl Sulfoxide Inclusion Compounds
指導教授：	李度 Tu Lee
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程與材料工程學系 Department of Chemical & Materials Engineering
畢業學年度：	98
語文別：	英文
論文頁數：	239
中文關鍵詞：	聯二萘酚
外文關鍵詞：	BINOL
相關次數：	點閱：8 下載：0
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近幾年來，有機材料由於製程容易、低成本、機械可撓性及可於室溫下鍍在不同的基材上等特性，在物理、化學、光學、工程領域方面有吸引相當多的研究投入。現在有機半導體材料用於有機發光二極體(OLEDs)及有機太陽電池(OPV Cells)大部分都具有共軛π電子結構的特色，例如: 8-羥基喹啉鋁(Alq3)及碳六十(Fullerene)。經過廣泛的文獻閱覽後，很少文獻將對掌性的影響帶入光電製程中。因此，我們選擇具有對掌性和可撓性的分子-消旋型聯二萘酚((R,S)-(±)-BINOL)及其左右旋型鏡像物((R)-(+)-BINOL, (S)-(-)-BINOL)，同時它也具備有共軛π電子結構可做為我們研究的對象。利用結晶工程技術，如降溫方法及揮發方法，可用來製備聯二萘酚(BINOL)-二甲亞碸(DMSO)的包合物, 此包合物的形成是藉由主-客分子間的O-H…S=O氫鍵所產生。除此之外，經由溶劑篩選法找出幾乎不能溶解聯二萘酚的溶劑-水分子(H2O), 我們將消旋型聯二萘酚((R,S)-(±)-BINOL)或左旋型聯二萘酚((S)-(-)-BINOL)固體預先溶解於二甲亞碸(DMSO)溶劑中，然後每次加入0.2毫升的水(H2O)或0.2毫升二甲亞碸(DMSO)經過光激發光(Photoluminescence, PL)的測試, 發現當溶液中水含量增加時，光激發光強度(PL intensity)隨之下降，此結果顯示水含量增加導致大量的消旋型聯二萘酚((R,S)-(±)-BINOL)或左旋型聯二萘酚((S)-(-)-BINOL)分子聚集而造成濃度消光(Concentration Quenching).
在固態相中，我們發現消旋型和左右旋型聯二萘酚分子(BINOL)和二甲亞碸(DMSO)形成的包合物(Inclusion Compounds)可使光激發光的強度(PL Intensity)增加和放射波峰(Emission Peaks)往較大的波長遷移，還有使激發波長範圍(Excitation Wavelength Range)
ii
變寬。這是因為二甲亞碸(DMSO)極性分子嵌入聯二萘酚(BINOL)晶格中改變聯二萘酚(BINOL)相鄰最近分子間的距離，使濃度消光(Concentration Quenching)減弱，且增加偶極-偶極(Dipole-Dipole)間的作用力。相較於一般半體導製程中常用的混摻法(Doping Method)和混合法(Blending Method)，結晶工程的技術 (Crystal Engineering Techniques)是一種同樣會在不改變主分子的情況下，微調放光性質(Emission Properties)的新技術。另外，我們藉由量測結晶分子幾合參數，如: 分子間的距離 (Intermolecular Distances)、二面角(Diheral Angles)、及氫鍵的長度(Hydrogen Bonding Lengths)，量化及探究光激發光與晶體結構的關係。

In recent years, organic materials have attracted much research in many fields, including physics, chemistry, optics, and engineering. These novel materials have exceptional features such as easy processing, low cost, mechanical flexibility, and low temperature deposition on variety of substrate materials. Nowadays, most of organic semiconductors used for organic light emitting diodes (OLEDs) and organic photovoltaic (OPVs) have conjugated π systems, such as Alq3 and C60. After studying an extensive of references, few papers introduced the chiral effect on opto-electronic processes. Therefore, we simply chose chiral and flexible molecules with a conjugated π system, racemic form of 2,2''-dihydroxy-1,1''-dinaphthyl (BINOL) and its (R)-(+)- and (S)-(-)-enantiomers, as model compounds to this research. Using the crystal engineering methods, such as a cooling and an evaporation method, we could prepare inclusion compounds formed between the host BINOL and the guest dimethyl sulfoxide (DMSO) by the O-H…O=S hydrogen bonds. In addition, using water as a bad solvent, we could prepare solutions of (R,S)-(±)-BINOL or (S)-(-)-BINOL solids dissolved DMSO solvent in advance then with addition of either 0.2-ml water or 0.2-ml DMSO each time to make a photoluminescence test and observed the increase water fraction content of a solution, the decrease photoluminescence intensity of either (R,S)-(±)-BINOL or (S)-(-)-BINOL solids. This result only reveals that increasing water content resulted in larger BINOL molecules aggregation to cause the concentration quenching.
iv
In solid phase, we observed that the inclusion compounds of a racemic form and enantiomeric forms of BINOL with DMSO all revealed that the emission peaks moved toward longer wavelength and the intensities enhanced upon photoluminescence. It is the observation that changing the intermolecular distances among nearest BINOL molecules and inserting DMSO (a polar solvent molecule) in the crystal lattice to make the decrease of concentration quenching and the increase of dipole-dipole interaction. Crystal engineering techniques would be novel techniques to tune the emission wavelength without changing the host molecule as compared to the doping method and blending method used in organic semiconductors.
