Home About us Contact | |||
Nonlinear Optical Properties (nonlinear + optical_property)
Kinds of Nonlinear Optical Properties Selected AbstractsReactions of [Et4N][Tp*W(,3 -S)(,-S)2(CuSCN)2] with Nitrogen Donor Ligands: Syntheses, Structures, and Third-Order Nonlinear Optical PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2009Zhen-Hong Wei Abstract Reactions of the preformed cluster [Et4N][Tp*W(,3 -S)(,-S)2(CuSCN)2] (1) with pyridine (py), 4,4,-bipyridine (4,4,-bipy), or 1,3-bis(4-pyridyl)propane (bpp) led to the formation of three neutral [Tp*W(,3 -S)(,-S)2Cu2]-based compounds [Tp*W(,3 -S)(,-S)2Cu2(SCN)(py)2] (2), [{Tp*W(,3 -S)(,-S)2Cu2(SCN)}2(4,4,-bipy)]·3.5H2O (3·3.5H2O), and [Tp*W(,3 -S)(,-S)2Cu2(SCN)(bpp)]2 (4), respectively. Compounds 2,4 were characterized by elemental analysis, IR spectra, UV/Vis spectra, 1H NMR, and X-ray analysis. There are two linkage isomers [Tp*W(,3 -S)(,-S)2Cu2(SCN)(py)2] and [Tp*W(,3 -S)(,-S)2Cu2(NCS)(py)2], each of which has its own enantiomeric pair in the crystal of 2. Compound 3 has a double butterfly-shaped structure in which two [Tp*W(,3 -S)(,-S)2Cu2(SCN)] fragments are linked with a single 4,4,-bipy bridge. For 4, the two butterfly-shaped [Tp*W(,3 -S)(,-S)2Cu2(SCN)] fragments are interconnected by a pair of bpp bridges. The third-order nonlinear optical (NLO) performances of 2,4 in DMF were also investigated by Z -scan techniques.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis, Structure, Conductivity, and Calculated Nonlinear Optical Properties of Two Novel Bis(triphenylphosphane)copper(I) Dithiocarbamates,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2009Abhinav Kumar Abstract A centrosymmetric binuclear [{Cu(PPh3)2}2(piperzdtc)] (1) [piperzdtc2, = piperazinebis(dithiocarbamate)] and another mononuclear [{Cu(PPh3)2}(BzMedtc)] (2) (BzMedtc, = N -benzyl- N -methyldithiocarbamate) complex have been synthesized and characterized by elemental analyses, IR, 1H, 13C, and 31P NMR spectroscopy and by X-ray crystallography. The nonlinear optical properties of 2 have been investigated by density functional theory and its electronic absorption bands have been assigned by time-dependent density functional theory (TD-DFT). Both complexes are weakly conducting (,rt , 10,8 S,cm,1) because of the absence of M···S/S···S intermolecular stacking and exhibit semiconductivity with band gaps of 0.94 and 1.24 eV, respectively.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] How Do the Different Defect Structures and Element Substitutions Affect the Nonlinear Optical Properties of Lacunary Keggin Polyoxometalates?EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2006A DFT Study Abstract Systematic DFT calculations have been carried out on the lacunary ,-Keggin polyoxometalate derivatives [PW11O39]7,, [XW9O34]n, (X = AlIII, SiIV, GeIV, PV, AsV, and SbV), [XW9M2O39]n,, and [XW9M3O40]n, (X = PV and SiIV, M = MoVI, VV, NbV, and TaV) to investigate the geometric structure and element substitution effects on the molecular nonlinear optical response. Analysis of the computed static second-order polarizability (,0) predicts that the molecular nonlinear optical activity of lacunary Keggin polyoxometalate derivatives can be modified by replacing the central heteroatom and the addenda metal atom. Substitution of the central Al atom or the addenda V atom causes significant enhancement in the molecular nonlinearity. Moreover, the ,0 values are substantially dependent on the defect structures. This class of inorganic complexes possesses remarkably large molecular optical nonlinearity, especially for the partial substitution complex [SiW9Nb2O39]10, (IIIc), which has a computed ,0 value of 2071.0 a.u. Thus, lacunary Keggin polyoxometalates could become excellent candidates in the field of second-order NLO. