Novel Copolymers of Styrene. 16. Halogen Ring-Disubstituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

Electrophilic trisubstituted ethylenes, ring-disubstituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂CH₃, where R is 2,5-dichloro, 3,5-dichloro, 2,3-difluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro, 2-chloro-5-nitro, and 2-chloro-6-nitro were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and methyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r₁) for the monomers is 4-Cl-3-F (4.87) > 2,3-F₂ (4.49) > 3-Cl-4-F (3.50) > 3-Cl-2-F (2.96) > 2-Cl-5-NO₂ (2.02) > 2,5-Cl₂ (1.54) > 2-Cl-6-NO₂ (1.00) > 3,5-Cl₂ (0.41). Relatively high T_g of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500ºC range with residue (1.5–34.5% wt), which then decomposed in the 500-800ºC range.     

Atomic and electronic structure of mixed and partial dislocations in GaN

Here we present a detailed study of mixed dislocations in GaN, in which the complexities of the atomic arrangement in the cores have been imaged directly for the first time using an aberration corrected scanning transmission electron microscope. In addition to being present as a full-core structure, the mixed dislocation is observed to dissociate into partial dislocations separated by a stacking fault only a few unit cells in length. The generation of this stacking fault appears to be impurity driven and its presence is consistent with theoretical predictions for dislocation dissociation in materials with hexagonal crystal symmetry.     

Magnetic alignment in nominally non-magnetic hexagonal metal hydrides: NMR

Powders of three hexagonal metal-hydrides or -deuterides are found to align in 4.4–8.3 T magnetic fields used for NMR. The field-alignment is unexpected, since all three systems have very small susceptibilities, as demonstrated by sharp NMR lines. The extent of alignment runs from nearly complete to barely detectable in ZrBe₂(H,D)_x, LuD₃, and YD₃, respectively. The preferred alignment direction in ZrBe₂(H,D)_x is with the crystallites’ c-axis perpendicular to B, while the c-axis and B tend to be parallel in LuD₃ and YD₃. The susceptibilities χ_|| and χ are determined from bulk magnetization measurements in aligned ZrBe₂H_1.4 powder. The alignment must be considered for proper analysis of NMR spectra in these and related materials.     

Evidence for 2D precursors and interdiffusion in the evolution of self-assembled CdSe quantum dots on ZnSe

The evolution of self-assembled CdSe quantum dots deposited on (and subsequently capped by) ZnSe was investigated on a series of samples grown by molecular beam epitaxy, with CdSe coverages from 0.5 to 2.6 monolayers. The samples were investigated by cross-sectional scanning transmission electron microscopy, as well as macro- and microphotoluminescence. The results clearly indicated a coexistence of 2D ZnCdSe platelets and 3D islands, showing clearly that the platelets act as precursors for the formation of the 3D islands.     

Zur Analyse der Baryumgruppe

Ohne Zusammenfassung     

A C2-symmetric analogue of dppf: synthesis and structures of the indenyl-diphosphine complex 1,3-(Ph2PSe)2(C9H6) and the racemic and meso isomers of the heterobimetallic complex Mo(CO)4(1-PPh2-η-C9H6)2Fe

The preparation, isolation and characterisation of 1,3-bis(diphenylphosphino)indene (1) from indene and chlorodiphenylphosphine is described. The reaction of 1 with selenium gives the diselenide adduct 1,3-bis(diphenylselenophosphino)indene (2) which was characterised crystallographically. Deprotonation of 1 and treatment with ferrous chloride gives the unstable tetraphosphine complex bis(1,3-bis(diphenylphosphino)indenyl)iron(II) (3). Complex 3 decomposes to the diphosphine complex bis(1-diphenylphosphinoindenyl)iron(II) (4) via replacement of one diphenylphosphine substituent per indenyl ligand by a hydrogen atom. Complex 4 was also prepared by treatment of two equivalents of 1-diphenylphosphinoindenide with ferrous chloride. The heterobimetallic complex tetracarbonyl(bis(1-diphenylphosphinoindenyl)iron(II))molybdenum(0) (5) was also prepared and crystal structures of both the meso (5a) and C₂-symmetric racemic (5b) isomers are reported.