Effect of Substituting Group on the Calculated Nonlinear Second－Order Optical Susceptibilities of Substituted Thiophene Derivatives with Quinoidlike Conformation

alculations of the nonlinear second-order optical susceptlbilities(β_(ijk))for sub- stituted tl1iophene derivative;with quinoidlike conformation are reported.These systetems possess small dipole moment;and large differences between dipole mo- ments of ground and first-excited states.Geometry optimizations of the molecules investigated were carried out using AM 1 method.The calculations were performed using INDO/CI method comboned with a sum-over-states expression for β_(jik). The calculated results sbw that the second-order susceptibility is a function of the na- ture and location of substituents and is larger for disubstituted molecules than monosubstituted molecules. Bipolymeric thiophenemetmne with NH_2/NO_2 groups was calctilated to have a β_μof 79. 920 × 10￣(-30) esu. It was found that the NH_2 and NO_2 groups in above disubstituted molecules are pull-pull groups in ground states,but are usual push-pull groups in the first excited states.

PREPARATION AND SECOND-ORDER OPTICAL NONLINEARITY OF NOVEL PHENOXYSILICON NETWORKS BY SOL-GEL PROCESS

Four phenoxysilicon networks for nonlinear optical (NLO) applications were designed and prepared by an extended sol-gel process without additional H2O and catalyst. All poled polymer network films possess high second-order nonlinear optical coefficients (d(33)) Of 10(-7)similar to 10(-8) esu. The investigation of NLO temporal stability at room temperature and elevated temperature (120 degreesC) indicated that these films exhibit high d(33) stability because the orientation of the chromophores are locked in the phenoxysilicon organic/inorganic networks.

A Theoretical Study of Nonlinear Second-Order Optical Properties of Substituted Silanes

On the basis of ZINDO method and according to the sum over states(SOS) expression, the program is devised for the calculation of nonlinear second order optical susceptibilites β ijk and studying how different substituents on the phenyl ring attached to the atom silicon influence on the nonlinear second order optical properties of substituted silane series of molecules. The properties of (CH 3) 3Si? ?has been studied particularly. The effect of the length of silica chains on the calculated values has been studied too. The regularity summarized from the calculated results has been explained micromechanically.

An 8-Connected Chiral Lanthanide Metal-organic Framework Constructed from Naturally Camphoric Acid:Crystal Structure,Vibrational Circular Dichroism Spectroscopy and Second-order Nonlinear Optical Effect

A chiral lanthanide metal-organic framework based on enantiopure camphoric acid （D-H2cam）, [Nd3（D-cam）8（H2O）4Cl]n （1）, has been synthesized and characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Crystal data for the title compound are as follows： orthorhombic system, space group P212121 with a = 13.8287（7）, b = 14.0715（7）, c = 25.7403（12） A^°, V = 5008.8（4） A^°3, Mr = 1333.08, Z = 4, F（000） = 2644, Dc = 1.768 g/cm^3, μ（MoKα） = 3.189 mm^-1, the final R = 0.0351 and wR = 0.0814 （I 〉 2σ（I））. Compound 1 displays an 8-connected bcu topology 3D framework and hydrogen-bonding interactions stabilize the solid-state structure. The vibrational circular dichroism （VCD） spectrum and second-order nonlinear optical effect of compound 1 have been studied in the solid state.

Synthesis, Structure, and the Second-order Nonlinear Optical Properties of a Borate-carboxylic Acid Compound: KB[L-（-）-C4H4O5]2·H2O