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis, Crystal Structure, and Second-Order Nonlinear Optical Properties of Ruthenium(II) Complexes with Substituted Bipyridine and Phenylpyridine LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2006Laurence Labat Abstract Two new ruthenium(II) complexes of formula [Ru(bpy)2(L1)][PF6] and [Ru(bpy)2(L2)][PF6]2 are reported. HL1 is a (nitrophenyl)ethenyl-substituted phenylpyridine ligand, and L2 is the bipyridine analogue of HL1. The X-ray crystal structure of [Ru(bpy)2(L1)][PF6] has been solved, and the compound is found to crystallize in the monoclinic C2/c space group. The electronic spectrum of the cyclometalated derivative [Ru(bpy)2(L1)][PF6] exhibits a low-lying transition that is red-shifted from 454 to 546 nm relative to that of the parent bipyridine-based complex, which reveals an important charge-transfer character. To support this assumption, the nonlinear optical properties were investigated by the hyper-Rayleigh scattering technique and indicate a molecular static hyperpolarizability (,0) equal to 230,×,10,30 cm5,esu,1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Second-Order Nonlinear Optical Properties of Tetraaza-Coordinated Nickel(II) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2003Santo Di Bella Abstract In this contribution, we report the design and theoretical analysis, using the INDO/SCI-SOS quantum chemical formalism, of novel molecular architectures based on planar [N4]-, (2-aminobenzylideneiminato)- and tetraazamacrocycle-coordinated nickel(II) complexes, having second-order nonlinear optical (NLO) properties. Calculations indicate that these molecules possess comparable, or even larger, second-order nonlinearity to the bis(salicylaldiminato)NiII Schiff-base analogues. The nonlinearity of substituted complexes is dominated by the nature and position of substituents on the tribenzo[b,f,l] and/or cyclotetradecine rings, and is determined by the relative directions of the ground- and excited-state dipole moments. Moreover, substitution with acceptor groups in the dibenzo[b,l] rings involves a significant octupolar contribution to optical nonlinearity. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] One-Pot Synthesis of Core-Modified Rubyrin, Octaphyrin, and Dodecaphyrin: Characterization and Nonlinear Optical PropertiesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 27 2007Rajeev Kumar Abstract Modified 26, rubyrin, 36, octaphyrin, and 54, dodecaphyrin systems have been synthesized in moderately good yields through acid-catalyzed condensations of terthiophene diols and tripyrranes. The product distributions are decided both by the acid catalyst concentration and by the nature of the meso substituents. For example, a new isomer of [26]hexaphyrin(1.1.1.1.0.0) (rubyrin) was obtained with 0.3 equiv. of p -toluenesulfonic acid, when the meso substituent was mesityl in at least one of the precursors. A change of the mesityl substituent for a p -methoxy substituent in terthiophene diol resulted in the formation of a [3,+,3,+,3,+,3] condensation product , [54]dodecaphyrin(1.1.1.1.0.0.1.1.1.1.0.0) , in addition to the expected rubyrin. Furthermore, an increase in the acid concentration to 0.6 equiv. resulted in the formation of a new [36]octaphyrin(1.1.1.1.1.1.0.0), in addition to the rubyrin and dodecaphyrin. A single-crystal X-ray analysis of octaphyrin represents the first example of a planar conformation of an octaphyrin with six meso links. In rubyrin 19, one thiophene ring, opposite to the terthiophene subunit, is inverted, while in octaphyrin 30 one pyrrole ring and two thiophene rings are inverted. The various conformational possibilities tested for the unsubstituted dodecaphyrin 28, at semiempirical level, suggest that the most stable conformation is a figure-eight. The final geometry optimization of figure-eight dodecaphyrin was done at the B3LYP/6-31G* level of DFT. Octaphyrins and dodecaphyrins bind trifluoroacetate anion effectively in their diprotonated forms, the binding constants (K) being 638 M,1 for dodecaphyrin 28, and 415 M,1 for octaphyrin 30. Electrochemical data reveal HOMO destabilization with increasing , electron conjugation, consistently with the large red shifts of the absorption bands. Preliminary studies on the use of these expanded porphyrins as third-order NLO materials were followed by measurements of their two-photon absorption (TPA) cross-sections [,(2)]. The ,(2) values increase upon going from the 26, rubyrins to the 54, dodecaphyrins, confirming our earlier observation that increases in ,-conjugated electrons increase the TPA values.