Approaches toward the synthesis of 2,5-disubstituted-1,3-thiazolidines

Synthetic approaches for new 2,5-disubstituted-1,3-thiazolidines are described. Steric and electronic effects of the N-substituent of the thiazolidine ring represent the major parameter in the rearrangement process. The nmr studies demonstrate that N-unsubstituted 2,5-disubstituted-1,3-thiazolidines exist as epimeric mixture, while the corresponding N-acetylated analogues exist as a conformer mixture.     

Noncommutative homology of some three-dimensional quantum spaces

We compute the Hochschild and cyclic homology of certain three-dimensional quantum spaces (type A algebras), introduced by Artin and Schelter. We show that the Hochschild homology is determined by the quasi-classical limit.     

The level structure of 114Cd from (n, γ) and (d,p) studies

Gamma rays and conversion electrons have been measured following thermal neutron capture in ¹¹³Cd using the crystal spectrometers GAMS and the β-spectrometer BILL at the High Flux Reactor of the ILL at Grenoble. Primary γ-rays following thermal and average resonance neutron capture at E_n = 2 keV and 24 keV were recorded at the High Flux Beam Reactor at the Brookhaven National Laboratory. The ¹¹³Cd(d, p)¹¹⁴Cd reaction was studied with the Q3D spectrograph at the Munich tandem accelerator. Combining all these experimental results an almost complete level scheme of ¹¹⁴Cd was constructed up to 3.3 MeV including 48 excited levels with spin and parity information. The level scheme is discussed in terms of particle-hole excitations across the Z = 50 closed shell coupled to collective states, as well as in an interacting boson configuration mixing scheme.     

Multilevel description of the Rh isotopes in the interacting boson-fermion model

We present a multilevel calculation within the framework of the interacting boson-fermion model (IBFM-1) of the odd-mass ^101–109Rh isotopes. We calculate both positive- and negative-parity states of the same hamiltonian, starting from the $\text{1g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$, $\text{2p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, $\text{2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$, $\text{lf}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ and $\text{2d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ single-particle orbitals. We discuss energy spectra, electromagnetic E2 transition rates and one-nucleon transfer properties. We also discuss the influence of the $\text{1f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ orbital on the one-nucleon transfer properties. The results of the calculation for the negative-parity states are compared with the results of the $\text{U(}\text{6}\text{12}$) supersymmetry scheme of the interacting boson model.     

Rational Design of Poly(2,7‐Carbazole) Derivatives for Photovoltaic Applications

A reliable model that can be used to estimate the electronic properties (i.e., the HOMO, LUMO, and band gap energies) of conjugated polymers would be a great tool for applications in organic electronics such as light‐emitting diodes, field‐effect transistors, and photovoltaic cells. Recently, poly(2,7‐carbazole) derivatives have shown promising results when used as an active donor layer in bulk heterojunction photovoltaic cells with power conversion efficiency exceeding 7%. By using a simple correlation between density functional theory (DFT) theoretical calculations performed on six model compounds (using the repeating unit) and experimental data from the six corresponding polymers, an accurate estimation of the HOMO energy level, the LUMO energy levels, and the band gap of several poly(2,7‐carbazole) derivatives was obtained. According to the theoretical data obtained for more than one hundred repeating units, fourteen new copolymers that can be used as p‐type materials in bulk heterojunction solar cells were selected and synthesized. Experimental data obtained from these materials were then used to refine the correlation between DFT and experimental data of poly(2,7‐carbazole) derivatives.

     

Diffusion Crosslinking Kinetics of Thermoset Polymers

The problem of the delayed crosslinking arising due to the diffusion of a crosslinker molecule from a vector particle within a thermoset polymer matrix is discussed. The crosslinker molecules, initially embedded in the vector particles, diffuse from the particle to the polymer matrix and react with the functional groups grafted to polymer chains. The two‐step diffusion crosslink kinetics is studied theoretically on the example of polyethylene functionalized with anhydride groups reacting with 1,4‐butanediol as a crosslinker molecule. This provides the independent of time limiting distribution functions of the concentration of crosslinks, unreacted and intermediate functional groups, which are shown to be rather sensitive to system parameters as rates of chemical reactions, ratio of diffusion coefficients of matrix to vector particles, stoichiometric composition of the reactive groups, etc. The nonmonotonic distribution of the crosslink concentration around the vector particles at certain range of the parameters is revealed.

     

Maharam's problem

We solve Maharam's problem [D. Maharam, An algebraic characterization of measure algebras, Ann. Math. 48 (1947) 154–167. [3]], also known as the Control Measure Problem. We construct a non-zero exhaustive submeasure on the algebra of clopen sets of the Cantor set that is not absolutely continuous with respect to a measure. To cite this article: M. Talagrand, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Photoinduced magnetism caused by charge-transfer excitations in tetracyanoethylene-based organic magnets

The photoinduced magnetism in Mn-tetracyanoethylene (TCNE) molecule-based magnets is ascribed to charge-transfer excitations from manganese to TCNE. Charge-transfer energies are calculated using density functional theory; photoinduced magnetization is described using a model Hamiltonian based on a double-exchange mechanism. Photoexciting electrons from the manganese core spins into the lowest unoccupied orbital of TCNE with photon energies around 3 eV increase the magnetization through a reduction of the canting angle of the manganese core spins for an average electron density on TCNE less than one. When photoexciting with a smaller energy, divalent TCNE molecules are formed. The delocalization of the excited electron causes a local spin flip of a manganese core spin.     

Synthesis, crystal structure and reactivity of uranium(IV) complexes with p-tert-butylcalix[4]arene ligands

Reactions of UCl4 with 25,27-dimethoxy-5,11,17,23-tetra-tert-butylcalix[4]arene (H2Me2calix) in THF or pyridine at 80 degrees C gave [UCl2(Me2calix)L2] [L = THF (1) or pyridine (2)]. Similar treatment of U(acac)(4) (acac = MeCOCHCOMe) with H2Me2calix in THF or pyridine afforded [U(acac)2(Me2calix)] (3). The bis-calixarene compound [U(Me2calix)(H2calix)] (4) was obtained by reaction of U(OTf)4 or U(OTf)3 with H2Me2calix in pyridine at 110 degrees C. Treatment of UCl4 with H2Me2calix in pyridine at 110 degrees C gave [Mepy][UCl2(Hcalix)(py)2] (5) resulting from demethylation and acid cleavage of the methoxy groups of the calixarene ligand of 2. Adventitious traces of air were responsible for the formation of [Hpy][Mepy]4[{UCl(calix)}3(mu3-O)][UCl6] (6) during the reaction of UCl4 and H2Me2calix, and of [{U(Me2calix)(mu3-O)LiCl(THF)}2] (7) during the reaction of 2 with tBuLi. The X-ray crystal structures of 1.2THF, 2.2py, 3.0.25L (L = THF and py), 4.2py, 5, 6.3py and 7.THF have been determined.