A new organic-inorganic hybrid noncentrosymmetric potassium bis(malic acid)-borates KB(L-(-)-C4H4O5)2·H2O was synthesized by solution method. It was characterized by elemental analysis, FT-IR, TGA and single-crystal X-ray crystallography. It crystallizes in the monoclinic space group P21/c with a = 5.546(6), b = 11.985(13), c = 9.952(11) ?, β = 97.522(17)°, V = 655.8(13) ?3, Z = 2, Dc = 1.682 g/cm3, μ(MoKa) = 0.46 mm–1 and F(000) = 340. 5009 reflections were measured and 2893 independent reflections(Rint = 0.051) were used for further refinement. Single-crystal X-ray diffraction reveals that the complex exhibits a threedimensional pseudo tunnel structure consisting of fundamental building block [B(L-(-)-C4H4O5)2]– anions. The small cavities are occupied by the H2O molecules, which stabilize the whole structure by O–H×××O hydrogen bonds. The complex exhibits nonlinear optical effect as high as 1.5 times that of KDP standard.

THE SYNTHESIS OF NEW POLED CROSSLINKED POLYMETHACRYLATES AND THEIR SECOND ORDER NONLINEAR OPTICAL PROPERTIES

Films were prepared from mixtures of copolymers of 4-nitro-4'-[N-methylacryloyloxyethyl, N'-ethyl] amino azobenzene with glycidyl methacrylate (chromophore content: 6 mol%) and copolymers containing anhydride units, which was obtained by the reaction of 4-nitro-4'-[N-hydroxyethyl, N'-ethyl] amino azobenzene with polymethacryloyl chloride (chromophore content: 25 mol %). During thermal poling process the anhydride reacts with the epoxy group and the resulting crosslinked network structure will stabilize the second harmonic generation in the poled film. The second harmonic generation of the poled film shows a maximum with the variation of composition this is presumed to be due to the effects of the increasing of concentration, orientation order as well as orientation stability of chromophore groups during crosslinking.

SECOND ORDER NONLINEAR OPTICAL PROPERTIES OF DICYANOPYRAZINES

Second order nonlinear optical active 2,3-dichloro-5,6-dicyanopyrazine (DCDCP) and its monoamine-substituted derivatives had been synthesized. Their facile synthesis, high melt point, high incidence af substantial SHG activity and increased transparency inthe blue and near infrared make this class compounds appealling for further investigation.

Fluorine-Mediated Benzothiadiazole Derivatives for Second-Order Nonlinear Optics

With increasing research interests in the field of light-matter interactions,various methods have been developed for regulating nonlinear optical(NLO)materials.However,the design and synthesis of organic molecular materials for second-order nonlinear optics remain a great challenge because of the strict requirement of the materials to possess a noncentrosymmetric structure.In this work,two benzothiadiazole(BTD)derivatives referred to as BTD-H and BTD-F were synthesized,and their NLO properties in the crystalline states were studied.It was found that introducing fluorine into the BTD backbone effectively tuned the crystal packing styles of BTD derivatives to a noncentrosymmetric system for effective second-order NLO responses.Such a strategy to induce the noncentrosymmetric structure by introducing the fluorine atoms and halogen interactions may provide guidance for future engineering of organic NLO molecular materials.

Synthesis of Imidazole Derivatives for Their Second-order Nonlinear Optics

The design and the synthesis of two conjugated donor acceptor imidazole derivatives(1, 2) were carried out for second order nonlinear optics. The thermal properties, the transparency and second order nonlinear optical properties of the molecules were investigated. The experimental results indicate that a good nonlinearity transparency thermal stability trade off is achieved for them.

Second-order Nonlinearities of CdS Nanoparticles Studied by Hyper-Rayleigh Scattering Technique

A series of CdS nanoparticles with different surfaces were prepared by colloidal chemical method and reverse micelle method. Their second-order nonlinear optical (NLO) properties were experimentally studied in solution by newly developed hyper-Rayleigh scattering (HRS) technique. The results show that 'per particle' first-order hyperpolarizability beta values are sensitive To the synthetic method and the surface chemical modification.

