The synthesis,X-ray crystal structure and optical properties of novel 1,3,5-triaryl pyrazoline derivatives

A series of novel 1,3,5-triaryl pyrazoline derivatives has been synthesized by the reaction of chalcone and 3-chloro-6-hydrazinylpyridazine in 47–82% yields. The structures of compounds obtained were determined by IR, ¹H NMR and HRMS spectra. Representatively, the spatial structure of compound 3d was determined by using X-ray diffraction analysis. Absorption and fluorescence spectral characteristics of the compounds were investigated in CHCl₃ by UV–vis absorption and emission spectra. The results showed that the absorption maxima of the compounds vary from 332 to 342 nm depending on the group bonded to benzene rings. The maximum emission spectra of compounds in CHCl₃ are dependent on groups in benzene ring in which a strong electron-donating group in benzene ring such as methoxyl group on C3 position of pyrazoline made the emission wavelength of 3e, 3f and 3g red shifted than that of compounds 3b, 3c and 3d with chlorine group. The intensity of absorption and fluorescence was also correlated with substituent on two aryl rings. In addition, the absorption spectra of these compounds change very little with increasing solvent polarity.     

L-alaninium perrhenate: crystal structure and non-linear optical properties

The crystal structure and non-linear optical properties of L-alaninium perrhenate, C₃H₈NO²⁺ ReO₄ ^?, are reported. The protonated amino acid and the perrhenate anion have their usual geometries. The three-dimensional hydrogen-bonded network can be seen as a stacking of layers parallel to the (100) planes. Each layer is formed by chains of alternating positive and negative ions along the b and c axes. Hydrogen bonding of adjacent layers forms alternating chains along the a axis. A high damage threshold and a second-harmonic generation efficiency three times that of KDP make this new material potentially useful in non-linear optics.      

Molecular and crystal structure of pyrylium squarylium dyes

The crystal structures of new dyes: 4-[[3-[[2,6-bis-(tert-butyl)-4H-pyran-4-ylidene]methyl]-2-oxido-4-oxo2-cyclobuten-]-ylidene]methyl]2,6-bis(tert-butyl)pyrylium (I) and its thio analog (II) were determined. Crystal data: space group P1 (I), P2₁/n (II); a = 5.960(9) Å (I), 10.400(4) Å (II); b = 9.366(3) Å (I), 12.242(4) Å (II); c = 13.948(3) Å (I), 14.482(6) Å (II); α = 70.43(2)° (I), 90.0° (II); ß = 84.82(9)° (I), 94.65(3)° (II); γ = 79.10(9)° (I), 90.0° (II); V = 720.0 ų (I), 1837.7 ų (II); Z = I (I), 2 (II); d_calc = 1.131 g/cm³ (I), 086 g/cm³ (II); R1(F) 0.049 (I), 0.045 (II). The substituents are trans-oriented relative to the planar 4-membered ring. Bond length distribution points to a considerable electron density delocalization over the whole molecule except the Bu^t groups. The pyrane rings are oriented differently relative to the central group; in II the rings lie in the same plane which is rotated through 7.7° with respect to the central fragment, whereas in I they lie in parallel planes which are 1.38 Å apart and deviate from the central fragment to opposite sides, forming with it dihedral angles of 12.8°. These conformational differences are possibly the result of the action of crystal field forces. In I molecules are arranged as overlapping stacks, whereas in II the pairwise parallel dye molecules are oriented in such a way that their long molecular axes are perpendicular to the long axes of the neighboring pair, resulting in a herringbone packing.     

Molecular and crystal structure of pyrylium squarylium dyes

The crystal structures of new dyes: 4-[[3-[[2,6-bis-(tert-butyl)-4H-pyran-4-ylidene]methyl]-2-oxido-4-oxo2-cyclobuten-]-ylidene]methyl]2,6-bis(tert-butyl)pyrylium (I) and its thio analog (II) were determined. Crystal data: space group P1 (I), P2₁/n (II); a = 5.960(9) ? (I), 10.400(4) ? (II); b = 9.366(3) ? (I), 12.242(4) ? (II); c = 13.948(3) ? (I), 14.482(6) ? (II); α = 70.43(2)° (I), 90.0° (II); ? = 84.82(9)° (I), 94.65(3)° (II); γ = 79.10(9)° (I), 90.0° (II); V = 720.0 ?³ (I), 1837.7 ?³ (II); Z = I (I), 2 (II); d_calc = 1.131 g/cm³ (I), 086 g/cm³ (II); R1(F) 0.049 (I), 0.045 (II). The substituents are trans-oriented relative to the planar 4-membered ring. Bond length distribution points to a considerable electron density delocalization over the whole molecule except the Bu^t groups. The pyrane rings are oriented differently relative to the central group; in II the rings lie in the same plane which is rotated through 7.7° with respect to the central fragment, whereas in I they lie in parallel planes which are 1.38 ? apart and deviate from the central fragment to opposite sides, forming with it dihedral angles of 12.8°. These conformational differences are possibly the result of the action of crystal field forces. In I molecules are arranged as overlapping stacks, whereas in II the pairwise parallel dye molecules are oriented in such a way that their long molecular axes are perpendicular to the long axes of the neighboring pair, resulting in a herringbone packing. Translated fromZhurnal Strukturnoi Khimii, Vol. 41, No. 4, pp. 781-787, July-August, 2000     

