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View of Chiral-Axial Project………………………………… MOLECULAR DESIGN FOR NONPOLAR CHIRAL-AXIAL QUADRATIC NONLINEAR OPTICS by GREGORY A. WIGGERS Submitted in partial fulfillment of the requirements For the degree of Doctor of Philosophy Dissertation Adviser: Dr. Rolfe G. Petschek Department of Physics CASE WESTERN RESERVE UNIVERSITY January, 2009 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation of _____________Gregory A. Wiggers______________ candidate for the ____________Ph.D_____________degree *. (signed)________________Rolfe Petschek_____________ (chair of the committee) _______________Ken Singer_________________ _______________Jie Shan___________________ _______________Christoph Weder____________ (date) ________July 31, 2008________ *We also certify that written approval has been obtained for any proprietary material contained therein. Table of Contents Table of Contents....................................................................... 1 List of tables............................................................................. 4 List of figures............................................................................ 6 Acknowledgements..................................................................... 10 Abstract.................................................................................. 11 Chapter 1: Introduction.................................................... 13 1.1 Introduction to Nonlinear Optics....................................... 13 1.1.1 Definition of Optical Susceptibility Tensors…………………. .... .............................1 6 1.1.1.1 Permutations and Kleinman Symmetry................ 18 1.1.1.2 Spatial Symmetry……………………………………… 19 1.1.2 Microscopic and Macroscopic Susceptibilities………………. 21 1.1.3 Quantum Description of Molecular Hyperpolarizability…… 23 1.2 Overview of Chiral-Axial Project…………………………………... 25 1.3 Molecular Design Strategies and Calculation of Hyperpolarizabilities………………………………………………... 30 1.3.1 Hartree-Fock Roothan Equations…………………………….. 34 1.3.2 Post Hartree-Fock Configuration Interaction………….…….. 40 1.3.3 Sample Calculation on a Λ -shaped Molecule and Discussion of Molecular Orbitals…………………………………………. 42 1.4 Introduction to this Thesis……………………………………….….. 47 1.5 References…………………………………………………………..... 50 Chapter 2: Truxenone derivatives………………………………… 54 2.1 “Synthesis and Characterization of New Truxenones for Nonlinear Optical Applications”…………………………………….….. 54 2.1.1 Introduction…………………………………………………….. 55 2.1.2 Experimental Section……………………………………….….. 56 2.1.3 Synthesis…………………………………………………….….. 69 2.1.4 Linear and NLO Properties…………………………………….78 2.1.5 Conclusion………………………………………………………..89 2.2 “Synthesis of Discotic Hexaalkoxytruxenones for Nonlinear Optical applications”…………………………………………………….. 91 2.2.1 Introduction……………………………………………………. 91 2.2.2 Synthesis………………………………………….…………….. 92 1 2.2.3 Linear Absorption……………………………………………… 99 2.2.4 Nonlinear Optical Properties…………………………………. 103 2.2.5 Mesogenic Properties………………………………………….. 107 2.2.6 Conclusion…………………………………………………….... 110 2.3 References……………………………………………………………. 112 Chapter 3: Triarylnaphtylmethyl Carbocations……………. 118 3.1 “Synthesis and Spectral Characterization of Bisnaphthylmethyl and Trinaphthylmethyl cations”………………………………………… 118 3.1.1 Synthesis………………………………………………………… 119 3.1.2 Spectral Characterization……………………………………… 121 3.2 References……………………………………………………………. 127 Chapter 4: Phenanthrenequinone Derivatives……………….. 129 4.1 “Synthesis, Structure and Properties of 3,6-disubstituted 9,10- Phenanthrenequinone Derivatives”………………………..…………... 129 4.1.1 Introduction……………………………………………………. 130 4.1.2 Synthesis……………………………………………………….. 132 4.1.3 Optical Properties and Electronic Structure Calculations…. 140 4.1.4 Conclusion……………………………………………………… 149 4.2 References……………………………………………………………. 152 Chapter 5: Two-level and Multi-level SOS Calculations onΛ -shaped Molecules……………………………….. 158 5.1 “Spectroscopic and Charge Transfer Calculations of Λ -shaped Molecules for Kleinman-Disallowed Quadratic Nonlinear optics”………………………………………………………………… 158 5.1.1 Introduction……………………………………………………. 159 5.1.2 Theory………………………………………………………….. 163 5.1.3 Materials……………………………………………………….. 169 5.1.4 Calculation Techniques……………………………………….. 175 5.1.5 Results I: two-level figure of merit…………………………… 176 5.1.6 Results II: multilevel calculations……………………………. 202 5.1.7 Conclusion……………………………………………………… 211 5.2 References……………………………………………………………. 212 2 Chapter 6: “Modulated Conjugation” as a Means of Maximizing the Hyperpolarizability?............................................. 219 6.1 Introduction to the problem………………………………………… 219 6.2 Comment on “Pushing the Hyperpolarizability to the limit”…….. 221 6.3 Further discussion of modulated conjugation……………………... 