In addition, we provide the insight to understand the relationship between photoluminescence spectra and crystal structures by measuring their molecular crystal geometrical parameters, such as intermolecular distances, dihedral angles, hydrogen bonding lengths.

Table of contents
摘要	i
Abstract	iii
Acknowledgement	v
Table of Contents ............................................................................................................................ vi List of Tables	xi
List of Figures	xv
Chapter 1      Extensive Summary	1
1.1	Introduction	1
1.1.1	Brief of Basics of Light Emission	3
1.1.2	Organic Opto-electronic Materials	4
1.2	Brief Introduction of 2,2''-Dihydroxy-1,1-Dinaphthyl	6
1.3	Conceptual Framework	7
1.4	References	10
Chapter 2      Analytical Instruments	15
2.1	Introduction	15
2.2	Thermal Analysis	19
2.2.1	Differential Scanning Calorimetry (DSC)	19
2.2.2	Thermogravimetric Analysis (TGA)	22
2.3	Microscopic Methods	25
2.3.1	Optical Microscopy (OM)	25
2.3.2	Low Vacuum Scanning Electron Microscopy (LVSEM)	27
2.4	Spectroscopic Analytical Methods	30
2.4.1	Fourier Transform Infrared Spectroscopy (FITR)	30
2.4.2	Photoluminescence Spectroscopy (PL)	32
2.4.3	Ultraviolet-visible Molecular Absorption Spectrometer (UV/vis)	35
2.5	Crystallographic Analysis Methods	38
2.5.1	Powder X-ray Diffraction (PXRD)	38
2.5.2	Single Crystal X-ray Diffraction (SXD)	41
2.6	Conclusions	44
2.7	References	45
Chapter 3      Solubility, Polymorphism, Crystal Habit and Crystallinity of Optically Active 2,2''-Dihydroxy-1,1''-dinaphthyl by Initial Solvent Screening	51
3.1	Introduction	51
3.1.1	Solubility	53
3.1.2	Crystal Habit	54
3.1.3	Crystallinity	55
3.1.4	Polymorphism and Solvatomorphism (Inclusion Compound)	56
3.2	Materials	60
3.2.1	(R)-(+)-BINOL	60
3.2.2	(R,S)-(±)-BINOL	64
3.2.3	(S)-(-)-BINOL	68
3.2.4	Solvents	72
3.3	Experimental Procedures	75
3.3.1	Initial Solvent Screening	75
3.3.2	Analytical Measurements	78
3.4	Results and Discussion	80
3.4.1	Solubility	80
3.4.2	Crystal Habit	97
3.4.3	Crystallinity	105
3.4.4	BINOL Inclusion Compounds	109
3.5	Conclusions	113
3.6	References	115
Chapter 4      Fine Tuning of Photoluminescence Properties of 2,2''-Dihydroxy-1,1''-dinaphthyl and Its Dimethyl Sulfoxide Inclusion Compounds………..	121
4.1	Introduction	121
4.2	Materials	125
4.2.1	Racemic BINOL, (R)-(+)-BINOL and (S)-(-)-BINOL	125
4.2.2	Organic solvents	128
4.3	Experimental Methods	128
4.3.1	Preparation of the Racemic Inclusion Compounds of (R,S)-(±)-BINOL•DMSO and (R,S)-(±)-BINOL•2DMSO	128
4.3.2	Preparation of the Enantiomeric Inclusion Compounds of             (R)-(+)-BINOL•2DMSO and (S)-(-)-BINOL•2DMSO	129
4.3.3	Solution Preparation of (R,S)-(±)-BINOL, (R)-(+)-BINOL, and S-(-)-BINOL in DMSO Solvent with The Addition of H2O	132
4.4	Analytical Measurements	133
4.4.1	Optical Microscopy (OM)	133
4.4.2	Differential Scanning Calorimetry (DSC)	133
4.4.3	Thermogravimetric Analysis (TGA)	134
4.4.4	Fourier Transform Infrared Spectroscopy (FTIR)	134
4.4.5	Powder X-ray Diffractometry (PXRD)	135
4.4.6	Single Crystal X-ray Diffraction (SXD)	135
4.4.7	Ultraviolet-visible Molecular Absorption Spectrometer (UV/vis)	135
4.4.8	Photoluminescence Spectroscopy (PL)	136
4.5	Results and Discussion	139
4.6	Conclusions	148
4.7	Supporting Information	169
4.7.1	OM Micrographs	169
4.7.2	DSC/TGA Traces	171
4.7.3	IR Spectra	174
4.7.4	PXRD and Calculated PXRD Patterns	180
4.7.5	Crystallographic Data	185
4.7.6	Crystallization Kinetics	193
4.8	References	200
Chapter 5      Conclusions and Future work	206
5.1	Initial Solvent Screening	206
5.2	Fine Tuning of Photoluminescence Properties of BINOL-DMSO Inclusion Compounds	207
 
