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101.
The heterodinuclear complex [LCuIIVIVO] 1 was synthesized by using a new unsymmetric dinucleating ligand based on 1,8-naphthalenediol, whereas the homodinuclear CuIICuII complex 2 has a bridging beta-diketimineamid unit. Here we report on the synthesis, molecular structures, and magnetic properties of 1 and 2. In the solid state, both complexes dimerize to tetranuclear entities 1(2) and 2(2). The intradimer interaction in both complexes is ferromagnetic because of the orthogonality of the magnetic orbitals (J12 = +45.6 cm(-1) in 1 and +4.8 cm(-1) in 2). The interdimer interaction in 1 is also ferromagnetic, giving a St = 2 ground state. 相似文献
102.
The following novel solvatochromic probes were synthesized: 2,6-dibromo-4-[(E)-2-(1-alkylpyridinium-4-yl)ethenyl] phenolate, where the alkyl groups are methyl, n-butyl, n-hexyl, and n-octyl, respectively. Solvatochromism of three of these probes (C(1), C(4), and C(8)) was studied in 36 protic and aprotic solvents. A modified linear solvation energy relationship has been applied to the data obtained at 25 degrees C. Correlation of (empirical) polarities with other solvent properties showed more dependence on lipophilicity than on basicity. A similar conclusion has been reached for a series of other solvatochromic indicators. Exceptions are those that carry acidic hydrogens, being biased toward solvent basicity. Thermosolvatochromism has been studied in mixtures of water with methanol, 1-propanol, acetonitrile, and DMSO. Thermosolvatochromic data have been treated according to a model that explicitly considers the presence in bulk solution of three "species": water, organic component, and solvent-water hydrogen-bonded aggregate. Solvation by the latter is favored over solvation by either of the two precursor solvents (aqueous DMSO is an exception). Temperature increase resulted in desolvation of the probes, due to concomitant decrease of the structures of the component solvents. The above-mentioned modified solvation equation has been successfully applied to solvatochromism in aqueous methanol and aqueous 1-propanol. 相似文献
103.
104.
Chen D Heberling MS Nakata M Hough LE Maclennan JE Glaser MA Korblova E Walba DM Watanabe J Clark NA 《Chemphyschem》2012,13(1):155-159
The B4 liquid crystal phase of bent-core molecules, a smectic phase of helical nanofilaments, is one of the most complex hierarchical self-assemblies in soft materials. We describe the layer topology of the B4 phase of mesogens in the P-n-OPIMB homologous series near the liquid crystal/glass interface. Freeze-fracture transmission electron microscopy reveals that the twisted layer structure of the bulk is suppressed, the layers instead forming a structure with periodic layer undulations, with the topography depending on the distance from the glass. The surface layer structure is modeled as parabolic focal conic arrays generated by equidistant parabolas whose foci are defect lines along the glass surface. Nucleation and growth of toric focal conics near the glass substrate is also observed. Although the growth of twisted nanofilaments, the usual manifestation of structural chirality in the B4 phase, is suppressed near the surface, the smectic layers are intrinsically chiral, and the helical filaments that form on top of them grow with specific handedness. 相似文献
105.
Zhu C Shao R Reddy RA Chen D Shen Y Gong T Glaser MA Korblova E Rudquist P Maclennan JE Walba DM Clark NA 《Journal of the American Chemical Society》2012,134(23):9681-9687
We report a bent-core liquid crystal (LC) compound exhibiting two fluid smectic phases in which two-dimensional, polar, orthorhombic layers order into three-dimensional ferroelectric states. The lower-temperature phase has a uniform polarization field which responds in an analog fashion to applied electric field. The higher-temperature phase is a new smectic state with periodic undulation of the polarization, structurally modulated layers, and a bistable response to applied electric field which originates in the periodically splay-modulated bulk of the LC rather than by surface stabilization at the cell boundaries. 相似文献
106.