X-ray crystal structure of trimethylsilylmethyllithium

The solid state structure of trimethylsilylmethyllithium has been determined by single crystal X-ray diffraction techniques. The compound crystallizes in the monoclinic system, space group P2₁/n. Cell dimensions were determined as follows: a 10.931(3), b 18.397(6), c 21.490(8) Å, β 96.0(2)°, V 4298(2) ų, Z = 4, and a final R_f 5.1% based on 2203 data with σ(I) ≥ 2.5σ(I). The compound is formed by hexameric units, {LiCH₂Si(CH₃)₃}₆, with two distinct classes of LiLi distances of 2.46 and 3.18 Å. There are also two LiC distances av 2.20 and 2.27 Å. The LiH distances to the methylene H atoms have been determined and are short varying between 2.0 and 2.3 Å to the closest lithium atom. The structure, including possible LiH interactions, is discussed and compared with the other known hexameric aggregates.     

Single crystal structure and magnetic properties of MnSbS2Cl

The new compound MnSbS₂Cl was synthesised from a mixture of MnS, MnCl₂ and Sb₂S₃ at 500 °C. Single crystal study indicates orthorhombic symmetry, space group Pnma (No. 62), with , , , and Z=4. The refinement converged to R=0.0374 and wR=0.0716 for 742 unique reflections and 32 parameters. The crystal structure of MnSbS₂Cl is isotypic with stibnite Sb₂S₃ and consists of waved layers of corner-sharing MnS₄Cl₂ octahedra along the a axis and edge-sharing octahedra along the b axis, which are separated by antimony atoms. MnSbS₂Cl susceptibility shows an antiferromagnetic behaviour below 40 K with an increase at about 23 K.     

Synthesis, crystal structure and optical limiting properties of some W---Se---Cu clusters

A nest-shaped cluster [(C₄H₉)₄N]₂[WOSe₃Cu₃Br_1.67Cl_1.33] (1) and a cage-shaped cluster [(C₄H₉)₄N]₃[WSe₄Cu₃Br₂Cl₂] (2) were synthesized and their structures were determined by single-crystal X-ray diffraction. It was found that cluster 1 showed better optical limiting properties under an 8 ns pulsed laser at 532 nm but poorer optical limiting properties under a 35 ps pulsed laser compared with its analogue [(C₄H₉)₄N]₂[MoOS₃Cu₃BrCl₂]. The influence of the peripheral ligands of the cluster to the optical limiting properties was also discussed.     

Single crystal X-ray structure determinations of the reaction products of cis- and trans-cyclohexanedicarboxylic anhydrides and methylhydrazine

The structures of two of the three isomeric products of the reactions between cis- and trans-cyclohexanedicarboxylic anhydrides and methylhydrazine were determined by single-crystal X-ray methods to ascertain their tautomeric forms and stereochemistries. One product was found to be cis-N-methylamino-1,2-cyclohexanedicarboximide and the other trans-hexahydro-2-methylcyclohexa[d]pyridazine-1,2-dione.     

Electrical and optical properties of some azo dyes

The dipole moments of six monoazo dyes were obtained from measurements of their static dielectric constants and refractive indices of dilute solutions in benzene and carbon tetrachloride at temperatures between 20°C and 40°C. Also their lightfastness and absorption spectra (λ_max) were measured.From the results obtained, it was found that there is a linear relationship between the dipole moment, lightfastness and maximum absorption (λ_max) of the monoazo dyes under investigation.     

Synthesis, crystal structure and non-linear optical properties of boronates derivatives of salicylideniminophenols

The condensation in one step of a series of salicylaldehydes and 2-amino-5-nitrophenol with 1-naphthylboronic acid, 2-naphthylboronic acid, and o-tolylboronic acid to give the corresponding boronates 1a-3a, 1b-3b and 1c-3d, is reported. The X-ray crystal structures of 1a, 2b and 3b allowed determining the α- and β-angle between the stilbene skeleton and the aryl or naphthylboronic fragments; these values are indicative of different conformations for the aryl moieties around the (B-C) boron-carbon bond which could potentially modulate the electronic properties on the boron stilbene compounds. All compounds were characterized by ¹H, ¹¹B and ¹³C NMR spectroscopy, UV, IR and mass spectrometry. Second- and third-order non-linear optical characterizations were also performed by EFISH and THG Maker Fringe techniques, respectively. Compounds 3a-3d containing an -N(Et)₂ donor group gave the best NLO response in second- and third-order.     