226 Appendix…………………………………………………………………. 240 6.4 References…………………………………………………………… 242 Chapter 7: Conclusion………………………………………………….. 244 7.1 Summary of thesis…………………………………………………... 244 7.2 Future Work…………………………………………………………. 246 Bibliography…………………………………………………………………. 248 3 List of Tables Table 2.1.1 Overview of all the truxenones synthesized here from indan-1,3- dione derivatives in methanesulfonic acid (110 ˚C, 3 hours)………..…….. 72 Table 2.1.2 Summary of the attempts to prepare truxenones from inden-1-one derivatives via the sequence of bromination (Br2) and pyrolysis(220 °C)... 72 Table 2.1.3 Overview of all the 4,9,14-tris(dialkylamino)truxenones obtained by nucleophilic substitution of the 4,9,14-trifluorotruxenone…………….. 74 Table 2.1.4 Structure of all the truxenones and the tris(dicyanomethylene) measured by KD-HRS in this study as well as the pnenylethynyl bridged truxenone synthesized by Lambert et al…………………………………… 83 Table 2.1.5 Rotational invariants (in units of 10-30 esu) measured by KD-HRS at 1560 nm. The calculated depolarization ratio is determined from KD-HRS measurements, while the experimental depolarization ratio is directly determined from 90 degree HRS measurements………………………….. 84 Table 2.1.6 Characteristics of different truxenone derivatives, where λmax is the maximum absorption of the lowest energy absorption peak; βunpolarized is the unpolarized hyperpolarizability values calculated from rotational invariants by the relation (I), and βunpolarized / βref is the ratio between the unpolarized hyperpolarizability values of the compound and that of Lambert’s compound………………………………………………………..………... 88 Table 2.2.1 Phase transitions temperatures and the decomposition temperatures (in °C) obtained by DSC at 10 °C/min under nitrogen. (a) Literature transition temperatures. (b) Phase change temperatures were obtained by polarizing optical microscopy at 10 °C/min. (c) A phase transition was not observed due to decomposition of the sample………….…………….... 107 Table 3.1 Spectroscopic properties of TAMC chromophores in ethanol solution -5 -1 -1 (ca 1.10 M). λmax is given in nm, ε in mol cm , and Δλ represents the Full width at half maximum in nm…………………………….………….. 122 Table 3.2 Absolute value of the rotational invariants of the hyperpolarzability (10-30esu) obtained from TCSPC-45º-HRS………….….………………… 126 Table 4.1 Synthesis of 3,6-dialkylamino phenanthrenequinone derivatives (I)…... 134 Table 4.2 Synthesis of 3,6-vinyl-p-conjugated substituted 9,10 phenanthrene- quinones (II)………………………………………………………………. 135 Table 4.3 Synthesis of 3,6 phenylethynyl phenanthrenequinones (III)…….…….. 137 Table 4.4 Synthesis of 3,6-disubstituted-dibenzo[a,c]phenazines (IV)……..……. 139 Table 4.5 Comparison of experimental oscillator strengths and transition energies with ZINDO calculations. Symmetries predicted by ZINDO (A-type or B-type) are also given. In some cases calculated oscillator strengths of the two nearest transitions are given when experimental peaks were not completely resolved. 4 Experimental oscillator strengths were determined using f = 0.043∫ ε (vdv ) , where vcm= λ −−11(), and []ε = M −1cm−1…………….……………………… 147 Table 5.1 Spectroscopic and two-level figure of merit calculation for 1-7…….... 178 Table 5.2 Spectroscopic and two-level figure of merit calculations for 8-12…..... 187 Table 5.3 Spectroscopic and two-level figure of merit calculations for 13-25…... 192 Table 5.4 Spectroscopic and two-level figure of merit calculations for 26-29…... 201 Table 5.5 A summary of all parameters used in the three-level model, denoting whether the parameter was determined by experiment or calculation (ZINDO). The 1ss component uses all of these parameters, while the 2mm does not depend on Dmga. The wavelengths are in nm; the dipole/ transition moments are in Debye, and the damping parameters are in 101 5rad s-1………………………………………………………..……….. 206 5 List of Figures Figure 1.1 The symmetry operations of the C2v group are depicted on a Λ -shaped object. The coordinate system shown will be adopted throughout this thesis………………………………………………………………………. 20 Figure 1.2 A typical linear “push-pull” organic molecule is shown, which displays a conjugated bridge with a donor (-NH2) and acceptor (-NO2) group at opposite ends: (a) parallel alignment; (b) anti-parallel alignment... 26 Figure 1.3 Maximized alignment schemes in D∞ media; (a) for C2v molecules the C2 axis is perpendicular to the bulk symmetry axis. The maximized D rotational angle (about the C2 axis) is ψ max = 45 ; (b) for D3 molecules the C3 axis is aligned with the bulk symmetry axis………….…………… 28 Figure 1.4 Sample molar absorption curve. Two clear peaks n be seen which result from two separate quantum transitions. By integrating to find the area under each peak the magnitude of the molecular transition moments μ01
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