List of Tables
Table 2.1  Brief descriptions of the analytical apparatuses in this study.	18
Table 3.1  The reflection parameters of single crystal X-ray data of (R)-(+)-BINOL.	62
Table 3.2  The IR characteristic bands of the enantiopure (R)-(+)-BINOL.	63
Table 3.3  The reflection parameters of single crystal X-ray data of (R,S)-(±)-BINOL.	66
Table 3.4  The IR characteristic bands of the (R,S)-(±)-BINOL.	67
Table 3.5  The reflection parameters of single crystal X-ray data of (S)-(-)-BINOL.	70
Table 3.6  The IR characteristic bands of the enantiopure (S)-(-)-BINOL.	71
Table 3.7  23 kinds of solvents in our experiments.	72
Table 3.8  Form space of (R)-(+)-BINOL at 25 oC.	81
Table 3.9  Form space of (R,S)-(±)-BINOL at 25 oC.	84
Table 3.10  Form space of (S)-(-)-BINOL at 25 oC.	88
Table 3.11  The molar enthalpy and entropy of dissolution of (R)-(+)-BINOL in different solvents.	92
Table 3.12  The molar enthalpy and entropy of dissolution of (R,S)-(±)-BINOL in different solvents.	94
Table 3.13  The molar enthalpy and entropy of dissolution of (S)-(-)-BINOL in different solvents.	96
Table 3.14  Aspect ratios of (R)-(+)-BINOL in 21good solvents.	100
Table 3.15  Aspect ratios of (R,S)-(±)-BINOL in 18 good solvents.	102
Table 3.16  Aspect ratios of (S)-(-)-BINOL in 21 good solvents.	104
Table 3.17  The enthalpy of melting and crystallinity of (R)-(+)-BINOL in 21 good solvents.	106
Table 3.18  The enthalpy of melting and crystallinity of (R,S)-(±)-BINOL in 18 good solvents.	107
Table 3.19  The enthalpy of melting and crystallinity of (S)-(-)-BINOL in 21 good solvents.	108
Table 3.20  The discovery of the inclusion compounds of three compounds, (R)-(+)-BINOL, (R,S)-(±)-BINOL, and (S)-(-)-BINOL,.	111
Table 3.21  Thermal analysis data for the inclusion compounds.	112
Table 4.1  Thermal analysis for the racemic and enantiomeric BINOL inclusion compounds.	131
Table 4.2  PL properties of solid-state crystal	149
Table 4.3  Hydrogen-bonding and dihedral angle of C2-C1-C1''-C2'' (º) of BINOL	150
Table S 1  Thermal analytical data for the BINOL inclusion compounds.	172
Table S2  IR bands of (R,S)-(±)-BINOL.	178
Table S3  IR bands of (R)-(±)-BINOL.	178
Table S4  IR bands of (S)-(-)-BINOL.	179
Table S5  The reflection parameters of single crystal X-ray data of (R,S)-(±)-BINOL.	182
Table S6  The reflection parameters of single crystal X-ray data of (R)-(+)-BINOL.	182
Table S7  The reflection parameters of single crystal X-ray data of (S)-(-)-BINOL.	182
Table S8  The reflection parameters of single crystal X-ray data of (R,S)-(±)-BINOL•DMSO.	183
Table S9  The reflection parameters of single crystal X-ray data of (R)-(±)-BINOL•2DMSO.	183
Table S10  The reflection parameters of single crystal X-ray data of (R,S)-(±)-BINOL•2DMSO.	183
Table S11  The reflection parameters of single crystal X-ray data of (S)-(-)-BINOL•2DMSO.	184
Table S12  Crystal data and data collection and final refinement parameters	185
Table S13  Selected Bond Lengths (Å) of (R,S)-(±)-BINOL, (R,S)-(±)-BINOL, (S)-(-)-BINOL, (R)-(+)-BINOL•2DMSO, (R,S)-(±)-BINOL•2DMSO, and (S)-(-)-BINOL•2DMSO.a	188
Table S14  Selected Bond Angles (°) of R,S-(±)-BINOL, (R)-(+)-BINOL, (S)-(-)-BINOL, (R)-(+)-BINOL•2DMSO, (R,S)-(±)-BINOL•2DMSO, and (S)-(-)-BINOL•2DMSO.a	190
Table S15  Tabulated Values of S0, τ, γ, and J0 of the Three Experimental Sets of Recrystallization of the (a) (R,S)-(±)-BINOL (MW= 286.32) ,(b) (R,S)-(±)-BINOL•DMSO (MW = 364.45), and (c) (S)-(-)-BINOL•DMSO (MW = 442.6), Having Different Initial Supersaturation Ratios of S0 That Were Shown Below.	197
