Functional Carbazole Liquid‐Crystal Block Codendrimers with Optical and Electronic Properties

The synthesis and characterisation of a family of block codendrimers consisting of highly versatile mesogenic and carbazole‐containing 2,2‐bis(hydroxymethyl)propionic acid (bis‐MPA) dendrons are reported. The liquid‐crystal behaviour was investigated by means of differential scanning calorimetry, polarised‐light optical microscopy and X‐ray diffraction. Depending on the chemical structure of the constituent dendrons, the codendrimers show lamellar or columnar mesophases. On the basis of the experimental results, models both at the molecular level and in the mesophase are proposed. The physical properties of the block codendrimers derived from the presence of the carbazole moiety in their structure were investigated: photoluminescence in solution and in the mesophase, electrochemical behaviour and hole transport. Electrodeposition of carbazole dendrons afforded a globular supramolecular conformation in which the mesogenic molecular side plays a key role.     

Residual currents and corridor of flow in the Rio de la Plata

The Rio de la Plata is a large and shallow water body that discharges onto the Atlantic Ocean. The main driving forces for the river flow are the bathymetry, tides, the outflow from the Paraná and Uruguay rivers and the winds. A numerical model covering the entire river was set up with the objective of increasing our understanding of the hydrographical features and morphological dynamics in the Estuary. The simulations revealed a counter-clockwise residual circulation in the Samborombón Bay and an eastward net flow near the Uruguayan coast. The residual flow is forced by both the tides and the bathymetry. The residence time for the entire river ranges from 40 to 80 days. However, residence times above 120 days was found in the Samborombón Bay. Three corridors of flow have been identified.     

Systematic studies of positron production in heavy-ion collisions near the Coulomb barrier

We present the results obtained from systematic studies of positron creation for a series of heavy-collision systems, with united chargeZ _u =Z ₁ +Z ₂ ranging fromZ _u =164 (Pb + Pb) toZ _u =184 (U+U) at bombarding energies close to the Coulomb barrier, using the Orangeβ-spectrometer at GSI. For each collision system studied, the dominating continuous distributions due to quasiatomic and nuclear positron emission are determined accurately. This is essential in obtaining the characteristics of the still unexplained monoenergetic positron lines which appear in the energy range between 200 keV and 400 keV. Our results are compared with coupled-channels calculations for quasi-atomic positron creation. The latter describe quite well the global features of the measured spectra, but overestimate systematically their absolute values. From the comparison, a common normalization factor of about 0.75 can be established for the calculated spectra. In particular, the dependence onZ _u of the measured emission probabilities was found to follow a power law (∝Z _u ^195±1), in fair agreement with the theoretical prediction.     

Synthesis of the insect antifeedant CDE molecular fragment of 12-ketoepoxyazadiradione and related compounds

A diastereoselective synthesis of the model insect antifeedant 29 a CDE molecular fragment of 12-ketoepoxyazadiradione has been achieved in ten steps from indenone 9 in 44% overall yield. Several of the compounds obtained along the synthesis related to model compound 29 show significant antifeedant activity against Spodoptera littoralis and Spodoptera frugiperda.     

Crystal and molecular structure of thiamine monochloride

The crystal and molecular structure of thiamine monochloride (C₁₂H₁₇N₄OSCl) was determined by X-ray diffraction and refined to a finalR value of 0.042. The compound crystallizes in the monoclinic system, space groupP2₁/a, with cell constantsa=18.929(4),b=11.663(2),c=6.376(2) Å and=96.72(8)°. The thiamine molecule is anhydrous and unprotonated, and the torsion angles at the methylene carbon show that it possesses anF conformation. The dihedral angle value of 84.16(6)° between thiazolium and pyrimidine rings is in the normal range found for the thiamine withF conformation, protonated or not, hydrated or not. Thiamine therefore has the same conformation notwithstanding protonation or hydration, with the rings similarly oriented in all the crystal structures containing thiamine.     

