Luminescence-detected phase transitions in lanthanide-containing liquid crystals

Complexes between lanthanide nitrates and a pro-mesogenic 18-membered diaza-substituted coronand are luminescent both as powders and liquid crystals (between 87 and 195 degrees C), and the phase transitions are detected by monitoring luminescence intensity and lifetime.     

A difluorosulfide as a Freon-free source of phosphonodifluoromethyl carbanion

The synthesis of difluoromethylphosphonates is becoming difficult due to environmental protective laws restricting the use of HCFCs and CFCs as starting chemicals. To circumvent this limitation, we report the preparation of a thioether as a new source of the lithiodifluoromethylphosphonate. This methodology avoiding the use of HCFCs involves a selective fluorination of sulfide followed by a thiaphilic addition of an organometallic reagent, which offers an alternative route to obtain phosphonodifluoromethyl carbanion. A contrasted reactivity, due to a medium effect, was also noted which allows addition of a wide range of electrophiles including nitroalkenes and DMF to thioethers.     

Stable lanthanide luminescence agents highly emissive in aqueous solution: multidentate 2-hydroxyisophthalamide complexes of Sm(3+), Eu(3+), Tb(3+), Dy(3+)

Efficient lanthanide (Ln) luminescent probes require good ligand-to-metal energy transfer and high aqueous stability. A family of ligands based on 2-hydroxyisophthalamide chelating units is reported. These form highly stable, eight-coordinate Ln complexes. Several of these (Ln = Sm, Eu, Tb, Dy) emit in the visible region with good ligand-to-lanthanide energy transfer. The absolute quantum yields of the two Tb complexes studies (Phi = 0.59, 0.61) and high absorbance make these the brightest luminescent probes for time-resolved detection; the emission spectrum of one complex can be seen down to 10-15 M. The low overlap of the four different Ln complexes enables their simultaneous detection and discrimination.     

Almost Connected Orders

One of the standard axioms for semiorders states that no three-point chain is incomparable to a fourth point. We refer to asymmetric relations satisfying this axiom as almost connected orders or ac-orders. It turns out that any relation lying between two weak orders, one of which covers the other for inclusion, is an ac-order (albeit of a special kind). Every ac-order is bracketed in a natural way by two weak orders, one the maximum in the set of weak orders included in the ac-order, and the other minimal, but not necessarily the minimum, in the set of weak orders that include the ac-order. The family of ac-orders on a finite set with at least five elements is not well graded (in the sense of Doignon and Falmagne, 1997). However, such a family is both upgradable and downgradable, as every nonempty ac-order contains a pair whose deletion defines an ac-order on the same set, and for every ac-order which is not a chain, there is a pair whose addition gives an ac-order.     

Electrochemical Synthesis of Trifluoromethane Sulfinic Acid Salt From CF3Br and SO2

The electroreduction of a mixture of SO₂ and CF₃Br in DMF, in an undivided cell with a soluble anode (Mg or Zn) lead to salt of trifluoromethane sulfinic acid in high yield.     

Access to new 4-fluorocyclohexa-2,5-dienimines using hypervalent iodine and pyridinium polyhydrogen fluoride

Nucleophilic para-fluorination of substituted anilines to afford 4-fluorocyclohexadieneimine derivatives is achieved in the presence of hypervalent iodine and pyridinium polyhydrogen fluoride.     

Convenient Preparation of Glycosyl Bromides

Glycosyl bromides were prepared in very good yields by bromination of the corresponding anomeric hydroxyl group using a 1:1 mixture of triphenyl phosphite and bromine as reagent.     

A Copper(I)-Catalyzed Sulfonylative Hiyama Cross-Coupling

An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO₂ molecule.