Table S16  Tabulated Values of S0, ΔGν, ΔGcr, J, rc, and i* of the Three Experimental Sets of Recrystallization of the (a) (R,S)-(±)-BINOL (MW= 286.32) ,(b) (R,S)-(±)-BINOL•DMSO (MW = 364.45), and (c) (S)-(-)-BINOL•DMSO (MW = 442.6), Having Different Initial Supersaturation Ratios of S0 That Were Shown Below.	198
Table S17  Tabulated Values of S0, Crystal Growth Time, RG, g, KGAt, and the End Point of the Three Experimental Sets of Recrystallization of the (a) (R,S)-(±)-BINOL (MW= 286.32) ,(b) (R,S)-(±)-BINOL•DMSO (MW = 364.45), and (c) (S)-(-)-BINOL•DMSO (MW = 442.6), Having Different Initial Supersaturation Ratios of S0 That Were Shown Below.  The crystal growth time and the end point measured the total amount of time required for desupersaturation from t = τ and from t =0.	198
List of Figures
Figure 1.1  The world-wide market for (a) organic light emitting panel display, and (b) organic photovoltaic (OPV) and dye-sensitized solar cell (DSC)-based PV.	2
Figure 1.2  Molecular structure of dopants and hosts for fluorescence OLEDs.	5
Figure 1.3  Model materials for photovoltaic cells: (a)-(d) are donors, (e) is an acceptor.	6
Figure 1.4  The molecular structures of (a) (R,S)-(±)-BINOL, (b) (R)-(+)-BINOL and (c) (S)-(-)-BINOL.	7
Figure 2.1  Schematic representations of (a) heat flux DSC cell and (b) powder compensated DSC. (S and R stand for sample and reference, respectively)	20
Figure 2.2  A typical DSC thermogram including common thermal behaviors, such as glass transition, crystallization, and melting.	21
Figure 2.3  Perkin Elmer DSC 7 differential scanning calorimetry at Precision Instrument Center in National Central University.	22
Figure 2.4  Perkin Elmer TGA 7 thermogravimetric analyzer.	24
Figure 2.5  A schematic representation of TGA thermogram of percentage weight loss (%) versus temperature (oC).  The percentage weight loss (%) of sample was estimated by the difference of the two points, one point corresponding to the weight loss (%) at Tonset and another one point corresponding to the weight loss (%) at Tend.  Tonset was the onset temperature of the beginning of the sample weight loss, and Tend was the temperature of which the weight loss (%) was almost no change and the decomposition of the solute in sample was about to occurred.	24
Figure 2.6  A schematic representation of an OM system.	26
Figure 2.7  Olympus BX-51 optical microscope and Linkam Scientific Instruments Ltd CI94 hot stage.	26
Figure 2.8  The types of signals produced by SEM including secondary electrons, back-scattered electrons (BSE), characteristic X-rays, Auger electron, and transmitted electrons.	28
Figure 2.9  Schematic view of a scanning electron microscope.	29
Figure 2.10  Hitachi S-3500N (Tokyo, Japan) scanning electron microscope at the Precision Instrument Center in National Central University.	29
Figure 2.11 A Schematic illustration of FTIR operation system.	31
Figure 2.12  Perkin Elmer Spectrum One Fourier transforms infrared spectrometer (Perkin Elmer, New York, USA)	31
Figure 2.13  The schematic illustration of luminescence processes.	34
Figure 2.14  Perkin Elmer LS-55 photoluminescence spectrometer (Norwalk, CT, USA) at the Bio-Inspired Materials and High-Throughput Screening Laboratory in National Central University.	34
Figure 2.15  The electromagnetic spectrum of all possible radiation occurred.	35
Figure 2.16  Different kinds of electronic excitation in energy level.	36
Figure 2.17  A double-beam recording spectrophotometer for the ultraviolet and visible regions.	37
Figure 2.18  Diffraction of Bragg’s Law	38
Figure 2.19  Operation system of the diffractometer.	40
