Chiro-optics của các hợp chất achiral - Kacey Claborn 2006

Claborn Chiro-optics of Achiral Compounds Kacey A. Claborn A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy University of Washington 2006 Program Authorized to Offer Degree: Department of Chemistry UMI Number: 3230740 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted.

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ProQuest Information and Learning Company 300 North Zeeb Road P. Box 1346 Ann Arbor, MI 48106-1346 University of Washington Graduate School This is to certify that I have examined this copy of a doctoral dissertation by Kacey A. Claborn and have found that it is complete and satisfactory in all respects, and that any and all revisions required by the final examining committee have been made. Chair of the Supervisory Committee: Sak oe 0- Bart Kahr Reading Committee: Sat ca ‘Bart Kahr _ c2 |decececiofXÃ Werner Kaminsky ĐẾN C Shear Ronald E.

Stenkamp Date: 6/1 P/o6 In presenting this dissertation in partial fulfillment of the requirements for the doctoral degree at the University of Washington, I agree that the Library shall make its copies freely available for inspection. I further agree that extensive copying of the dissertation is allowable only for scholarly purposes, consistent with “fair use” as prescribed in the U. Requests for copying or reproduction of this dissertation may be referred to Proquest Information and Learning, 300 North Zeeb Road, Ann Arbor, MI 48106- 1346, 1-800-521-0600, to whom the author has granted “the right to reproduce and sell (a) copies of the manuscript in microform and/or (b) printed copies of the manuscript made from microform.” Signature Z¿x{22»⁄ Date c/ xí OG University of Washington Abstract Chiro-optics of Achiral Compounds Kacey A. Claborn Chair of the Supervisory Committee: Professor Bart Kahr Department of Chemistry Chirality is not a necessary condition for the presence of chiro-optical properties in some oriented media.

The non-enantiomorphous point symmetries Dog, S4, C2, and C; also admit optical activity. The optical rotation tensors of some achiral crystals were determined and interpreted with respect to molecular and electronic structure. The isomorphous crystals (D4) of the Group 14 tetraphenyls (C(C¿Hs)a, Si(CeHs)a, Ge(CsHs)4, Sn(Ce6Hs)4, Pb(C6Hs)4) were compared and interpreted according to a classical dipole-dipole interaction theory for crystals. Pentaerythritol (C(CH;OH)¿) crystals (S4) were measured to facilitate comparison with computations for a single molecule according to semi-classical quantum theory.

The computational effort was extended to water (C2,), the simplest common molecule that supports natural optical rotation, for which the generation of optical rotation according to a modified Rosenfeld equation was interpreted in terms of classical electrodynamics. Although the sign of optical rotation or circular dichroism in achiral materials does not distinguish absolute configuration as for chiral point symmetries (O, T, Dn, Cạ), it does establish the absolute direction of the axes. As an alternative to measuring optical rotation and circular dichroism in molecular crystals wherein intermolecular contributions can be significant, dyed crystals were investigated. The guest molecules are then not only well separated from one another, but are well-oriented within individual sectors of the host crystal.

These dyed crystals gave strong chiro-optical signals that were consistent with the host symmetry, but were inconsistent with an intrinsic effect when the wave vector was reversed. The observed optical effects were given the phenomenological names anomalous azimuthal rotation when measured by incident linearly polarized light and anomalous circular extinction when measured by differential circularly polarized light. The new experimental effects are sensitive to the sense of inclination (clockwise or counterclockwise) of the embedded dipoles from the eigenmodes of the host. The signals therefore provide information about the absolute orientation of the adsorbate, a supramolecular stereochemical quality that cannot be distinguished by polarized absorption measurements alone.

TABLE OF CONTENTS Page I0» 1. vi List of Tables mồ. HH TH TH HH HH1 E70 1 n9 ao.2 History of Polarimetry and Polarized Light MicrOSCODV.3 Crystal CHhITO-ODEICS.- Án ng HH TH TH HT 0 101 ke 9 1.1 Discovery of Rotatory Polar1ZafiOI.2 Necessary Conditions for Optical AC{IVILY.3 Interpretations of Optical ACIVI[V.4 Notes to Chapter Ì. ch HH HH HH 100 kh 19 Chapter 2: Optical Rotation of Achiral Medla.1 Optical Rotation of the Group 14 TetraphenyÌs.2 Tnt€rpr€fatIOI.

«kh k 1H HH TH HT ng HH tk 36 2.2 Optical Rotation of PentaerythrIfOÏ. ca ràng HH re 39 2.1 Optical Rotation Measure€TI.- có S nà nhe Hệ 40 2.2 Circular Differential Reflection.-- ác cà nành re44 2.- («G9 ng ng ve47 2.3 Optical Rotation Of ẤWA€T.- nh HH1 1201 T4 HT HH1 0 0x.1 Quantum Cal€ulatiOrnS.- --- G cà 111 HH cry 62 2.2 Int€TPr€fafiOI.- ch HH HH TH HH hư66 2.1 Synthesis of Tetraphenylmethane.2 Crystal Growth and Sample Preparation.3 Refractive Index Determination.- -- + cv tt 1111411 cey 80 2.2 Pentaerythritol oe eeeesescersteceecesecseceseesesseseseseessesssesessesesseessenees 84 2.2 Absolute Structure Determination.3 Quantum CaÌCuÌatiOnS.3 Quantum Calculations Of WAat€T.-- G TS HS neo 91 2. 95 Chapter 3: Absolute Orientation of Embedded Oscillators .1 Oriented Gasses in Single Crystal MatrIC€S.2 Introduction to Dyed CTYyS(AÌS.- án Hy HH T1 11 0g gyn 105 3. cc ố ốốố ốố.

