Orientational Order of Liquid-Crystalline 4-Alkyl-N-(p-cyanophenyl)piperidines by 2H and 13C NMR Spectroscopies

The orientational order of nematic 4-alkyl-N-(4-cyanophenyl) piperidines (I) has been determined from H-2 and C-13 NMR spectra. Molecular-order parameters are derived from the carbon-13 chemical shift of the cyano carbon atom in the nematic and the isotropic phases; the sign of the diamagnetic anisotropy is positive. Deuterium quadrupolar splittings from the partially deuterated piperidine ring of I are then related to various C-D bonds.

Photobehavior of crystalline 4-styrylcoumarin dimorphs: structure-reactivity correlations

4-Styrylcoumarin crystallizes from chloroform and hexane mixture in two morphologically different modifications. The monoclinic form (needles, P2(1)/c) undergoes stereospecific photodimerization producing anti head-to-tail dimer across pyrone double bond, whereas the triclinic modification (prisms, P ($) over bar 1) dimerizes yielding photodimer of the same configuration, but across styrenic double bond. Single crystal X-ray analyses of the dimorphs reveal the packing differences permitting rationalization of the regio- and stereochemistry of the photoproducts. The significantly low dimer yield from the prismatic crystals is rationalized.

Physical characterization of the organic nonlinear optical crystal � 3-methoxy 4-hydroxy benzaldehyde

We highlight our recent experimental work on an efficient molecular nonlinear optical crystal, 3-methoxy 4-hydroxy benzaldehyde (MHBA). Optical quality single crystals of MHBA were grown from mixtures of solvents and from melt. The overall absorption and transparency window were improved by growing them in a mixture of chloroform and acetone. The grown crystals were characterized for their optical transmission, mechanical hardness and laser damage. We have observed a strong correlation between mechanical properties and laser induced damage.

Synthon polymorphism and pseudopolymorphism in co-crystals. The 4,4 `-bipyridine-4-hydroxybenzoic acid structural landscape

Co-crystals of 4,4'-bipyridine and 4-hydroxybenzoic acid (1 : 2) show synthon polymorphism with the former being more stable. A 2 : 1 co-crystal is pseudopolymorphic within the same structural landscape with the structural roles of the two bipyridine N-atoms being distinct, as evidenced by mimicry by 4-phenylpyridine.

Synthesis based on cyclohexadienes: Part 10 synthesis of 5,5-dimethyl-7-methoxy-4-oxatricyclo[4.3.1.0]decan-2-ones

Synthesis of 5, 5-dimethyl- 7-methoxy-4 -oxatricyclo[4,3,1,0(3,7)]- decan-2-one 3a, a novel heterocyclic ring system present in morellin 1, and its 3-substituted derivatives 3b-e, is described from the Diels-Alder adducts 7, available from 1-methoxycyclohexa-1,4-dienes 4. Two routes, which involved the halocyclisation and the oxidative addition, were investigated for the conversion of the adducts 7 into 3. While the halocyclisation method resulted in mixtures, excellent yields of the target molecule were obtained by the second method. Solvolysis of the bromoether 9 resulted in a mixture of rearranged products 10, 13, 15 and 16.

Synthesis of 5,5-Dimethyl-7-methoxy 4-oxatricyclo [4,3,1,03,7]decan-2-ones

Two new synthetic routes for the preparation of the title compound and its 3-substituted derivatives, a novel ring system present in morellin and other related natural products, are reported from the readily available dihydroanisoles.

Synthesis, Crystal Structure, and Magnetic Properties of a Ferromagnetically Coupled Angular Trinuclear Copper(11) Complex [Cu3(02CMe)4(bpy)s(HzO)](PF)62

The synthesis, X-ray crystal structure, and magnetic properties of an angular trinuclear copper(II) complex [Cu3(O2CMC)4(bpy)3(H2O)](PF6)2 (1), obtained from a reaction of Cu2(O2CMe)4(H2O)2 With 2,2'-bipyridine (bpy) and NH4PF6 in ethanol, are reported. Complex 1 crystallizes in triclinic space group P1BAR with a = 11.529(1) angstrom, b = 12.121(2) angstrom, c = 17.153(2) angstrom, alpha = 82.01(1)-degrees, beta = 79.42(1)-degrees, gamma = 89.62(1)-degrees, and Z = 2. A total of 6928 data with I > 2.5sigma(I) were refined to R = 0.0441 and R(w) = 0.0557. The structure consists of a trinuclear core bridged by four acetate ligands showing different bonding modes. The coordination geometry at each copper is distorted square-pyramidal with a CuN2O2...O chromophore. The Cu...Cu distances are 3.198(1) angstrom, 4.568(1) angstrom, and 6.277(1) angstrom. There are two monoatomic acetate bridges showing Cu-O-Cu angles of 93.1(1) and 97.5(1)-degrees. Magnetic studies in the temperature range 39-297 K show the presence of a strong ferromagnetically coupled dicopper(II) unit (2J = +158 cm-1) and an essentially isolated copper(II) center (2J' = -0.4 cm-1) in 1. The EPR spectra display an axial spectrum giving g(parallel-to) = 2.28 (A(parallel-to) = 160 X 10(-4) cm-1) and g(perpendicular-to) = 2.06 (A(perpendicular-to) = 12 X 10(-4) cm-1) for the normal copper and two intense isotropic signals with g values 2.70 and 1.74 for the strongly coupled copper pair. The structural features of 1 compare well with the first generation models for ascorbate oxidase.