Figure 2.20  Bruker Axs D8 Advance Powder X-ray Diffractometer.	40
Figure 2.21  The schematic diagram of the incident direction and diffracted x-ray beams.	43
Figure 2.22  Siemens SMART CCD-based X-ray diffractometer equipped with an Oxford Cryosystems low temperature device.	43
Figure 3.1  Crystallization process by cooling path and solubility curve.	54
Figure 3.2  Schematic diagram of polymorphism for a chemical compound.	57
Figure 3.3  Solubility curves of two enantiotropically related Form I and Form II.	58
Figure 3.4  Solubility curves of two monotropically related Form I and Form II.	59
Figure 3.5  The molecular structure of (R)-(+)-BINOL.  The asterisk was indicated chiral center.  The origin of chirality in BINOL was the restricted rotation around C1-C1'' single bond between the two nearly perpendicular naphthalene rings.	61
Figure 3.6  (a) DSC thermogram of commercial (R)-(+)-BINOL was obtained from Sigma Aldrich.  (b) PXRD pattern (upper) of (R)-(+)-BINOL obtained from Sigma Aldrich and compared with calculated pattern (below) from single crystal X-ray diffraction (SXD) represented by red column bar.  The reflection parameters of single crystal X-ray data were listed in Table 3.1.  (c) The FT-IR spectrum of (R)-(+)-BINOL obtained from Sigma Aldrich.  The characteristic peaks were listed in Table 3.2.	62
Figure 3.7  The molecular structure of (R,S)-(±)-BINOL.  The origin of chirality in BINOL was the restricted rotation around C1-C1'' single bond between the two nearly perpendicular naphthalene rings.	65
Figure 3.8  (a) DSC thermogram of commercial (R,S)-(±)-BINOL was obtained from Sigma Aldrich.  (b) PXRD pattern (upper) of (R,S)-(±)-BINOL obtained from Sigma Aldrich and compared with calculated pattern (below) from single crystal X-ray diffraction (SXD) represented by red column bar.  The reflection parameters of single crystal X-ray data were listed in Table 3.3.  (c) The FT-IR spectrum of (R,S)-(±)-BINOL obtained from Sigma Aldrich.  The characteristic peaks were listed in Table 3.4.	66
Figure 3.9  The molecular structure of (S)-(-)-BINOL.  The asterisk was indicated chiral center.  The origin of chirality in BINOL was the restricted rotation around C1-C1'' single bond between the two nearly perpendicular naphthalene rings.	69
Figure 3.10  (a) DSC thermogram of commercial (S)-(-)-BINOL was obtained from Sigma Aldrich.  (b) PXRD pattern (upper) of (S)-(-)-BINOL obtained from Sigma Aldrich and compared with calculated pattern (below) from single crystal X-ray diffraction (SXD) represented by red column bar.  The reflection parameters of single crystal X-ray data were listed in Table 3.5.  (c) The FT-IR spectrum of (S)-(-)-BINOL obtained from Sigma Aldrich.  The characteristic peaks were listed in Table 3.6.	70
Figure 3.11  The solvent screening procedures for solubility measurement and solid recrystallization.	77
Figure 3.12  Solubility curves of (R)-(+)-BINOL in 21 good solvents.	82
Figure 3.13  Solubility curves of (R,S)-(±)-BINOL in 18 good solvents.	85
Figure 3.14  Solubility curves of (S)-(-)-BINOL in 21 good solvents.	89
Figure 3.15  The plots of ln x versus 1/T of (R)-(+)-BINOL in 21 good solvents.	91
Figure 3.16  The plots of ln x versus 1/T of (R,S)-(±)-BINOL in 18 good solvents.	93
Figure 3.17  The plots of ln x versus 1/T of (S)-(-)-BINOL in 21 good solvents.	95
Figure 3.18  OM images of R-(+)-Binol solids grown in various solvents:	99
Figure 3.19  OM images of (R,S)-(±)-BINOL solids grown in various solvents:	101
Figure 3.20  OM images of S-(-)-Binol solids grown in various solvents:	103
