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, Growth and Characterization of Organic Nonlinear Optical Single Crystals of 4-Bromo-4’-Methyl Benzylidene Aniline

Organic nonlinear optical material of 4-bromo-4’-methyl benzylidene aniline (BMBA) was synthesized and single crystal of BMBA was grown by solvent evaporation method at room temperature using ethanol as solvent. The crystalline nature of the grown crystals was confirmed using powder X-ray diffraction studies. The crystals were also characterized by single crystal X-ray diffraction method and their lattice parameters were determined. Thermal properties of BMBA were evaluated with thermogravimetric, differential thermal and differential scanning calorimetric analyses. Fourier transform infrared and FT-Raman spectral studies were carried out on the BMBA material to confirm the synthesized compound. 1H and 13C-nuclear magnetic resonance spectral studies were recorded to elucidate the structure of the grown crystals. Fluorescence spectrum recorded shows a peak at 485 nm. UV-Vis-NIR spectral analysis shows transmittance of ~92% in the visible region. The mechanical stability was analyzed by Vickers microhardness tester and the work hardening coefficient of the grown crystal was calculated. Second harmonic generation efficiency of the grown crystal measured by Kurtz powder technique is ~1.8 times that of potassium dihydrogen orthophosphate.

Preparation of Organic Nanoparticle Colloids by Laser Ablation and Their Nonlinear Optical Properties

Suspension of micrometer-sized 1,4-bis（4-methylstyryl）benzene（p-MSB） was converted into colloidal nanocrystal solution by irradiation with an femtosecond laser（800 nm, 1 kHz）. The prepared nanocrystals were rectangular with ca. 100 nm in size. The same crystal structure as that of bulk crystals was confirmed by X-ray diffraction measurement. UV-Vis spectra and emission spectra of the nanoparticle dispersions in dichloromethane（poor solvent） were examined. The nanocrystal exhibits large quantum yield（89%）. The nonlinear optical properties of the nanocrystals were further studied by Z-scan technique with femtosecond laser duration of 120 fs at a wavelength of 800 nm. The results show that the nanocrystals exhibit strong nonlinear absorption.

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, 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.

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.

ORGANIC NONLINEAR OPTICAL CRYSTAL:N-(4-NITROPHENYL)-(s)-(+)-2-PYRROLIDINEMETHYLENE TOSYLATE(NPP-OTs)

Large crystal NPP-OTs has been obtained by growth from solution,its powder SHG efficiency is 1/3 of urea.It shows it is a new convenient approach to obtain organic second-order NLO crystal:the dipole-dipole interaction is oppos- ed by introducing a large side group.

NEW ORGANIC NONLINEAR OPTICAL MATERIALS OF CINNAMYLIDENE-ACETOPHENONE DERIVATIVES

we have synthesised a series of new optically nonlinear organic materials of cinnamylidene-acetophenone derivatives which have large nonl inear optical susceptibilities and short cut-off wavelengths.

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.

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.

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.

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.

Synthesis and Nonlinear Optical Property of a Series of New Chromophores Containing Furan Ring as the Only Conjugation Bridge

This paper reports the synthesis and the nonlinear optical property of a series of new chromophores which contain furan ring as the only conjugation bridge for the first time. They are characterized by UV-VIS, FT-IR, H-1 NMR, MS and elemental analysis. Their dipole moment and the first-order molecular hyperpolarizability (beta) are calculated and compared with those or the analogues containing either benzene or thiophene as file conjugation bridge.

AN EPOXY/(METHYL METHACRYLATE)INTERPENETRATING POLYMER NETWORK FOR NONLINEAR OPTICS

An interpenetrating polymer networks (IPN) consisting of an epoxy-based polymer network and a polymethyl methacrylate network were synthesized and characterized. The IPN showed only one T-g, and hence a homogeneous-phase morphology was suggested. The second-order nonlinear optical coefficient (d(33)) of the IPN was measured to be 1.72 X 10(-7) esu. The study of NLO temporal stability at room temperature and elevated temperature (100 degrees C) indicated that the IPN exhibits a high stability in the dipole orientation due to the permanent entanglements of two component networks in the IPN system. Long-term stability of second harmonic coefficients was observed at room temperature for more than 1000 h.

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.

Nonlinear Optical Response of Conjugated Polymer to Elec tric Field

The organic π-conjugate d polymers are of major interest materials for the use in electro-optical and no nlinear optical devices. In this work, for a selected polyacetylene chain, the optical absorption spectra in UV/Vis regime as well as the linear polarizabiliti y and nonlinear hyperpolarizability are calculated by using quantum chemical ab initio and semiempirical methods. The relationship of its optical property to el ectric field is obtained. Some physical mechanism of electric field effect on mo lecular optical property is discussed by means of electron distribution and intr amolecular charge transfer.

Synthesis, Crystal Growth and Characterization of Organic NLO Material: M-Nitroacetanilide

Single crystals of m-Nitroacetanilide (mNAa) were successfully grown by slow evaporation method at a constant temperature 40°C from methanol solution. The solubility studies for mNAa were estimated. The cell dimensions were obtained by single crystal X-ray diffraction (XRD) study. The functional groups have been confirmed using Fourier transform infrared (FTIR) analysis. The placement of protons was identified from Nuclear Magnetic Resonance Spectroscopy (NMR) spectral analysis. UV-visible and fluorescence spectral analyses were carried out for the grown crystals. Thermo gravimetric analysis and differential thermal analysis were carried out to determine the thermal properties of the as grown crystal. The Second Harmonic Generation (SHG) efficiency of mNAa was also determined.

Theoretical investigation of nonlinear properties of electrooptical chromophores

Organic electrooptical （EO） chromophores are now gaining more attention because the property of organic photorefrative （PR） materials could be controlled by doped EO chromophores. In this paper, nonlinear optical （NLO） properties of a new group of organic electrooptical chromophores, synthesized recently in our laboratory, were elucidated theoretically with the quantum chemical density functional theory （DFT） and the intermediate neglect of differential overlap Hamilton and the configuration interaction （INDO/CI）, as well as semiemperical Austin Model 1 （AM1） methods. The electronic transition intensity, dipole moment and the second-order polarizability were obtained. The results show this group of chromophores possess appropriate optical absorption property and good electrooptical property and optical activity. The second-order polarizabilities β are as large as the order of 10-29 to 10-28 ESU, indicating the promising applications in the future. The physical mechanism of NLO is discussed by means of molecular orbital and electronic charge distribution.

Influence of Kerr Effect on Second-Order Nonlinearity Induced Transparency

We theoretically study the effect of Kerr effect on the second-order nonlinearity induced transparency in a double-resonant optical cavity system.We show that in the presence of the Kerr effect,as the strength of the Kerr effect increases,the absorption curve exhibits an asymmetric-symmetric-asymmetric transition,and the zero absorption point shifts with the increase of the Kerr effect.Furthermore,by changing the strength of the Kerr effect,we can control the width of the transparent window,and the position of the zero-absorption point and meanwhile change the left and right width of the absorption peak.The asymmetry absorption curve can be employed to improve the quality factor of the cavity when the frequency detuning is tuned to be around the right peak.The simple dependence of the zeroabsorption point on the strength of Kerr effect suggests that the strength of Kerr effect can be measured by measuring the position of the zero-absorption point in a possible application.