Andreas Helmstedt Marc D. Sacher Aaron Gryzia Alexander Harder Armin Brechling Norbert Müller Ulrich Heinzmann Veronika Hoeke Erich Krickemeyer Thorsten Glaser Samuel Bouvron Mikhail Fonin 《Journal of Electron Spectroscopy and Related Phenomena》2012,184(11-12):583-588
X-ray absorption spectroscopy studies of the [MnIII6CrIII]3+ single-molecule magnet deposited as a microcrystalline layer on gold substrates are presented. The oxidation state of the manganese centers changes from MnIII to MnII due to irradiation with soft X-rays. The influence of the charge-neutralizing anions on the stability of [MnIII6CrIII]3+ against soft X-ray exposure is investigated for the different anions tetraphenylborate (BPh4?), lactate (C3H5O3?) and perchlorate (ClO4?). The exposure dependence of the radiation-induced reduction process is compared for [MnIII6CrIII]3+ with the three different anions. 相似文献
107.
Martins MA Rossatto M Prola LD Pizzuti L Moreira DN Campos PT Frizzo CP Zanatta N Bonacorso HG 《Ultrasonics sonochemistry》2012,19(2):227-231
The synthesis of 14 novel N-propargylic β-enaminones from the reaction of β-alkoxy vinyltrihalomethyl[carboxyethyl] ketones [R3C(O)CHC(R1)OMe, where R3 = CF3, CCl3, CO2Et and R1 = Me, Et, Pr, Bu, i-Pent, CH2CH2CO2Me] with propargyl amines [R2NHCH2CCH, where R2 = Pr, PhCH2] is reported. Yields, solvents and reaction times needed for reaction completion, by microwave irradiation (MW), conventional thermal heating (TH) and under ultrasound irradiation (US) are compared. The best results were obtained under US irradiation in good to excellent yields (70-93%). 相似文献
108.
Fabrina R.S. Bentlin Clarissa M.M. dos Santos Érico M.M. Flores Dirce Pozebon 《Analytica chimica acta》2012
This paper deals with the determination of the fourteen naturally occurring elements of the lanthanide series in red wine. Ultrasound (US) was used for sample preparation prior lanthanides determination using ICP-MS. Flow injection (FI) and pneumatic nebulization/aerosol desolvation were used for nebulization of aliquots of 50 μL of sample and its subsequent transportation to plasma. Sample preparation procedures, matrix interference and time of sonication were evaluated. Better results for lanthanides in red wine were obtained by sonication with US probe for 90 s and sample 10-fold diluted. The limits of detection of La, Ce, Nd, Sm, Gd, Pr, Eu, Tb, Dy, Ho, Er, Tm, Lu and Yb were 6.57, 10.8, 9.97, 9.38, 2.71, 1.29, 1.22, 0.52, 2.35, 0.96, 2.30, 0.45, 0.24 and 1.35 ng L−1, respectively. Red wines of different varieties from three countries of South America were discriminated according to the country of origin by means of multivariate analysis of lanthanides concentration. 相似文献
109.
Marija Matković Krešimir Molčanov Robert Glaser Kata Mlinarić-Majerski 《Tetrahedron》2012,68(42):8795-8804
2-(1-Adamantyl)-β-butyrolactones 3a and 3b were synthesized using very common peptide coupling reagents under mild conditions and their ring-opening reactions were then studied. These novel lactones showed pronounced stability and were resistant to cleavage upon acidic water extraction and column chromatographic purification. The adamantane moiety plays an important function in lowering the lactone reactivity by protecting the electrophilic sites on the four membered ring via steric hindrance. However under certain conditions, both O–C(carbonyl) and O–C(alkyl) bond-cleavage ring-opening reactions were observed. Bond-cleavage at physiological temperature makes these novel lactones especially noteworthy. Novel adamantyl-β-butyrolactones have a potential to act as biomembrane soluble amphiphiles that might exhibit a combination of stability and biological activity with the latter hopefully predominating. 相似文献
110.