Figure 3.21  Optical microscopic image of (a) (R)-(+)-BINOL•2DMSO, (b) (R,S)-(±)-BINOL•DMSO, (c) (R,S)-(±)-BINOL•2DMSO, and (d) (R)-(+)-BINOL•2DMSO solvates.  (All scale bars were 200 μm)	111
Figure 3.22 TGA and DSC curves for the inclusion compounds in this research.	112
Figure 4.1  Structures of the three isomers of 2,2''-dihydroxy-1,1''-dinaphthyl and their respective enantiomers (R-(+)- and S-(-)- forms).	124
Figure 4.2  The molecular structures of (a) (R,S)-(±)-BINOL, (b) (R)-(+)-BINOL and (c) (S)-(-)-BINOL.	126
Figure 4.3  DSC/TGA traces of (a) (R,S)-(±)-BINOL, (b) (R)-(+)-BINOL and (c) (S)-(-)-BINOL.	126
Figure 4.4  The FT-IR spectra of (a) (R,S)-(±)-BINOL, (b) (R)-(+)-BINOL and (c) (S)-(-)-BINOL obtained from Sigma Aldrich.	127
Figure 4.5  The step-by-step procedure for the preparation of BINOL-DMSO inclusion compounds.	130
Figure 4.6  DSC/TGA traces of (a) (R,S)-(±)-BINOL•DMSO, (b) (R)-(+)-BINOL•2DMSO (c) (R,S)-(±)-BINOL•2DMSO, and (d) (S)-(-)-BINOL•2DMSO.	131
Figure 4.7  Solid-state photoluminescence excitation (dashed traces) and emission spectra (solid traces) of (a) (R,S)-(±)-BINOL, (b) (R)-(+)-BINOL, (c) (S)-(-)-BINOL, (d) (R,S)-(±)-BINOL•DMSO, (e) (R)-(+)-BINOL•2DMSO, (f) (R,S)-(±)-BINOL•2DMSO, and (g) (S)-(-)-BINOL•2DMSO	149
Figure 4.8  (a) ORTEP view of the coordination environments at 50 % probability level for (R,S)-(±)-BINOL, (b) crystal structure of (R,S)-(±)-BINOL viewed along the c-axis, (c) the 21 helical structure consisting of (R)-(+)-BINOL molecules, and (d) the 21 helical structure consisting of (S)-(-)-BINOL molecules.  The hydroxyl moieties of (R)-(+)-BINOL and (S)-(-)-BINOL were denoted as R head and S head respectively, while the naphthyl moieties of them were denoted as R tail and S tail, respectively.  Hydrogen bonds were shown by dotted lines.	152
Figure 4.9  (a) ORTEP view of the coordination environments at 50 % probability level for (R)-(+)-BINOL, (b) crystal structure of (R)-(+)-BINOL viewed along the b-axis, (c) the side view of 31 helical structure formed by the hydrogen bonding between hydroxyl groups of neighboring molecules.  Hydrogen bonds were shown by dotted lines.	154
Figure 4.10  (a) ORTEP view of the coordination environments at 50 % probability level for (S)-(-)-BINOL, (b) crystal structure of (S)-(-)-BINOL viewed along the b-axis, (c) the side view of 32 helical structure formed by the hydrogen bonding between hydroxyl groups of neighboring molecules.  Hydrogen bonds were shown by dotted lines.	155
Figure 4.11  UV spectra of (R,S)-(±)-BINOL in DMSO (0.087 mM, solid line) and (S)-(-)-BINOL in DMSO (0.087 mM, dashed line).  Naphthalene group on (R,S)-(±)- BINOL (or (S)-(-)- BINOL) has a characteristic absorption spectrum with three distinct maxima in the range from 250 to 300 nm (the major band was at 278 nm and the other minor band was at 269 and 290 nm).  Moreover, there were two additional local maxima at 329 nm and 341 nm.	156
Figure 4.12  UV spectra of (A) (R,S)-(±)- BINOL in DMSO (0.087 mM) with a volume of 2 ml prior to the DMSO-addition, then spectral changes by the addition of (B) 0.2 ml DMSO, (C) 0.4ml DMSO, (D) 0.8ml DMSO were recorded in the solution of (R,S)-(±)- BINOL in DMSO (0.087 mM).	156
Figure 4.13  UV spectra of (A) (R,S)-(±)-BINOL in DMSO (0.087 mM) with a volume of 2 ml prior to the water-addition, then spectral changes by the addition of (B) 0.2 ml water, (C) 0.4ml water, (D) 0.8ml water were recorded in the solution of (R,S)-(±)- BINOL in DMSO (0.087 mM).	157
