Electrooptical Chromophores for Nonlinear Optical and Photorefractive Applications

Large Quadratic Hyperpolarizabilities with Donor–Acceptor Polyenes Exhibiting Optimum Bond Length Alternation: Correlation Between Structure and Hyperpolarizability

Donor-acceptor polyenes of various lengths, and that combine aro- matic electron-donating moieties with powerful heterocyclic electron-withdraw- ing terminal groups, have been synthe- sized and characterized as efficient non- linear optical (NLO) chromophores. Their linear and nonlinear optical proper- ties have been investigated, and variations in these properties have been related to ground-state polarization (dipole p) and structure. In particular, unprecedented quadratic hyperpolarizabilities (p) have been achieved (up to p(0) =I500 x 10-30esu) by reduction of the bond- length alternation (BLA) in the polyenic chain. In each series of homologous com-

Spectral and electrooptical absorption and emission studies on internally hydrogen bonded benzoxazole `double' derivatives: 2,5-bis(benzoxazolyl)hydroquinone (BBHQ) and 3,6-bis(benzoxazolyl)pyrocatechol (BBPC). Single versus double proton transfer in the excited BBPC revisited

Abstract Ground and excited state dipole moments and polarizabilities of 2,5-bis(benzoxazolyl)hydroquinone (BBHQ) and 3,6-bis(benzoxazolyl)pyrocatechol (BBPC) are determined by means of electrooptical absorption and emission measurements. BBHQ is found to exhibit a small, while BBPC a large increase of the static polarizability in the Franck–Condon (FC) excited singlet state. The change of the dipole moments upon excitation to the FC state is zero within experimental error. However, both molecules show dipole moments in the fluorescent states of their phototautomers, of about 5 D, the major component being parallel to the long molecular axis. The experimental and theoretical results strongl…

Elongated push–pull diphenylpolyenes for nonlinear optics: molecular engineering of quadratic and cubic optical nonlinearities via tuning of intramolecular charge transfer

Abstract Push–pull polyenes are of particular interest for nonlinear optics (NLO) as well as model compounds for long-distance intramolecular charge transfer (ICT). In order to tune the ICT phenomenon and control the linear and nonlinear optical properties, we have synthesized and investigated several series of soluble push–pull diphenylpolyenes of increasing length and having various donor (D) and acceptor (A) end groups. Their linear and NLO properties have been studied by performing electro-optical absorption measurements (EOAM) and third-harmonic generation (THG) experiments in solution. Each push–pull molecule exhibits an intense ICT absorption band in the visible characterized by an i…

Organic Materials for Non-Linear Optics: The 2D Approach

Conventional organic molecules for applications in second-order non-linear optics are donor–acceptor substituted π systems that show only one intense charge-transfer (CT) transition. Thus, only a single element of the second-order polarizability tensor, β, is significant in these one-dimensional systems. The advantages and optimization strategies for two new classes of molecules with multiple CT transitions and two-dimensional second-order polarizability are reviewed. These are donor–acceptor substituted π systems that lack a dipole and have a molecular symmetry of C3 or higher, and dipolar molecules of symmetry C2v. A basic introduction to the field is also given.

Guanidyl and phosphoraniminyl substituents: New electron donors in second-order nonlinear optical chromophores

Quantitative interpretation of the red edge excitation (REE) effect of 9,9′-bianthryl in polyisobutene by band shape analysis of the temperature-dependent optical fluorescence spectra

Optical fluorescence spectra of 9,9′-bianthryl (BA) in polyisobutene (PIB) were measured as a function of the excitation wavelength at various temperatures between 210 and 293 K. Irradiation at the red edge of the absorption spectra selectively excites distinct conformers with respect to the torsional angle. This leads to a strong dependence of the vibronic band shape of the fluorescence spectra on the excitation wavelength. The marked temperature dependence of the band shape may be attributed to the viscosity-dependent deceleration of the torsional relaxation of BA in the highly viscous polymer which prevents the excited state ensemble from reaching thermal equilibrium. The predominant bro…

Dipolar NLO-phores with large off-diagonal components of the second-order polarizability tensor

Effect of S1 Torsional Dynamics on the Time-Resolved Fluorescence Spectra of 9,9‘-Bianthryl in Solution

Time-resolved fluorescence spectra of 9,9‘-bianthryl (BA) were measured in methylcyclohexane (MCH) and a Decalin−isooctane (D−ISOO) mixture at several temperatures between 127 and 200 K. A suitable...