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis, Characterisation and Nonlinear Optical Properties of Two-Dimensional Octupolar Systems Based on Phthalocyanine CompoundsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2005Maurizio Quintiliani Abstract Four phthalocyanine-based compounds with pseudo D3h symmetry have been synthesised and fully characterised. Palladium cross-coupling methodologies were employed in order to synthesise 1,3,5-tris[(phthalocyaninyl)ethenyl]benzene (Heck) and 1,3,5-tris[(phthalocyaninyl)ethynyl]benzene (Sonogashira) derivatives. Knoevenagel condensation conditions were then applied to the synthesis of 1,3,5-tris[cyano(phthalocyaninyl)ethenyl]benzene and 2,4,6-tris[(phthalocyaninyl)ethenyl]-1,3,5-triazine. Preliminary second-order nonlinear optical studies, by hyper-Rayleigh scattering measurements, revealed that the compounds containing ethenyl linkers induce a strong octupolar effect while the ethynyl-containing compound does not show any octupolar enhancement. The introduction of a triazine central core does not modify significantly the nonlinear optical behaviour of the compound. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Linear and Nonlinear Optical Properties of Ag Nanowire Polarizing Glass,ADVANCED FUNCTIONAL MATERIALS, Issue 18 2006Q.-Q. Wang Abstract An R2O,B2O3,SiO2 (R,=,Li, Na, K) polarizing glass containing Ag nanorods is prepared by thermal elongation,reduction technology. The transverse and longitudinal plasmon absorption peaks of the embedded Ag nanorods are near 460 and 720,nm, respectively. When the polarization of the laser is parallel to the long axis of the Ag nanorods, the nonlinear absorption coefficient ,,=,0.82,cm,GW,1 and the nonlinear refractive index n2,=,,1.5,×,10,4,cm2,GW,1. When the polarization of light is perpendicular to the long axis of the Ag nanorods ,,=,0.12,cm,GW,1 and n2,=,,7.2,×,10,5,cm2,GW,1 and the appropriate one- and two-photon figures of merit (FOM), W,=,1.6 and T,=,0.16, respectively, are obtained, which satisfies the demand, W,>,1 and T,<,1, for applications in all optical switching, where W is a one-photon FOM, and T is a two-photon FOM. [source] Atom Transfer Radical Polymerization and Third-Order Nonlinear Optical Properties of New Azobenzene-Containing Side-Chain PolymersMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 4 2007Najun Li Abstract The atom transfer radical polymerization (ATRP) technique has been successfully applied to synthesize a series of nonlinear optically (NLO) active homopolymers, 4-(4-nitrophenyl-diazenyl) phenyl acrylate (P - NPAPA) and 4-(4-methoxyphenyl-diazenyl) phenyl acrylate (P - MPAPA), containing azobenzene groups on the side chain. The third-order NLO properties of the polymer films were measured by the degenerated four-wave mixing (DFWM) technique. A dependence of the ,(3) values and response times of polymers on their number-average molecular weight and the electronic effect of the substituent (nitro- or methoxy-) on the azobenzene group have been evidenced. The increasing ,(3) value of the polymer films at the magnitude of about 10,10 was displayed with increasing molecular weight and the presence of the push-pull electronic system contributes much in enhancing the third-order NLO susceptibility of polymers. [source] Study of Nonlinear Optical Properties of Multilayer Langmuir,Blodgett Films Containing Bacteriorhodopsin,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2000Yu. O. Barmenkov ABSTRACT Multilayer oriented Langmuir,Blodgett films of bacteriorhodopsin were prepared and their nonlinear optical properties, including second harmonic generation and photoresponse at a two phase-modulated beams mixing, were investigated. The nonlinear component of refractive index of the films was measured. [source] Switching the Cubic Nonlinear Optical Properties of an Electro-, Halo-, and Photochromic Ruthenium Alkynyl Complex Across Six States,ANGEWANDTE CHEMIE, Issue 42 2009Drei Schalter in einem Molekül: Die Titelverbindung (siehe Schema) enthält addressierbare Module, die unabhängig voneinander auf Protonierung (Alkinylligand,Vinylidenligand), elektrochemische (Metallredoxzentrum: RuII,RuIII) und photochemische Reize (Dithienylperfluorcyclopenten: Ringöffnung,Ringschluss) ansprechen. Die sechs Zustände wandeln sich über sieben Pfade ineinander um, wobei sich jeweils die nichtlinearen optischen Eigenschaften in bestimmter Weise ändern. [source] ChemInform Abstract: Compounds of Superatom Clusters: Preferred Structures and Significant Nonlinear Optical Properties of the BLi6X (X: F, LiF2, BeF3, BF4) Motifs.CHEMINFORM, Issue 8 2009Ying Li Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Synthesis and Study of Novel Benzothiazole Derivatives with Potential Nonlinear Optical Properties.CHEMINFORM, Issue 2 2008Ivica Sigmundova Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] How Do the Different Defect Structures and Element Substitutions Affect the Nonlinear Optical Properties of Lacunary Keggin Polyoxometalates?CHEMINFORM, Issue 49 2006A DFT Study. Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] New Skeletal 3D Polymeric Inorganic Cluster [W4S16Cu16Cl16]n with Cu in Mixed-Valence States: Solid-State Synthesis, Crystal Structure, and Third-Order Nonlinear Optical Properties.CHEMINFORM, Issue 8 2006Ya Cai Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access the actual ChemInform Abstract, please click on HTML or PDF. [source] ChemInform Abstract: Thermal and Nonlinear Optical Properties of Ca4YO(BO3)3.CHEMINFORM, Issue 1 2002J. Luo Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Observing Second-Order Nonlinear Optical Properties by Symmetry Breaking in Centrosymmetric Furan-Containing Oligoaryl CyclophandienesCHEMISTRY - A EUROPEAN JOURNAL, Issue 47 2009Hsin-Chieh Lin Dr. Abstract Centrosymmetric furan-containing cyclophandienes 3 and 4, synthesized by our furan annulation protocol, have been shown to exhibit extraordinarily large Stokes shifts and second-order nonlinear optical , values. The , values for 3 and 4 measured at 1.32,,m are 208 and 530×10,30,esu, respectively. The , values of 3 and 4 are similar to those of respective cyclophenes 1,a and 7 in which strong hyperpoarizable interactions between two twisted ,-systems (oligoaryl and bridging double bond) might take place. Symmetry breaking due to the resonance contribution (cf. 2) and the unique structural features of 3 and 4 has been used to account for this unusual photophysical behavior. [source] Synthesis, Structure, and Nonlinear Optical Properties of Cross-Conjugated Perphenylated iso -PolydiacetylenesCHEMISTRY - A EUROPEAN JOURNAL, Issue 1 2005Yuming Zhao Prof. Abstract Monodisperse, cross-conjugated perphenylated iso- polydiacetylene (iso- PDA) oligomers, ranging from monomer 15 to pentadecamer 25, have been synthesized by using a palladium-catalyzed cross-coupling protocol. Structural characteristics elucidated by X-ray crystallographic analysis demonstrate a non-planar backbone conformation for the oligomers due to the steric interactions between alkylidene phenyl groups. The electronic absorption spectra of the oligomers show a slight red-shift of the maximum absorption wavelength as the chain length increases from dimer 17,b to pentadecamer 25, a trend that has saturated by the stage of nonamer 22. Fluorescence spectroscopy confirms that the pendent phenyl groups present on the oligomer framework enhance emission, and the relative emission intensity consistently increases as a function of chain length n. The molecular third-order nonlinearities, ,, for this oligomer series have been measured via differential optical Kerr effect (DOKE) detection and show a superlinear increase as a function of the oligomer chain length n. Molecular modeling and spectroscopic studies suggest that iso- PDA oligomers (n>7) adopt a coiled, helical conformation in solution. [source] Structural and Nonlinear Optical Properties of Aligned Heterotrinuclear [RuII -(Spacer)-MII -(Spacer)-RuII] Complexes (M=Pd, Pt; spacer=4-ethynylpyridine)CHEMISTRY - AN ASIAN JOURNAL, Issue 6 2009Qingchun Ge Abstract Optical alloy: "Linear" heterotrinuclear assemblies, with the metals separated by 4-ethynylpyridine spacers [RuCp(CCpy-4)(dppf)]2[MCl2] (M=Pd, Pt), have been structurally identified. They are electrochemically active and show good cubic nonlinear optical responses. Lewis addition between the metalloligand [RuCp(CCpy-4)(dppf)] (1) (dppf=(C5H4PPh2)2Fe) and MCl2(CH3CN)2 gives [RuCp(CCpy-4)(dppf)]2[MCl2] (M=Pd (2) and Pt (3)), all of which have been spectroscopically and crystallographically characterized. The mixed-metal adducts show the d6 -d8 -d6 metal alignment maintained by the trans disposition of the directionally rigid 4-ethynylpyridine at the centrosymmetric square-planar metal center. Electrochemical studies of these and the related known complexes trans -[RuCl(CCpy-4)(dppm)2] (4) and [trans -RuCl(CCpy-4)(dppm)2]2[MCl2] (dppm=Ph2PCH2PPh2) (M=Pd (5) and Pt (6)) suggest that the spacer-linked heterotrinuclear