SYNTHESIS AND CHARACTERIZATION OF NOVEL SOL-GEL DOPED ORGANIC/INORGANIC HYBRID NONLINEAR OPTICAL MATERIALS

hydroxy-4-nitro azobenzene (NHA) and 4-amino-4-nitro azobenzene (DO3) were prepared respectively from p-nitrophenylamine as a precursor compound. Two kinds of doped organic/inorganic hybrid nonlinear optical (NLO) materials containing NHA and DO3 were synthesized by Sol-Gel process. The preparation and properties of two NLO materials were studied and characterized by FTIR, 1H-NMR, UV-VIS, SEM, DSC and SHG measurements. The results show that the maximum doping amounts of NHA and DO3 in two doped hybrid NLO materials are 7.2(wt)% and 11.3(wt)% respectively, and the corresponding second-order NLO coefficients (d33 values) are 2.91×10 8esu and 6.14×10 8esu. Two doped NLO materials have relatively good RT stability, after 90 days at RT the d33 values can maintain about 85% of their initial values, but after 10h at 100℃ can only maintain about 50% of their initial values. In this report, the reasons for high-temperature instability of doped materials were discussed, and the possible improvements were also suggested.

Nonlinear Optical Properties of Two Different Nanoassemblies of Polydiacetylene (PDA): PDA Nanovesicles and PDA Nanocrystals

We have synthesized and characterized two different nanoassemblies of polydiacetylene (PDA), PDA nanovesicles and PDA nanocrystals, in order to study the influence of chain packing geometry of the two nanoassemblies on their third order nonlinear optical properties. The second molecular hyperpolarizability γ(-ω,ω,-ω,ω)of the two samples was investigated by antiresonant ring interferometric nonlinear spectroscopic (ARINS) technique using femtosecond modelocked Ti:sapphire laser in the spectral range of 720 nm - 820 nm. The observed spectral dispersion of γ has been explained in the framework of three-essential states model involving the ground state, a one-photon excited state and a two-photon excited state. The observed optical nonlinearity has been correlated with the electronic structure of the two samples. The energy of two-photon state, transition dipole moments and line width of the transitions have been estimated. Our studies show that the arrangement of polymer chains in polydiacetylene nanocrystals is more favorable for higher nonlinearity.

Nonlinear optical properties of Au/PVP composite thin films

Colloidal Au and poly（vinylpyrrolidone） （PVP） composite thin films are fabricated by spin-coating method. Linear optical absorption measurements of the Au/PVP composite films indicate an absorption peak around 530 nm due to the surface plasmon resonance of gold nanoparticles. Nonlinear optical properties are studied using standard Z-scan technique, and experimental results show large optical nonlinearities of the Au/PVP composite films. A large value of χ^（3）/α up to 0.56× 10-^10esu·cm is obtained, which is comparable to the best values reported in metal/oxlde composite films.

MOLECULAR DESIGN STUDY ON THE NEW ORGANIC NONLINEAR OPTICAL MATERIALS

In this paper,the second-order nolinear-optical coefficients of a series of conjugated substituted polyenes have been colculated by the semi-empirical CNDO/S-CI method.we have studied in deiail the influence on the number of substituents,the location of the substituents and the conjugation length in motecules to the NLO coefficient Bvace The results showed that the introduetion of the electroinc donor and acceptor groups and the increase in the distance between the substituents and the conjugated length may lead to enhanced NLO responses.It is also shown that the caiculoted In Bvec is linear with the number of double bonds in planar and linear tians substituted polyenes.A saturation effect in substitution is also presented.Based on these discussion one can provide the theorilical guidelines for designing and synthesizing of molecules with larger NLO coefficients.

LENGTH DEPENDENCE OF THE NONLINEAR OPTICAL SECOND-ORDER SUSCEPTIBILITY ON CONJUGATED ORGANIC MOLECULES

It is known that organic conjugated molecules with delocalized π-electron systems exhibit large nonlinear optical responses. The conjugated length is an important factor contributing to the nonlinear optical susceptibility.