The role of steric and electronic interactions in the stereocontrol of the asymmetric 1,3-dipolar reactions of 5-ethoxy-3-p-(S)-tolylsulfinylfuran-2(5H)-ones with diazoalkanes: theoretical calculations and experimental evidences

The addition of diazomethane and diazoethane to (5S,SS)- and (5R,SS)-5-ethoxy-3-p-tolylsulfinylfuran-2(5H)-ones (1a and 1b) and their 4-methylderivatives (2a and 2b) proceeded in almost quantitative yields and complete regioselectivity. The observed pi-facial selectivity is determined by the configurations at both C-5 and the sulfinyl group, the later being the most important. The syn adducts were almost exclusively obtained from 1a and 2a in apolar solvents but the pi-facial selectivity was strongly decreased in more polar solvents. On the other hand, the major adducts from 1b and 2b were the anti ones and such predominance was slightly increased with solvent polarity. The exo-selectivity was complete in all the cases except for the anti approach to compounds 2a (in polar solvents) and 2b. The role of the sulfinyl group in this behavior was inferred by comparison of these results with those obtained in reactions of diazoalkanes with 5-methoxyfuran-2(5H)-one (3). Steric interactions seem to be the main ones responsible for the observed exo selectivity of reactions with diazoethane, but electronic factors, which can be modulated by the solvent, are also significant in the pi-facial selectivity control. DFT computational methods are able to correctly predict the reactivity, regioselectivity, and pi-facial selectivity exhibited by 5-alkoxyfuranones as well as their changes with the solvent polarity. A C-H.O hydrogen bond, involving the oxygen atom of the 5-alkoxy group at dipolarophiles and the endo-hydrogen atom at dipoles, seems to play a key role in the electronic interactions influencing the stereochemical course of these reactions.     

Understanding the catalytic role of flexible chiral δ-amino alcohols: the 1-(2-aminoethyl)norbornan-2-ol model

An empiric first approach to the knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction. For this purpose, a selected small library of seven norbornane-based chiral ligands, bearing well-defined structural variations to allow a comparative study, that is, variation of the relative configuration and steric hindrance at the C(2), C(3) and/or C(7) norbornane positions, has been synthesized and probed in the mentioned test reaction. The experimental results obtained have been rationalized empirically using diastereomeric Noyori-like transition states, demonstrating that the conformational flexibility of the δ-amino-alcohol ligands, contrary to the more studied and rigid β-amino-alcohols, plays a crucial role on the catalytic behavior of such ligands (stereochemical sense and degree of the stereodifferentiation in the asymmetric process), which makes such structural factors, important for the improved design of new related chiral catalysts. In this sense, a robust crude empirical model for the prediction of the catalytic behavior of such δ-amino-alcohol-based ligands is proposed.     

Some palladium(II) and platinum(II) lead bonded complexes

Complexes of the type M(PPh₃)₂(PbPh₃)₂ [M = Pd, (Ia) and Pt, (Ib)] have been prepared by oxidative addition of hexaphenyldilead to M(PPh₃)₄. The compound Pt(PPh₃)₂(PbPh₃)₂, (Ib), slowly decomposes in dichloromethane to give cis-Pt(PPh₃)₂(PbPh₃)Ph, (II). which can also be obtained by treating (Ib) with the stoichiometric amount of LiPh. Reaction of Pt(PPh₃)₄ with hexamethyldidead gives the complex Pt(PPh₃)₂(PbMe₃)Me directly.The MPb bonds are easily cleaved by bromine, iodine and hydrogen bromide. The X-ray structure of (II) has been determined using three-dimensional counter data and refined by the least-square method (R = 0.07). The crystals are monoclinic a = 22.501, b = 10.502, c = 24.120 Å, β = 113.43°, space group P2₁/c with Z = 4. The complex exhibits a cis configuration, with the coordination around the platinum atom essentially square-planar: the PtPb and PtC(phenyl)bond lengths are 2.698(1) and 2.055(3)Å, respectively.     

Theoretical studies of stereoselectivities of intramolecular aldol cyclizations catalyzed by amino acids

The effects of different amino acid catalysts and substrate substituents on the stereoselectivity of the title reactions have been studied with the aid of density functional theory methods. Experimental data available in the literature have been compiled. B3LYP/6-31G(d) calculations match the general experimental trends and provide useful insights into the origins of the variations in stereoselectivities. Acyclic primary amino acids allow a greater conformational flexibility in the aldol transition states compared with proline. This makes them poorer enantioselective catalysts with triketone substrates with a methyl ketone side chain. The steric repulsion upon substitution at the terminal methyl group increases the energy difference between anti- and syn-chairs with primary amino acid catalysts and, consequently, the stereoselectivities. Proline, in contrast, is a poor catalyst for the latter reactions because the substituent's steric bulkiness raises the activation energy of the favored C-C bond-forming pathway.