network is able to stabilize the oxidized RuIII better than the metalloligand precursor. Cubic nonlinear optical responses are also generally higher for the heterometallic complexes. The ,real value of the PdRu2 dppm complex 5 is among the largest for linear organometallic complexes. [source] Nonlinear Optical Properties of Ferrocene- and Porphyrin,[60]Fullerene DyadsCHEMPHYSCHEM, Issue 7 2007Evangelia Xenogiannopoulou Dr. Abstract A series of novel [60]fullerene,ferrocene and [60]fullerene,porphyrin dyads, in which a fullerene and an electron donating moiety are attached through a flexible triethylene glycol linker are synthesized and their nonlinear optical (NLO) response studied. Specifically, the third-order susceptibility ,(3) of all fullerene derivatives are measured in toluene solutions by the optical Kerr effect (OKE) technique using 532 nm, 35 ps laser pulses and their second hyperpolarizability , are determined. All fullerene dyads studied exhibit enhancement of their NLO response compared to pristine fullerenes which has been attributed to the formation of a charge separated state. All experimentally measured hyperpolarizability , values are also calculated by the semiempirical methods AM1 and PM3. A good correlation is found between the theoretical and experimental values, suggesting that simple semiempirical methods can be employed for the designing and optimization of the fullerene-containing dyads displaying improved nonlinear responses. [source] Fabrication of Ultrathin Films with Large Third-Order Nonlinear Optical PropertiesCHEMPHYSCHEM, Issue 3 2005Li Jiang Abstract An ultrathin composite film containing anionic Ag-His complexes (His: L -Histidine) and oppositely charged BH-PPV was fabricated by means of the electrostatic layer-by-layer self-assembly technique. UV/Vis spectra showed a continuous deposition process of Ag-His complexes and BH-PPV. The film structure was characterized by using small-angle X-ray diffraction, AFM, and SEM. The nonlinear optical properties of the ultrathin film were studied by using the Z -scan technique with a laser duration of 8 ns at a wavelength of 532 nm. The film sample exhibited a strong nonlinear saturated absorption, with an ,2value of ,3.9×10,5m,W,1and a self-defocusing effect with an n2value of ,4.78×10,12m2,W,1. [source] Theoretical Study on Second-order Nonlinear Optical Properties of Substituted Thiazole DerivativesCHINESE JOURNAL OF CHEMISTRY, Issue 4 2001Yong-Jun Liu Abstract On the basis of ZINDO program, we have designed a program to calculate the nonlinear second-order polarizability ,yk and ,, according to the SOS expression. The second-order nonlinear optical properties of 4-nitro-4,-dimethylamino-stilbene and a series of its thiazole derivatives were studied. The calculated results were that: When replacing a benzene ring in 4-nitro-4,-dimethylamino-stilbene by a thiazole ring, the influence on , values depends on the position of thiazole ring. When the thiazole ring connects with nitro group (acceptor), the , values increase significantly compared with corresponding stilbene derivatives. The , values of 2-(p -donor-,-styryl)-5-nitro-thiazole derivatives (2,7) are larger than those of 2-(p -nitro-,-styryl)-5-donor-thiazole derivatives (8,13) and 2-(p -donor-phenyl)-azo-5-nitro-thiazole derivatives (14,19). The 2-(p -donor-,-styryl)-5-nitro-thiazole derivatives (2,7) are good candidates as chromophores duo to their high nonlinearities and potential good thermal stability. [source] Nonlinear optical properties of poly-ortho-toluidine films implantated by N+ ions with different energyPOLYMER COMPOSITES, Issue 10 2009Yan Shaolin This article reports experimental work on the effect of N+ ion implantation on third-order nonlinear optical properties of POT films. Using K2Cr2O7 as oxidizing agent, poly- ortho -toluidine (POT) was synthesized in 1 M hydrochloric. The POT films were prepared by spin-coating method and then implantated by N+ ions (15,30 KeV) at a dose 1.9 × 1016 ions/cm2. The films were characterized by FT-IR spectroscopy, visible spectroscopy and SEM, their third-order nonlinear optical susceptibility (,(3)) were also examined by a degenerate four-wave mixing (DFWM) system at 532nm. Compared to pristine POT films, the optical band gap obtained from visible spectra decreased from 3.58 to 3.48 eV when the energy was 30 KeV. Also, The ,(3) value of implantated POT films increased from 3.31 × 10,10 esu to 4.04 × 10,9 esu when the implantated energy was 25 KeV. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers [source] Nucleation kinetics and growth of nonlinear optical bis (dimethyl sulfoxide) manganese mercury thiocyanate single crystalsCRYSTAL RESEARCH AND TECHNOLOGY, Issue 10 2008C. M. Raghavan Abstract Nonlinear optical (NLO) material of bis (dimethyl sulfoxide) manganese mercury thiocyanate (MMTD) was synthesized by two step reaction method. The solubility and metastable zonewidth were experimentally determined in order to optimize the growth parameters. Bulk crystals of MMTD were grown by slow cooling and slow evaporation methods. The structure of the grown crystal was confirmed by X-ray diffraction analysis. Presence of functional groups and the coordination of Lewis base ligand of dimethyl sulfoxide (DMSO) were confirmed by FT-IR analysis. Optical transparency of the grown crystals was studied by UV-Vis spectroscopy. Nonlinear optical property of the grown crystal was confirmed by Kurtz powder method. Etching studies reveal the formation of triangular hillock etch patterns, indicative of 2D nucleation mechanism. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Preparation, physicochemical and third order nonlinear optical properties of bis(tetrabutylammonium)bis(2-thioxo-1,3-dithiole-4,5-dithiolato)mercurate(II)CRYSTAL RESEARCH AND TECHNOLOGY, Issue 6 2009X. Q. Wang Abstract Bis(tetrabutylammonium)bis(2-thioxo-1,3-dithiole-4,5-dithiolato)mercurate(II) was prepared and characterized by elemental analyses, electronic absorption, infrared and X-ray powder diffraction spectroscopy. The specific heat of the crystal was measured to be 1878.2 J.mol,1K,1 at 300 K. The thermal decomposition process was investigated by means of thermogravimetric analysis and differential thermal analysis measurements in air together with infrared and X-ray powder diffraction spectra. The third-order nonlinear optical properties at 800 nm were measured by femtosecond optical Kerr gate technique by using CS2 as reference. The third-order optical susceptibility of its acetone solution at the concentration of 9.27 × 10,4 M was obtained to be 2.53 × 10,14 esu. The second-order hyperpolarizability was estimated to be 1.7 × 10,32 esu and the response time was about 226 fs. The third order nonlinear optical properties at 532 nm were investigated by using the Z-scan technique with 20 ps. It exhibited self-focusing effect and saturable absorption. The second molecular hyperpolarizability was estimated to be 8.4 × 10,32 esu. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Synthesis, Crystal Structure, and Second-Order Nonlinear Optical Properties of Ruthenium(II) Complexes with Substituted Bipyridine and Phenylpyridine LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2006Laurence Labat Abstract Two new ruthenium(II) complexes of formula [Ru(bpy)2(L1)][PF6] and [Ru(bpy)2(L2)][PF6]2 are reported. HL1 is a (nitrophenyl)ethenyl-substituted phenylpyridine ligand, and L2 is the bipyridine analogue of HL1. The X-ray crystal structure of [Ru(bpy)2(L1)][PF6] has been solved, and the compound is found to crystallize in the monoclinic C2/c space group. The electronic spectrum of the cyclometalated derivative [Ru(bpy)2(L1)][PF6] exhibits a low-lying transition that is red-shifted from 454 to 546 nm relative to that of the parent bipyridine-based complex, which reveals an important charge-transfer character. To support this assumption, the nonlinear optical properties were investigated by the hyper-Rayleigh scattering technique and indicate a molecular static hyperpolarizability (,0) equal to 230,×,10,30 cm5,esu,1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] New Organic Nonlinear Optical Polyene Crystals and Their Unusual Phase Transitions,ADVANCED FUNCTIONAL MATERIALS, Issue 11 2007O-P. Kwon Abstract A series of new nonlinear optical chromophores based on configurationally locked polyenes (CLPs) with chiral pyrrolidine donors are synthesized. All CLP derivatives exhibit high thermal stability with decomposition temperatures Td at least > ,270,°C. Acentric single crystals of enantiopure D - and L -prolinol-based chromophores with a monoclinic space group P21 exhibit a macroscopic second-order nonlinearity that is twice as large than