Enantioenriched dihydropyrones from beta-lactone templates

[reaction: see text] Optically active 4-substituted 2-oxetanones provide conduits for preparing 2,3-dihydro-4H-pyrone heterocycles. Enantioenriched beta-lactones are prepared by asymmetric catalytic acyl halide-aldehyde cyclocondensation reactions. Hydrazone anion-mediated beta-lactone ring opening and ensuing cyclization-dehydroamination of the derived beta-ketohydrazone afford the desired dihydropyrones (68-81%). Optimized lactone ring-opening-cyclization reaction conditions render a variety of optically active 4-substituted-2-oxetanones as effective precursors to enantioenriched 2,3-dihydro-4H-pyrones.     

Cyclohexanecarboxamide

The title compound, C₇H₁₃NO, forms R²₂(8) N—H...O hydrogen‐bonded dimers and C4 N—H...O‐linked chains, which are further stabilized by a C—H...O interaction. The combination of these interactions results in a hydrogen‐bonded network parallel to (100), with a motif that can be described by the secondary graph set R⁴₆(16). The existence of the same hydrogen‐bonding motif in 1‐phenylcyclopentanecarboxamide and 1‐(2‐bromophenyl)cyclohexanecarboxamide [Lemmerer & Michael (2008). CrystEngComm, 10 , 95–102 indicates that replacing the H atom on position 1 with a more bulky group does not necessarily disrupt the observed hydrogen‐bonding pattern. The presence of a C—H...O interaction to stabilize the R⁴₆(16) network does, however, seem to be required. In addition, the title compound is isomorphous with a previously published structure of cyclopentanecarboxamide [Winter et al. (1981). Acta Cryst. B 37 , 2183–2185].     

CONTROLLING THE 3D NANOSCALE ORGANIZATION OF BULK HETEROJUNCTION POLYMER SOLAR CELLS

In this study,the three dimensional nanoscale organization in the photoactive layers of poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM) is revealed by transmission electron tomography.After annealing treatment,either at elevated temperature or during slow solvent evaporation,nanoscale interpenetrating networks are formed with high crystalline order and favorable concentration gradients of both components through the thickness of the photoactive layer.Such a tailored morphology acco...     

Surface orientation of 3,4,5-tris-substituted benzoic acid amphiphiles

Regarding the molecular orientation on flat substrates, thin films have been studied of a series of wedge-shaped molecules (3,4,5-tris-substituted benzoate-benzo crown ether compounds) consisting of a hydrophobic outer rim and a polar group at the thin end which form columnar mesomorphic and crystalline structures. For most substrates studied here, autophobic dewetting is demonstrated to be caused by the formation of a monomolecular adlayer in which the molecules are oriented normal to the substrate surface with the hydrophobic tails directed away from the substrate. For thick films, this adlayer is shown to cause an "in-plane" orientation of the axis of the columnar state. An ordered in-plane oriented adlayer is observed only for highly ordered pyrolytic graphite as the substrate. In this case, specific interactions with the substrate cause formation of a well-ordered 2D pattern that might favor homeotropic orientation of the columnar structures but has to be optimized by further structural variation. The structure of the adsorbed monolayer is elucidated by combining contact angle measurements, plasmon resonance spectroscopy, and optical and scanning tunneling microscopy.     

Synthesis and characterization of tris-methacrylated 3,4,5-tris

The synthesis of liquid crystalline 3,4,5-tris(11-methacryloylundecyl-1-oxybenzyloxy)benzoic acid, 2-methyl-(1,4,7,10,13-pentaoxacyclopentadecane)-3,4,5-tris[4-(11-methacryloylundecyl-1-oxy)benzyloxy] benzoate and its 1:1 complex with sodium triflate is described. The observed mesophases were identified, by polarized optical microscopy and contact preparation techniques, to be of hexagonal columnar disordered structure. The amphiphiles form lyotropic columnar phases in concentrated methacrylate solvents, while at low solute contents supramolecular organogels emerge.     

Self‐organization of liquid crystalline 3,4,5‐tris[(11‐methacryloyl‐undecyl‐1‐oxy)‐4‐benzyloxy]benzoates in low‐shrinkage methacrylate mixtures

Crystallization and supramolecular aggregation of 3,4,5‐tris[(11‐methacryloyl‐undecyl‐1‐oxy)‐4‐benzyloxy]benzoate (1), 2‐methyl‐(1,4,7,10,13‐pentaoxabenzocyclopentadecane)‐3,4,5‐tris[(11‐methacryloyl‐undecyl‐1‐oxy)‐4‐benzoxyloxy]benzoate (2) and its 1 : 1 sodium triflate complex (2a) are described in solutions of methacrylate monomers. Formation of gels and subsequent polymerization yielded “supramolecular interpenetrating networks” consisting of an isotropic polymethacrylate resin, percolated by supramolecular aggregates of the solute, which are covalently connected to the resin phase. Compound 1 formed whisker‐type crystals, while 2 self‐organizes in networks of elongated supramolecular fibrils with diameters corresponding to the twofold length of one molecule. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 631–640, 2000     

Luminescence-Based Oxygen Sensors: ReL(CO)3Cl and ReL(CO)3CN Complexes on Copolymer Supports

A new class of luminescent rhenium complexes has been tested as oxygen sensors based on luminescent quenching. ReL(CO)₃Cl and ReL(CO)₃CN (L = 2,2-bipyridine or 1,10-phenanthroline and substituted analogues) have several features that seem to indicate suitability as oxygen sensors. These include simple synthesis, long excited-state lifetimes, and high luminescence quantum yields. Intensity and lifetime oxygen quenching measurements were used to study the complexes in various polymer supports including homopolymers of PDMS (polydimethylsiloxane), a methacryloxy containing PDMS (Gp-163), and trimethylsilylmethylmethacrylate (T3642), and copolymers containing Gp-163 and T3642. In contrast to previous studies utilizing [Ru(4,7-diphenyl-1,10-phenanthroline)₃]²⁺ as an oxygen sensor, quenching of the Re complexes proved much more sensitive to the polymer support. With suitable supports, the rhenium chloro complexes demonstrated significant quenching; but the cyano complexes, in spite of being robust in solution, exhibited severe photochemical instability in polymers. The potential of this class of complexes as oxygen sensors and as molecular probes as well as the ramifications in the design of new and different types of sensors is discussed.