Synthesis, crystal structure and optical properties of BiMgVO5

The new vanadate BiMgVO₅ has been prepared and its structure has been determined by single crystal X-ray diffraction: space group P2₁/n, , , , β=107.38(5)°, wR₂=0.0447, R=0.0255. The structure consists of [Mg₂O₁₀] and [Bi₂O₁₀] dimers sharing their corners with [VO₄] tetrahedra. The ranges of bond lengths are 2.129-2.814 Å for Bi-O; 2.035-2.167 Å for Mg-O and 1.684-1.745 Å for V-O. V-O bond lengths determined from Raman band wavenumbers are between 1.679 and 1.747 Å. An emission band overlapping the entire visible region with a maximum around 650 nm is observed.     

Correlating the crystal structure of a thiol-protected Au25 cluster and optical properties

The total structure determination of thiol-protected Au clusters has long been a major issue in cluster research. Herein, we report an unusual single crystal structure of a 25-gold-atom cluster (1.27 nm diameter, surface-to-surface distance) protected by eighteen phenylethanethiol ligands. The Au25 cluster features a centered icosahedral Au13 core capped by twelve gold atoms that are situated in six pairs around the three mutually perpendicular 2-fold axes of the icosahedron. The thiolate ligands bind to the Au25 core in an exclusive bridging mode. This highly symmetric structure is distinctly different from recent predictions of density functional theory, and it also violates the empirical golden rule "cluster of clusters", which would predict a biicosahedral structure via vertex sharing of two icosahedral M13 building blocks as previously established in various 25-atom metal clusters protected by phosphine ligands. These results point to the importance of the ligand-gold core interactions. The Au25(SR)18 clusters exhibit multiple molecular-like absorption bands, and we find the results are in good correspondence with time-dependent density functional theory calculations for the observed structure.     

Synthesis,crystal structure and non-linear optical properties of a new cyanide-containing compound

Reaction of K₃[Fe(CN)₆], NiCl₂ and diethylenetriamine (dien) resulted in the formation of a cyanide-containing heterometallic compound [Ni(dien)₂]₂[Fe(CN)₆]·4H₂O 1. The structure consists of two octahedral [Ni(dien)₂]²⁺ cations, one octahedral [Fe(CN)₆]^4? anion and four crystallization water molecules, which are held together by hydrogen-bonding interactions. Its TG curve exhibits two stages of mass loss. Compound 1 in DMF solutions has a very strong third-order non-linear optical (NLO) behavior with an absorption coefficient and refractive index α₂?=?1.10?×?10^?11?m?w^?1, n ₂?=??3.05?×?10^?19?m²?w^?1, respectively, and third-order NLO susceptibility χ⁽³⁾ 4.34?×?10^?13?esu.     

一种锰的超分子化合物的制备、结构及非线性光学 性质研究

用MnSO4·H2O,KSCN,六次甲基四胺(HMTA)制备出超分子化合物[Mn(NCS)2(H2O)2(HMTA)2][Mn(NCS)2(H2O)4](H2O)2,并测定了其晶体结构。该化合物由[Mn(NCS)2(H2O)2(HMTA)2],[Mn(NCS)2(H2O)4]和H2O三部分组成,每一个HMTA配体中仅有一个N原子与Mn原子配位,剩余的3个N分别与[Mn(NCS)2(H2O)4]中的H2O及结晶H2O之间形成氢键。[Mn(NCS)2(H2O)2(HMTA)2]和[Mn(NCS)2(H2O)4]之间通过N…H—O氢键边接成无限延伸的线性长链,链与链、以及链和结晶H2O之间通过七种形式的氢键构成三维结构的超分子。用Z-扫描法测定该化合物在DMF溶液中的三阶非线性光学性质,发现它具有自聚焦效应,三阶非线性折射系数n2=9.52×10^-9m^2·W^-1,非线性极化率χ^(3)=3.41×10^-12esu.     

Studies of third-order optical nonlinearities and optical limiting properties of azo dyes

In order to protect optical sensors and human eyes from debilitating laser effects, the intensity of the incoming laser light has to be opportunely reduced. Here, we report our results on the third-order optical nonlinearity and optical limiting properties of three azo dyes exposed to a 532nm continuous wave laser. We have observed low power optical limiting based on nonlinear refraction in our samples.     

Chemical degradation and X-ray crystal structure of rosaramicin

The X-ray crystal structure of rosaramicin is reported.     

A new type of liquid crystal involving hydrogen bonding: single crystal X-ray structure characterization and properties of the liquid crystal

A new liquid crystal involving hydrogen bonding between 4-hexyloxybenzoic acid and 4-octyloxylphenylethynylpyridine has been investigated by DSC, polarizing optical microscopy and X-ray diffraction. The mesogen shows a nematic phase and an unknown liquid crystalline phase. The liquid crystal crystallizes with a triclinic space group P-1 with the parameters: a = 8.879(2)Å, b = 10.137(2)Å, c = 17.629(4)Å; α = 104.16(3)°, β = 95.47(3)°, γ = 101.48(3)°; V = 1490.3(6)ų; Z = 2; F(000) = 572; μ = 0.076 mm^?1; λ(MoK_α) = 0.71073 Å; final R ₁ = 0.0435. The complex is formed by strong intermolecular hydrogen bonding.     

The relationship between the crystal structure and optical properties for isomeric aminopyridinium iodobismuthates

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