First hyperpolarizabilities of 1,3,5-tricyanobenzene derivatives: origin of larger beta values for the octupoles than for the dipoles.

A series of donor-acceptor substituted stilbene and diphenylacetylene derivatives and their octupolar analogues have been synthesized and the linear and nonlinear optical properties (beta) studied by both experiments and theoretical calculation. The lambda(max) of the dipoles increases with the conjugation length and is always larger when the C=C bond is used, instead of the C[triple bond]C bond, as the conjugation bridge. Although the lambda(max) values of the octupoles show no clear trend, they are much larger than those of the dipoles. The beta(0) values of the dipoles increase with conjugation length and as the conjugation bridge is changed from the C[triple bond]C to C=C bond. This increase is accompanied by an increase in either lambda(max) or the oscillator strength. Similarly, the beta(0) values of the octupoles increase with the conjugation length and with a change in the donor in the order: NEt2 < N(i-amyl)Ph < NPh2. Moreover, beta(yyy)/beta(zzz) ratios are in the range of 1.6-3.9 and decrease with the conjugation length. Beta values calculated by the finite-field and sum-over-states methods are in good agreement with the experimental data. Also, there is a parallel relationship between the calculated beta values and bond length alternation (BLA). From these results, the origin of the larger beta values for octupoles than for dipoles is assessed.

[1]  Christoph Lambert,et al.  Subchromophore interactions in tricyanovinyl-substituted triarylamines—a combined experimental and computational study , 1999 .

[2]  Joseph Zyss,et al.  Multipolar molecules and multipolar fields: probing and controlling the tensorial nature of nonlinear molecular media , 1998 .

[3]  Joseph Zyss,et al.  Nonlinear optics in multipolar media: theory and experiments , 1994 .

[4]  Antao Chen,et al.  From molecules to opto-chips: organic electro-optic materials , 1999 .

[5]  J. Oudar,et al.  Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment , 1977 .

[6]  H. L. Carrell,et al.  Crystal Engineering of Some 2,4,6-Triaryloxy-1,3,5-triazines: Octupolar Nonlinear Materials , 1998 .

[7]  B. Cho,et al.  Novel azo octupoles with large first hyperpolarizabilities , 2003 .

[8]  B. Cho,et al.  Synthesis and Nonlinear Optical Properties of 1,3,5-Tricyano-2,4,6-tris[2-(thiophen-2-yl)vinyl]benzene Derivatives , 2002 .

[9]  J. Ward,et al.  Optical Third Harmonic Generation in Gases by a Focused Laser Beam , 1969 .

[10]  E. Barbu,et al.  Nondipolar Structures With Threefold Symmetry For Nonlinear Optics , 1997 .

[11]  B. Cho,et al.  Synthesis and nonlinear optical properties of 1,3,5-methoxy-2,4,6-tris(styryl)benzene derivatives. , 2002, Organic letters.

[12]  Nam Woong Song,et al.  Improved method for measuring the first-order hyperpolarizability of organic NLO materials in solution by using the hyper-Rayleigh scattering technique , 1996 .

[13]  Eric Hendrickx,et al.  Hyper-Rayleigh Scattering in Isotropic Solution , 1998 .

[14]  Siegler,et al.  Optimized Two-Dimensional NLO Chromophores with a Threefold Symmetry Axis The authors would like to thank the Volkswagenstiftung and the Fonds der Chemischen Industrie for generous financial supports of this work. , 2000, Angewandte Chemie.

[15]  J. Zyss,et al.  Zinc(II) as a versatile template for the design of dipolar and octupolar NLO-phores. , 2002, Journal of the American Chemical Society.

[16]  B. Cho,et al.  Nonlinear optical and two-photon absorbtion properties of 1,3,5-tricyano-2,4,6-tris(styryl)benzene-containing octupolar oligomers. , 2002, Chemistry.

[17]  S. J. Cyvin,et al.  Theory of Hyper-Raman Effects (Nonlinear Inelastic Light Scattering): Selection Rules and Depolarization Ratios for the Second-Order Polarizability , 1965 .

[18]  Y. K. Lee,et al.  1,3,5-Tricyano-2,4,6-tris(vinyl)benzene derivatives with large second-order nonlinear optical properties. , 2001, Journal of the American Chemical Society.

[19]  C. H. Wang,et al.  Solvent dependence of the first molecular hyperpolarizability of p-nitroaniline revisited , 1997 .

[20]  J. Zyss,et al.  Propeller-shaped molecules with giant off-resonance optical nonlinearities , 2001 .

[21]  Rüdiger Wortmann,et al.  Optimierte zweidimensionale NLO‐Chromophore mit dreizähliger Symmetrieachse , 2000 .

[22]  Inge Asselberghs,et al.  Highly unusual effects of pi-conjugation extension on the molecular linear and quadratic nonlinear optical properties of ruthenium(II) ammine complexes. , 2003, Journal of the American Chemical Society.

[23]  Yoh-Han Pao,et al.  Double‐Quantum Light Scattering by Molecules , 1966 .

[24]  C. H. Wang,et al.  Effects of Two-Photon Fluorescence and Polymerization on the First Hyperpolarizability of an Azobenzene Dye , 1997 .

[25]  Joseph Zyss,et al.  Chiral metal complexes with large octupolar optical nonlinearities , 1995, Nature.

[26]  Kenneth D. Singer,et al.  Polymers for second-order nonlinear optics , 1995 .

[27]  Joseph Zyss,et al.  Second order optical nonlinearity in octupolar aromatic systems , 1992 .

[28]  Joseph Zyss,et al.  Synthesis and Nonlinear Optical, Photophysical, and Electrochemical Properties of Subphthalocyanines , 1998 .

[29]  C. Bräuchle,et al.  Cationic π-electron systems with high quadratic hyperpolarisability , 2001 .

[30]  Joseph Zyss,et al.  High Efficiency and Quadratic Nonlinear Optical Properties of a Fully Optimized 2D Octupolar Crystal Characterized by Nonlinear Microscopy , 2005 .

[31]  C. Bräuchle,et al.  Synthesis and Nonlinear Optical Properties of Three‐Dimensional Phosphonium Ion Chromophores , 1998 .

[32]  R. Wortmann,et al.  Organic Materials for Second-Order Non-Linear Optics , 1999 .

[33]  Inge Asselberghs,et al.  Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores. , 2002, Journal of the American Chemical Society.

[34]  M. Cho,et al.  Molecular Polarizability and First Hyperpolarizability of Octupolar Molecules: Donor-Substituted Triphenylmethane Dyes , 1998 .

[35]  Mark A. Ratner,et al.  Design and construction of molecular assemblies with large second-order optical nonlinearities. Quantum chemical aspects , 1994 .

[36]  B. Cho,et al.  Two-photon absorption and nonlinear optical properties of octupolar molecules. , 2001, Journal of the American Chemical Society.

[37]  Joseph Zyss,et al.  Through-Space Charge Transfer and Nonlinear Optical Properties of Substituted Paracyclophane , 2000 .

[38]  B. Cho,et al.  First hyperpolarizabilities of 1,3,5-tricyano-2,4,6-tris(styryl)benzene derivatives: ab initio studies and Hammett correlation , 2005 .

[39]  Jeffrey S. Moore,et al.  Solvophobically Driven π-Stacking of Phenylene Ethynylene Macrocycles and Oligomers , 2000 .

[40]  David J. Williams,et al.  Introduction to Nonlinear Optical Effects in Molecules and Polymers , 1991 .