HH HH HH Tu HH Hà HT HH hệt 109 3.3 Circular Dichroism Imaging MICTOSCODY. cà SH Hee.1 Anomalous Birefringence of 1,8-Dihydroxyanthraquinone Crystals "¬—.2 Enantiomorphous Twin Domains .4 Absolute Ori€n†af1ON. -- HH TH HH HT in 120 3.1 Lithium Potassium Sulfate CrystaÌS.2 Anomalous Circular EXIInCEION.1 Anomalous Circular EXtHInCfIOI.2 Anomalous Azimuthal RotatIon. - ch nọ ng ting ng hà 133 3.7 Experimental nh nh .1 Dyed Lithium Potassium Sulfate CrystalÌs.

cọ HH He 139 3.2 Sample Preparat1OI.3 Linear Birefringence and Linear Dichroism.4 Anomalous Circular Extinction.5 Anomalous Azimuthal Rotation. HH HH KH 142 3.2 Linear Birefringence and Linear Dichroism. óc kh ng ng nh kh 142 ili 3.8 Notes to Chapter 3. HH HH 1g rà 144 Chapter 4: Polarimetry and Polarized Light MICTOSCODY.- sọ St sreee re.1 Intensity Expressions Using the Jones Formalism.2 High Accuracy Universal PolarimetrV.- uc HH HH HH 10 HH HH HH ng 163 4.2 Anomalous Azimuthal Rotation .3 Data AnalÌySI1S.

«LH HH TH HH HT g1 ng gu 171 4.4 Tilter SD€CIÍICALÏODS. sa HH TH TH HH 01001 110111 HH ng 177 Ấn .-- HH ng TH TT TH Ti nhện 179 4.2 Anomalous Circular Extimction 0.1 Linear BirefrIng€nC€.-- -- co cv nàn TH HT T1 H1 01 1 Hàng cư 188 4.2 Linear DiChrO1SIN.3 MetriPol SD€CIfICALiODS. ác HH nàng 1 ng tàu 194 4.5 Notes to Chapter 4.- HH HH HH 0 HT HH HT HH TH Hà Hành 196 Chapter 5: Mathematical Background.--‹ s12 HH HH g1 0111 11 re, 201 bái sàn.2 Levi-Civita OD€TA[IOIA. ánh SH HH TH g1 1011 1 1 ky205 1V 5.3 Physical Properties of CTWSfaÌS.4 Examples: Determination of Elements Present for Second Rank AXial “T€TISOFS.2 Classical Theory of Optical ROfAtIOn.- nàn HH HH nu 213 5.3 Quantum Mechanical Theory of Optical Rotation.4 Notes to Chapter nh.

228 Appendix A: Mathematica Worksheet — Optical Rotation Intensity Expression for the Tilter Method Using the Jones FormaliSm.- c1 1119111111111 2 1 101101 người 252 Appendix B: Mathematica Worksheet —- Anomalous Azimuthal Rotation Intensity Expression for the Tilter Method Using the Jones Formalism.-- ‹- + c<<ss«2 266 LIST OF FIGURES Page Figure 1-1. Double Refraction in Two Stacked Calcite Crystals. 6 cc sec 6 Figure 1-2. Biot’s Illustration of Optical Rotatory Dispersion.

Fresnel’s Model of Optical Rotation. Representation Surface of Optical Rotation for d-Tartaric Acid Crystals. Crystal Habit and Unit Cell for Tetraphenyltin Crystals. Dipole-Dipole Interaction Theory for Optical Rotation.

Calculated Optical Rotation for the Group 14 Tetraphenyl Crystals. Calculated Anisotropic Polarizabilities for the Group 14 Tetraphenyl Crystals stasensensensceatesscesessessessesssessusessessscusesssssssonsosassasensunensesssussasesussesssseassssseseansestensossssussusassnssassegens 3 Figure 2-5. Helical Paths in Group 14 Tetraphenyl Molecules. Measured Optical Rotation of a Pentaerythritol Crystal.

Optical Rotatory Power and Its Representation Surface for a Pentaerythritol CTYS(AÌ. HH H411 1101111 HH TH TT TT TH HT Hy 43 Figure 2-8. Reflection Effect in the Optical Rotation Measurement of a Pentaerythritol Crystal oc eecccccscscessesecenesseessesssesessesssssesesscsesssesesssscscssscsssevevsusasscssssssavavsssavesecasasecaanaeaeas 46 Figure 2-9. Reflection Effect and Its Representation Surface for a Pentaerythritol crystal mg.