A Crystallization Technique For the Enantiomer Resolution of Conglomerates- (+/-)-4-Methoxyphenyl 1-Phenylethyl Ketone

The sorting of crystals of (+/-)-4-methoxyphenyl 1-phenylethyl ketone into its enantiomers is facilitated by crystallisation in a cellular grid made of filter paper.

Enantioselective Synthesis of Possible Diastereomers of Heptadeca-1-ene-4,6-diyne-3,8,9,10-tetrol; Putative Structure of a Conjugated Diyne Natural Product Isolated from Hydrocotyle leucocephala

Enantioselective synthesis of possible diastereomers of heptadeca-1-ene-4,6-diyne-3,8,9,10-tetrol, a structure proposed for the natural product isolated from Hydrocotyle leucocephala is accomplished. The reported spectral data of the natural product did not match those of any of the isomers that were synthesized and established that the structure proposed for the natural product is not correct and requires revision.

4-Hydroxy-6-(4-methoxyphenyl)-4-phenyl-1,3-diazinane-2-thione

In the title compound, C17H18N2O2S, the 1,3-diazinane-2-thione ring system is not coplanar with the benzene ring and methoxyphenyl ring system, the dihedral angle between the planes being 65.58 (13) and 89.18 (10)degrees, respectively. The crystal structure is characterized by intermolecular O-H...S, N-H...S, N-H...O and C-H...S hydrogen bonding.

Enantioselective synthesis of both (+)- and (-)-derivatives of bicyclo[4.3.0]nonan-8-one and 3,8-diones from R-carvone

Enantioselective synthesis of both the enantiomeric forms of the hydrindane derivatives mentioned in the title, potential chiral precursors in terpenoid synthesis, starling from R-carvone employing two different cyclopentannulation methodologies is described.

Exceptionally long crystal formation from 4-(3-bromopropyloxy)salicylaldehyde. X-ray crystallographic investigation

Unusually long (>14 cm) crystalline needles grow from 4-(3-bromopropyloxy)salicylaldehyde 1 presumably as a consequence of Br ... Br interactions; the powdered form of 1 shows one order of magnitude greater SHG activity realtive to urea.

Linear electro-optic effect and temperature coefficient of birefringence in 4-nitro-4script-methylbenzylidene aniline single crystals

A study of the linear electro?optic effect in single crystals of the organic compound, 4?nitro�4??methylbenzylidene aniline is reported. The reduced half?wave voltages have been found to have values 2.8, 1.3, and 1.1 kV at 632.8, 514.5, and 488.0 nm, respectively and the corresponding values of the largest linear electro?optic coefficient have been calculated. The thermal variation of the birefringence has also been investigated and the temperature variation of the refractive index difference is found to have the value, d?n/dT = 15.8 × 10?5 K?1.

Influence of poling methods on the orientational dynamics of 2-methyl-4-nitro-aniline in poly(methyl methacrylate) studied by second harmonic generation

The magnitude and stability of the induced dipolar orientation of 2-methyl-4-nitroaniline (MNA)/poly(methyl methacrylate) (PMMA) guest/host system is investigated. The chromophores are aligned using both the corona discharge and contact electrode poling techniques. The magnitude of order parameter (also an indicator for the second order nonlinear susceptibility) is measured by recording absorbances of the poled (by the two different techniques) and unpoled PMMA films at different concentrations of MNA. Under the same conditions the corona poling technique creates a higher alignment of molecules along the field direction. The time dependence of the second harmonic intensity of the MNA/PMMA film prepared by the two techniques can be described by a Kohlrausch-Williams-Watts stretched exponential. The temperature dependence of the decay time constant is found to generally follow a modified Williams-Landel-Ferry (WLF) or Vogel-Tamann-Fulcher (VTF) equation. The glass transition temperature seems to be the single most important parameter for determining the relaxation time tau(T).