Figure 4.14  UV spectra of (A) (S)-(-)- BINOL in DMSO (0.087 mM) with a volume of 2 ml prior to the DMSO-addition, then spectral changes by the addition of  (B) 0.2 ml DMSO, (C) 0.4ml DMSO, (D) 0.8ml DMSO were recorded in the solution of (S)-(-)-BINOL in DMSO (0.087 mM).	157
Figure 4.15  UV spectra of (A) (S)-(-)-BINOL in DMSO (0.087 mM) with a volume of 2 ml prior to the water-addition, then spectral changes by the addition of (B) 0.2 ml water, (C) 0.4 ml water, (D) 0.8 ml water were recorded in the solution of (S)-(-)-BINOL in DMSO (0.087 mM).	158
Figure 4.16  Solution phase excitation (dashed line) and emission (solids line) of (R,S)-(±)-BINOL in DMSO (0.087mM, Bold) and (S)-(-)-BINOL in DMSO (0.087 mM, non-bold line).  (R,S)-(±)-BINOL (or (S)-(-)- BINOL) in DMSO has a fluorescence spectrum with two excitation maxima in the range from 250 to 300 nm (the major band was at 338 nm and the other minor band was at 282 nm).  Emission maxima showed the wavelength of 380 nm.	158
Figure 4.17  Solution phase excitation (dashed line) and emission (solids line) spectra of (A) 0.087 mM of (R,S)-(±)-BINOL in DMSO with a volume of 2 ml, then spectral changes by the addition of (B) 0.2 ml DMSO, (C) 0.4 ml DMSO, (D) 0.8 ml DMSO were recorded in the solution of (R,S)-(±)-BINOL in DMSO (0.087 mM).	159
Figure 4.18  Solution phase excitation (dashed line) and emission (solids line) spectra of (A) 0.087 mM of (R,S)-(±)-BINOL in DMSO with a volume of 2ml, then spectral changes by the addition of (B) 0.2 ml water, (C) 0.4ml water, (D) 0.8ml water were recorded in the solution of (R,S)-(±)-BINOL in DMSO (0.087 mM).	159
Figure 4.19  Solution phase excitation (dashed line) and emission (solids line) spectra of (A) 0.087 mM of (S)-(-)-BINOL in DMSO with a volume of 2ml, then spectral changes by the addition of (B) 0.2 ml DMSO, (C) 0.4ml DMSO, (D) 0.8ml DMSO were recorded in the solution of (S)-(-)-BINOL in DMSO (0.087 mM).	160
Figure 4.20  Solution phase excitation (dashed line) and emission (solids line) spectra of (A) 0.087 mM of (S)-(-)-BINOL in DMSO with a volume of 2ml, then spectral changes by the addition of (B) 0.2 ml water, (C) 0.4ml water, (D) 0.8ml water were recorded in the solution of (S)-(-)-BINOL in DMSO (0.087 mM).	160
Figure 4.21  Crystal structure of (a) (R,S)-(±)-BINOL•DMSO viewed along the b-axis, (b) hydrogen bondings in (R,S)-(±)-BINOL•DMSO consisting of (R)-(+)-BINOL molecules, and (c) hydrogen bondings in (R,S)-(±)-BINOL•DMSO consisting of (S)-(-)-BINOL molecules.  The hydroxyl moieties of (R)-(+)-BINOL and (S)-(-)-BINOL were denoted as R head and S head respectively, while the naphthyl moieties of them were denoted as R tail and S tail respectively.  Hydrogen bonds were shown by dotted lines.	162
Figure 4.22  (a) ORTEP view of the coordination environments at 50 % probability level for (R)-(+)-BINOL•2DMSO, (b) crystal structure of (R)-(+)-BINOL•2DMSO viewed along the b-axis, (c) the hydrogen bonding in (R)-(+)-BINOL•2DMSO.  Hydrogen bonds were shown by dotted lines.	164
Figure 4.23  (a) ORTEP view of the coordination environments at 50 % probability level for (R,S)-(±)-BINOL•2DMSO, (b) crystal structure of (R,S)-(±)-BINOL•2DMSO viewed along the b-axis, (c) hydrogen bondings in (R,S)-(±)-BINOL•2DMSO consisting of (R)-(+)-BINOL molecules, and (d) hydrogen bondings in (R,S)-(±)-BINOL•2DMSO consisting of (S)-(-)-BINOL molecules.  The hydroxyl moiety of (R)-(+)-BINOL and (S)-(-)-BINOL was denoted as R head and S head respectively, while the naphthyl moiety of them was denoted as R tail and S tail respectively.  Hydrogen bonds were shown by dotted lines.	166