Intramolecular charge transfer in elongated donor-acceptor conjugated polyenes

Abstract Intramolecular charge transfer (ICT) has been investigated by electro-optical absorption measurements for two series of donor-acceptor polyenes of increasing length. Each molecule undergoes an increase in dipole moment upon photoexcitation. The experimental results indicate that lengthening the polyenic chain linking the donor and acceptor end groups results in a bathochromic shift of the ICT absorption band and induces marked increases of both excited state and transition dipoles, whereas the ground-state dipole is relatively unaffected. As a result, marked photoinduced changes in the dipole moment (up to 33 D) were obtained with the longest molecules (up to 27 A) leading to highl…

The use of simulation methods to obtain the structure and conformation of 10-cyano-9,9′-bianthryl by electron diffraction and high-resolution imaging

Abstract Experimental electron diffraction patterns and high-resolution images were used to determine the space group and unit cell dimensions of 10-cyano-9,9′-bianthryl. Subsequently the molecular conformation was calculated by semi-empirical quantum-mechanical methods. The molecule was then placed with the appropriate symmetry into the unit cell and the conformational as well as the packing energy deduced by an iterative procedure until good agreement was obtained between experiment and theory.

Intramolecular charge transfer and enhanced quadratic optical non-linearities in push pull polyenes

Abstract Push-pull polyenes, which have an electron-donating group (D) and an electron-withdrawing group (A) grafted on opposite ends of a conjugated polyenic chain, are of particular interest as model compounds for long-distance intramolecular charge transfer (ICT), as well as potent non-linear optical chromophores. Several series of push-pull polyenes of increasing length, combining aromatic donor moieties and various acceptor groups, have been prepared and studied. Their linear and non-linear optical properties have been investigated by performing electro-optical absorption measurements (FOAM) and electric-field-induced second-harmonic generation (EFISH) experiments in solution. Each mol…

Enhanced nonlinear optical properties and thermal stability of donor-acceptor substituted oligothiophenes

Abstract Linear and nonlinear optical properties of a series of novel donor-acceptor substituted α-oligothiophenes were investigated by means of electrooptical absorption measurements (EOAM) and electric field induced second harmonic generation (EFISH). The second-order polarizabilities β(−2ω; ω, ω) were related to dipole changes Δμ ag and transition dipoles μ ag associated with low-lying charge-transfer (CT) excitations by using the perturbational two-level approximation. Systematic variation of the donor and acceptor groups led to compounds with exceptional nonlinearity and thermal stability. Too strong donor/acceptor pairs, however, yielded structures in the charge-resonance (CR) limit w…

Excited state dipole moments and polarizabilities of centrosymmetric and dimeric molecules. I. Model study of a bichromophoric molecule

Abstract Refractometric, dielectric and electro-optical absorption measurements are reported for 1-dimethylamino-2,6-dicyano-4-methyl-benzene (I) and 1,4-bis(4′-dimethylamino-3′,5′-dicyanophenyl)bicyclo[2.2.2]octane (II). The evaluation leads to dipole moments and polarizabilities of the ground state as well as the first dipole allowed singlet state. The experimental res excellently substantiate the method of electro-optical absorption measurements in solution. It is shown that the excited dimer wavefunctions of the bichromophoric molecule II localize by solvent induced local site perturbations.

Nondipolar Structures With Threefold Symmetry For Nonlinear Optics

Deviations from Kleinman symmetry of the second-order polarizability tensor in molecules with low-lying perpendicular electronic bands

Abstract 4-Nitroaniline (pNA) and 3,5-dinitro-aniline (3,5-DNA) were studied by electric field induced second harmonic generation (EFISH) and electrooptical absorption measurements (EOAM) in dioxane solution at T = 298 K. The measurements were carried out for two polarization conditions, the electric field vector of the linearly polarized incident light being parallel or perpendicular to the static electric field. The second-order polarizability tensor of pNA is confirmed to be Kleinman symmetric, while a strong deviation from index permutation symmetry is observed for 3,5-DNA. The latter is quantitatively interpreted by contributions of a low-lying electronic band with transition dipole pe…

ChemInform Abstract: Organic Materials for Non-Linear Optics: The 2D Approach

Conventional organic molecules for applications in second-order non-linear optics are donor–acceptor substituted π systems that show only one intense charge-transfer (CT) transition. Thus, only a single element of the second-order polarizability tensor, β, is significant in these one-dimensional systems. The advantages and optimization strategies for two new classes of molecules with multiple CT transitions and two-dimensional second-order polarizability are reviewed. These are donor–acceptor substituted π systems that lack a dipole and have a molecular symmetry of C3 or higher, and dipolar molecules of symmetry C2v. A basic introduction to the field is also given.