The Design of Second-order Nonlinear Optical Dendrimers:From"Branch Only"to"Root Containing"

Dendrimers are considered as a promising family of organic second-order nonlinear optical （NLO） polymers because of their well-defined structures, easily modified peripheral functional groups, interior branches and central cores. In order to obtain NLO materials with high performance, dendrimer structures have been optimized in the past years, such as the ＂branch only＂ and the ＂root containing＂ type dendrimers. This feature article highlights the achievements in exploring the rational design of dendrimers, partially marked by their macroscopic NLO performance.

Dendronized Polymers with High FTC-chromophore Loading Density:Large Second-order Nonlinear Optical Effects, Good Temporal and Thermal Stability

In this study,two new dendronized nonlinear optical(NLO)polymers were synthesized with high FTC chromophore loading density by introduction of high generation chromophore dendrons on the side chains.Due to their suitable molecular weights,both of them possessed good solubility in common solvents.They also inherited the advantages of dendrimers(large NLO coefficient),especially for PG2 whose NLO coefficient d33 value was as high as 282 pm·V^–1.Also,PG2 had a good temporal stability with 80%of its maximum value being retained at the temperature as high as 129℃.

Laser molecular-beam epitaxy and second-order optical nonlinearity of BaTiO_3/SrTiO_3 superlattices

A series of c-axis oriented BaTiO3/SrTiO3 superlattices with the atomic-scale precision were epitaxially grown on single-crystal SrTiO3(100) substrates using laser molecular-beam epitaxy (LMBE). A periodic modulation of the intensity of reflection high-energy electron diffraction (RHEED) in BaTiO3 and SrTiO3 layers was observed and attributed to the lattice-misfit-induced periodic variation of the terrace density in film surface. The relationship between the second-order nonlinear optical sus-ceptibilities and the superlattice structure was systematically studied. The experimental and theoretical fitting results indicate that the second-order nonlinear optical susceptibilities of BaTiO3/SrTiO3 superlattices were greatly enhanced with the maximum value being more than one order of magnitude larger than that of bulk BaTiO3 crystal. The mechanism of the enhancement of the second-order optical non-linearity was discussed by taking into account the stress-induced lattice distortion and polarization

Synthesis and characterization of thermally crosslinked polyimide with second-order nonlinear optical chromophore

Synthesis of three novel crosslinked polyimides with push pull azobenzene group has been developed. 4 Nitro 4′ [N,N bis(2 aminoethyl)]aminoazobenzene was first prepared, then poly(amic acid) prepolymer, one crosslinkable component, was obtained by aminolysis of alternating styrene maleic anhydride copolymer, alternating thiophene maleic anhydride copolymer or alternating benzofuran maleic anhydride copolymer with it, and at last the crosslinked second order nonlinear optical polyimide was synthesized by crosslinking and imidizing poly(amic acid) prepolymer with corresponding alternating copolymer. The crosslinking and imidizing processes were studied by IR and UV Vis spectra. The chromophore density in one of the crosslinkable components, poly(amic acid) prepolymer, and the thermal stability of crosslinked polyimide thin film were measured by UV Vis spectra.

Theoretical Studies on Electronic Spectra and Second-order Nonlinear Optical Properties of Glucosyl Substituted Barbituric Acid Derivatives

AMI semi-empirical method was used to optimize the barbituric acid derivatives substituted with glucosyl B1-5 （series B）, and the thiobarbituric acid derivatives substituted with glucosyl T1-5 （series T）. Based on the optimized structures, INDO/CI method was adopted to calculate the electronic spectra. Meanwhile, the second-order nonlinear optical （NLO） coefficients βμ were calculated with the sum-over-state （SOS） formula. The results show that when the number of glucosyl units was increased, ｜βμ｜ values of the barbituric and thiobarbituric acid derivatives were both enhanced, especially for thiobarbituric acid derivatives. It indicates that non-conjugated substituted group could also improve NLO properties of materials when the number of repeated units was increased. Additionally, the absorption bands appearing in UV area are consistent with the proper change of the number of glucosyl units, and consequently it can be concluded that the high transparencies of all systems were scarcely varied.