Novel Chiral Bis-dipolar 6,6'-Disubstituted Binaphthol Derivatives for Second-Order Nonlinear Optics: Synthesis and Linear and Nonlinear Optical Properties
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- 作者：H.-J. Deussen ; E. Hendrickx ; C. Boutton ; D. Krog ; K. Clays ; K. Bechgaard ; A. Persoons ; and T. Bj
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- 刊名：Journal of the American Chemical Society
- 出版年：1996
- 出版时间：July 24, 1996
- 年：1996
- 卷：118
- 期：29
- 页码：6841 - 6852
- 全文大小：459K
- 年卷期：v.118,no.29(July 24, 1996)
- ISSN：1520-5126
文摘
A number of thermally and optically stable, bis-dipolar chiralmolecules based on two geometries of thebinaphthol (BN) system with different acceptors/substituents have beensynthesized for the first time, and the syntheticroutes are reported: optically pure 6,6'-disubstituted2,2'-diethoxy-1,1'-binaphthyls {R, R'= -Br, -CHO,-CH=C(CN)(COOEt), -CH=C(CN)2, -CH=CHCN,-CH=CH(p-NO2Ph)} and opticallypure 9,14-disubstituted dinaphtho[2,1-d:1',2'-f][1,3]dioxepins {R,R' = -Br, -CHO, -CH=C(CN)(COOEt),-CH=C(CN)2, -CH=CHCN,-CH=CHSO2CH3, -CH=CHCHO,-CH=CHCH=C(CN)2}. All molecules possesstwo equal donor-acceptorsystems linked together to give a bis-dipolar system. Twomono-dipolar 6-substituted 2-butoxynaphthalene (R =-CH=C(CN)2, -CH=C(CN)(COOEt))donor-acceptor systems were prepared as references. The linearopticalproperties including solvatochromic shifts of absorption andfluorescence revealed strong charge transfer excitationsin the new dipolar systems. The molecules show a high firsthyperpolarizability 
(up to (344-364) ×10-30 esu)as measured by electric-field-induced second-harmonic generation(EFISHG) and hyper-Rayleigh scattering (HRS).A model is developed to express the first hyperpolarizability ofthe bis-dipolar molecules in terms of the moleculargeometry and the of the monomeric donor-acceptorunits. The tensor components were determinedexperimentallyusing this model and data from HRS and EFISHG. These techniquesprobe different combinations of the componentsof the molecular hyperpolarizability tensor. The results obtainedare found to be in excellent mutual agreement.
(up to (344-364) ×10-30 esu)as measured by electric-field-induced second-harmonic generation(EFISHG) and hyper-Rayleigh scattering (HRS).A model is developed to express the first hyperpolarizability ofthe bis-dipolar molecules in terms of the moleculargeometry and the of the monomeric donor-acceptorunits. The tensor components were determinedexperimentallyusing this model and data from HRS and EFISHG. These techniquesprobe different combinations of the componentsof the molecular hyperpolarizability tensor. The results obtainedare found to be in excellent mutual agreement.