Calculated Optical Rotation for a Pentaerythritol Crysfal. Hydrogen-Bonding Motif in Pentaerythritol Crystals. Most Optically Rotatory Directions in a Pentaerythritol Molecule. Barron’s Illustration of Optical Rotation for a Water Molecule.

Calculated Optical Rotation for a Water MolecuÌe. Qualitative Molecular Orbitals of Water. Calculated Molecular Orbitals of Water. Molecular Orbital Overlap in the B; Transition of Water.

Interpretation of Rotatory Power from the B, Transitions of Water. Interpretation of Rotatory Power from the B; Transitions of Water. Interpretation of Rotatory Power from the A, Transitions of Water. Rosenfeld’s Interpretation of the Rotatory Power of Water.

Refractive Index Determination for the Group 14 Tetraphenyl Crystals. Preparation of Pentaerythritol Crystal Samples. Simultaneous Reflections in Three-Beam Diffraction. Three-beam Intensity Profiles as a Function of the \Ứ-scan.

Three-beam Intensity Profiles of Crystalline Pentaerythritol. Optical Transformations Consistent with Intrinsic and Apparent Chiro-optical Effects TƯ ,zs,nnẦNŨỚNỪỮ. Schematic of a Two-Dimensional Crystals with Enantiomorphous Facets. Ambiguity in Polarized Absorption Measuremen(s.

Molecular Packing in Crystals of 1,8-Dihydroxyanthraquinone Figure 3-5. Linear Birefringence Micrographs of 1,8-Dihydroxyanthraquinone Crystals Figure 3-6. Circular Dichroism Micrograph and Spectrum of 1,8-Dihydroxyanthraquinone Crystals vil Figure 3-7. Variations in Circular Dichroism Micrographs of 1,8- Dihydroxyanthraquinone CTYy§SfAÌS.

-- c1 v1 vn HH TH TH HT HT HH HH ưưc 118 Figure 3-8. Production of Elliptically Polarized Light from Circular Dichroism. Lithium Potassium Sulfate Crystal Habit and Twin Planes. Polarized Light Micrographs of Chicago Sky Blue-Dyed Lithium Potassium Sulfate Crystals NA".

Polarized Light Micrographs of Pyranine-Dyed Lithium Potassium Sulfate Crystals Figure 3-12. Circular Extinction Spectra of Dyed Lithium Potassium Sulfate Crystals. Model of Anomalous Circular Extinction. Absolute Orientation of Dipoles in Dyed Lithium Potassium Sulfate Crystals 1.

Anomalous Azimuthal Rotation of Chicago Sky Blue-Dyed Lithium Potassium Sulfate CTYStalS. Projection of an Inclined Dipole onto the Eigenmodes of a Crystal. Model of Anomalous Azimuthal Rotation. Lithium Potassium Sulfate LLattiC€.

Poincaré Polarization Sphere.- ¿c1 v9 91H HH ng Heo 151 Figure 4-2. Matrix Method for Tracking the Polarization State of Light. Schematic of the Tilter Polarimet€r-.--‹- + tt tt rệc 164 Figure 4-4. Algorithm for Analyzing Tilter Data.

óc tt ng re, 174 Figure 4-5. Schematic of the U-Pol Microscope. SG TH SH HH nếu 181 Figure 4-6. Variation of the Phase Factor in Polarimetric Measurements.

Schematic of the MetriPol MiCTOSCOP€.- HH HH net 189 Figure 5-1. Representation Surfaces, Tensor Elements, and Examples of Crystals from Optically Active Point Groups T8. 202 ix LIST OF TABLES Table 2-1. Fractional Coordinates of Tetraphenylstannane.

Input and Output Data from Optact Calculation of Optical Rotation for the Group 14 Tetraphenyl CTYSfAÌS. cà tt nh HH HH the 34 Table 2-3. Structural Parameters of the Group 14 Tetraphenyl Molecules in the Crystalline Phase.- nh 1Á 011 11t T111 101011010110 KH H10 110110 k6 ke 38 Table 2-4. Fractional Coordinates of Pentaerythr1fOÏ.- co senhhHhHhHHhhhihưee 44 Table 2-5.

Calculated Optical Rotation Tensor Elements for a Pentaerythritol Molecule With Cz SVImIN€TY.- «5 ng TH TH TH TH TH TH HH1 T710 4T 11 111111010 k0 1kg 35 Table 2-6. Calculated Optical Rotation Tensor Elements for a Pentaerythritol Molecule With C2 SYImIN€FV.á- Ác nh HH ng HH ng H1 T11 14. 810 T1 th t1 9101 ti ng kh 56 Table 2-7. Calculated Transition Moments of Water that Contribute to Optical Rotation _—.

Calculated Rotational Strength Tensor Elements for a Water Molecule. Measured Refractive Indices of the Group 14 Tetraphenyl Crystals. Structure Coordinates for Tetraphenylmethane. Structure Coordinates for Tetraphenylsilane.

Structure Coordinates for Tetraphenyl germane. Structure Coordinates for Tetraphenylstannane. Structure Coordinates for Tetraphenylplumbane .