Figure 4.24  (a) ORTEP view of the coordination environments at 50 % probability level for (S)-(-)-BINOL•2DMSO, (b) crystal structure of (R)-(+)-BINOL•2DMSO viewed along the b-axis, (c) hydrogen bondings in (S)-(-)-BINOL•2DMSO.  Hydrogen bonds between BINOL and DMSO were shown by dotted lines.	168
Figure 4.25  PL intensity was plotted against shortest O1-O2 distances of neighboring BINOL molecules.	168
Figure S1  Optical micrographs of (a) (R,S)-(±)-BINOL, (b) (R)-(+)-BINOL, (c) (S)-(-)-BINOL, (d) (R,S)-(±)-BINOL•DMSO, (e) (R)-(+)-BINOL•2DMSO,        (f) (R,S)-(±)-BINOL•2DMSO, and (g) (S)-(-)-BINOL•2DMSO.	169
Figure S2  DSC/TGA traces of (a) (R,S)-(±)-BINOL, (b) (R)-(+)-BINOL, (c) (S)-(-)-BINOL, (d) (R,S)-(±)-BINOL•DMSO, (e) (R)-(+)-BINOL•2DMSO, (f) (R,S)-(±)-BINOL•2DMSO, and (g) (S)-(-)-BINOL•2DMSO.	171
Figure S3  IR spectra of (a) (R,S)-(±)-BINOL (Table S1(a)), (b) (R)-(+)-BINOL (Table S1(b)), (c) (S)-(-)-BINOL (Table S1(c)), (d) (R,S)-(±)-BINOL•DMSO,                   (e) (R)-(+)-BINOL•2DMSO, (f) (R,S)-(±)-BINOL•2DMSO, and (g) (S)-(-)-BINOL•2DMSO.  (Range: 4000 – 2000 cm-1)	174
Figure S4  IR spectra of (a) (R,S)-(±)-BINOL (Table S1(a)), (b) (R)-(+)-BINOL (Table S1(b)), (c) (S)-(-)-BINOL (Table S1(c)), (d) (R,S)-(±)-BINOL•DMSO,(e) (R)-(+)-BINOL•2DMSO, (f) (R,S)-(±)-BINOL•2DMSO, and (g) (S)-(-)-BINOL•2DMSO.  The shift towards to lower energy of S = O band was weaker because of the hydrogen bonding formation of S = O…H－O.  (Range: 2000 – 980 cm-1)	175
Figure S5  IR spectra of (a) (R,S)-(±)-BINOL (Table S1(a)), (b) (R)-(+)-BINOL (Table S1(b)), (c) (S)-(-)-BINOL (Table S1(c)), (d) (R,S)-(±)-BINOL•DMSO,                  (e) (R)-(+)-BINOL•2DMSO, (f) (R,S)-(±)-BINOL•2DMSO, and (g) (S)-(-)-BINOL•2DMSO.  (Range: 1000 – 400 cm-1)	176
Figure S6 PXRD patterns (upper, black line) of (a) (R,S)-(±)-BINOL (Table S3(a)), (b) (R)-(+)-BINOL (Table S3(b)), (c) (S)-(-)-BINOL (Table S3(c)), (d) (R,S)-(±)-BINOL•DMSO (Table S3(d)), (e) (R)-(+)-BINOL•2DMSO     (Table S3(e)), (f) (R,S)-(±)-BINOL•2DMSO (Table S3(f)), and (g) (S)-(-)-BINOL•2DMSO (Table S3(g)). All calculated PXRD patterns based on single crystal x-ray diffraction (SXD) were represented as red column (below).	180
Figure S7  Experimental Z-shaped curves of the concentration of the IPA racemic solution of (R,S)-(±)-BINOL versus time with initial supersaturation ratios of (a) S0 = 1.46 (□), (b) S0 = 1.48 (○), and (c) S0 = 1.50 (?) at 40 oC.  The dashed line represented the solubility value of (R,S)-(±)-BINOL•DMSO in the IPA-DMSO racemic solution at 25 oC.  Equilibrium concentration was denoted as dashed line.	196
Figure S8  Experimental Z-shaped curves of the concentration of the IPA-DMSO racemic solution of (R,S)-(±)-BINOL•DMSO versus time with initial supersaturation ratios of (a) S0 = 1.61 (□), (b) S0 = 1.77 (○), (c) S0 = 1.94 (?), and (d) S0 = 2.10 (?)  at 40 oC.  The dashed line represented the solubility value of (R,S)-(±)-BINOL•DMSO in the IPA-DMSO racemic solution at 25 oC.  Inset represented induction time (0-30 min) section of Figure (b).  Equilibrium concentration was denoted as dashed line.	196
Figure S9  Experimental Z-shaped curves of the concentration of the IPA-DMSO enantiomeric solution of (S)-(-)-BINOL•2DMSO versus time with initial supersaturation ratios of (a) S0 = 1.49 (□), (b) S0 = 1.52 ,and (c) S0 = 1.54 (?) at 40 oC. The dashed line represented the solubility value of (S)-(-)-BINOL•2DMSO in the IPA-DMSO enantiomeric solution at 25 oC.  Inset represented induction time (0-20 min) section of Figure (b).  Equilibrium concentration was denoted as dashed line.	197

                                

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