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.

ZINDO-SOS Studies on Second-order Nonlinear Optical Properties of Thiophene S,S-Dioxide Chromophores

The second-order nonlinear optical properties of thiophene S,S -dioxides derivatives were studied by using the ZINDO-SOS method. The computed results show that the thiophene S,S -dioxide derivatives exhibit larger second-order polarizabilities than their thiophene precursors. In order to clarify the origin of the different NLO responses among these chromophores, their electron properties and frontier orbital properties were investigated as well. These thiophene S,S -dioxides derivatives are good candidates for their application in electro-optical device due to their high nonlinearities, good thermal and photo stabilities.

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.

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.

General Formulations of Finite-field Method Classifiedby Symmetry for Molecular Linear and Nonlinear Polarizabilities

The formulations of the finite-field approach to calculate the linear and non-linear optical coefficients (i, (ij, (ijk and (ijkl of a molecular system with different symmetries have been deduced and summarized. The possible choices of the energy sets of the 48 frequent point groups have been optimized and categorized into 11 classes. With the restriction of symmetry operators, a minimum of 9, no more than 21 energy points have to be calculated in order to determine the coefficients, except in the case of the first class to which C1 point group belongs and in which the 34 non-relative energy points selected in our uniform and general scheme are all needed. The symmetric operators that cause some of the tensor components to vanish have been demonstrated as well.

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.

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.

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.

Second-order Nonlinear Optical Properties of a Series of Benzothiazole Derivatives

The second-order nonlinear optical (NLO) properties of a series of benzothiazole derivatives were studied by use of the ZINDO-SOS method. These chromophores are formed by a donor-π-bridge-acceptor system, based on a nitro group connected with benzothiazole as the acceptor and a hydroxyl-functional amino group as the donor. For the purpose of comparison, we also designed molecules in which nitrobenzene is an acceptor. The calculation results indicate that benzothiazole derivatives exhibit larger second-order polarizabilities than nitrobenzene derivatives. In order to clarify the origin of the NLO response of these chromophores, their electron properties were investigated as well. The benzothiazole derivatives are good candidates for application in electro-optical device due to their high optical nonlinearities, good thermal and photonic stability.

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

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℃.

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.

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.

DFT Studies on Second-order Nonlinear Optical Response of Ir(C∧N)2(pic)Complexes

Density flmctional theory(DFT)was employed to calculate the geometrical structures,UV-Vis absorption spectra and second-order nonlinear optical(NLO)properties of a family of iridium(Ⅲ)complexes,which possess of different cyclometallated ligands(C∧N)and ancillary ligands[pyridme-2-carboxylate(pic)].It was found that the mo-dification of the LUMO energy levels was achieved by changing pic ligands and the energy gaps between the HOMO and LUMO were notably increased or decreased.In addition,the degree of conjugation was significantly changed with the substituent groups varied,which led to that the first hyperpolarizabilityβcould be effectively modulated.Through the analysis of time-dependent DFT(TD-DFT)results,we predicted that these studied complexes withπ→π^*charge transfer was beneficial to the large second-order NLO properties.Therefore,we hope that these studied iridium(III)complexes can be considered as versatile second-order NLO materials.

Middle-infrared Second-order Nonlinear Optical Chalcogenides and Halides Containing Multiple Anions

The second-order nonlinear optical(NLO)materials play an important role in the application and development of laser techniques.For various candidates,those in the middle infrared(MIR)region are far from the market’s requirement.Therefore,it is necessary to explore new ones with better performance.For their exploration,the inclusion of multiple anions in one structure has been proved to be a successful strategy.The NLO property contains several aspects,and different anions may contribute to different aspects.Therefore,the multiple anions’combination may give an opportunity to obtain NLO materials with desirable properties.Here,we make a short but clear summary on the MIR NLO-active chalcogenides and halides containing multiple anions,as most of them exhibit nice NLO performances.

Theoretical study on second-order nonlinear optical properties of unsymmetric bis (phenylethynyl) benzene series derivatives

On the basis of ZINDO methods, according to the sum-overstates (SOS) expression, the program for the calculation of the second-order nonlinear optical susceptibilities βijk and βμ of molecules was devised, and the structures and nonlinear optical properties of unsymmetric bis(phenylethynyl) benzene series derivatives were studied. The influence of the molecular conjugated chain lengths, the donor and the acceptor on βμ was examined.

Size Dependence of First-order Hyperpolarizability of CdS Nanoparticles Studied by Hyper-Rayleigh Scattering

The second-order optical nonlinearity of CdS nanoparticles with different diameters of 28.0, 30.0, 31.5, 50.0, and 91.0 A was studied by hyper-Rayleigh scattering technique. Results show that the first-order hyperpolarizability P value per CdS partiele decreases as size is reduced to diameter of 31.5 A; however, as CdS size further decreases, this trend is reversed and (J value increases. Substantially, the normalized P value per CdS formula unit, β0, exhibits systematic enhancement with decreasing size. This phenomenon is interpreted in terms of a so-called surfaee contribution mechanism.