that of analogous dimethylamino-based crystal. This is attributed to a strong hydrogen-bonded polar polymer-like chain built by these molecules, which is aligned along the polar crystallographic b -axis. Five ,-phase CLP crystals with different donors grown from solution exhibit a reversible or irreversible thermally induced structural phase transition to a ,-phase. These phase transitions are unusual, changing the crystal symmetry from higher to lower at increasing temperatures, for example, from centrosymmetric to non-centrosymmetric, enhancing their macroscopic second-order nonlinear optical properties. [source] Theoretical study on the second-order nonlinear optical properties of nonconjugated D-,-A chromophoresINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 7 2009Guochun Yang Abstract Density functional theory calculations have been carried out on nonconjugated D-,-A chromophores to investigate the different electron donors and conjugated bridges effects on the molecular nonlinear optical response. The results show that the large second-order polarizability values can be achieved through careful combination of available electron donors, conjugated bridges for our studied nonconjugated D-,-A chromophores. The calculations also provide a clear explanation for the second-order polarizability changes from the standpoint of transition energies, oscillator strengths, electron density difference, and bond length alternation. Solvent effect has great influence on the second-order polarizability and electronic absorption spectrum. It is hoped that the results presented in this article will give some hints to the interrelated studies. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Nonempirical calculations of nonlinear optical properties of p -nitroaniline in acetone: Comparison of supermolecule and semicontinuum approachesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2007Marina Yu. Abstract The comparison of the conventional continuum, supermolecule, and semicontinuum models for the description of solvent effect on the (hyper)polarizability of p -nitroaniline (PNA) in acetone is performed. The supermolecule approach is used for the clusters containing PNA and one or two acetone molecules. The account of the specific solute,solvent interactions via the hydrogen bonds formation is shown to result in the enhancement of (hyper)polarizability values. The continuum approach exploited in the framework of polarizable continuum model (PCM) was shown to describe mainly the solvent effect on (hyper)polarizability. The semicontinuum approach, accounting explicitly the interaction between PNA and solvent molecules and treating the rest of the solvent as a continuum, results in a moderate increase of the (hyper)polarizability values compared to those obtained within the conventional PCM approach. All the calculations of (hyper)polarizabilities are performed at the Hartree,Fock level in the aug-cc-pVDZ' Dunning basis set. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Coupled-perturbed Hartree,Fock theory for quasi,one-dimensional periodic systems: Calculation of static and dynamic nonlinear optical properties of model systemsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2003A. Martinez Abstract An alternative method to solve the coupled-perturbed Hartree,Fock (CPHF) equations for infinite quasi,one-dimensional systems is presented. The new procedure follows a proposal made by Langhoff, Epstein, and Karplus to obtain perturbed wavefunctions free from arbitrary phase factors in each order of perturbation. It is based on the intermediate orthonormalization of the perturbed wavefunctions (which is different from the usual one) and a corresponding selection of the Lagrangian multipliers. In this way it is possible to incorporate the orthonormalization conditions into the set of CPHF equations. Moreover, a new, advantageous procedure to determine the derivatives of the wavefunction with respect to the quasimomentum k is presented. We report calculations of the dipole moment, the polarizability ,, and the first hyperpolarizability , for different polymers (poly-HF, poly-H2O, trans-polyacetylene, polyyne, and polycarbonitrile) for different frequencies. These results are extensively compared with oligomer calculations. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 251,268, 2003 [source] |