New vanadium selenites: centrosymmetric Ca2(VO2)2(SeO3)3(H2O)2, Sr2(VO2)2(SeO3)3, and Ba(V2O5)(SeO3), and noncentrosymmetric and polar A4(VO2)2(SeO3)4(Se2O5) (A = Sr2+ or Pb2+)

Five new vanadium selenites, Ca(2)(VO(2))(2)(SeO(3))(3)(H(2)O)(2), Sr(2)(VO(2))(2)(SeO(3))(3), Ba(V(2)O(5))(SeO(3)), Sr(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), and Pb(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), have been synthesized and characterized. Their crystal structures were determined by single crystal X-ray diffraction. The compounds exhibit one- or two-dimensional structures consisting of corner- and edge-shared VO(4), VO(5), VO(6), and SeO(3) polyhedra. Of the reported materials, A(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)) (A = Sr(2+) or Pb(2+)) are noncentrosymmetric (NCS) and polar. Powder second-harmonic generation (SHG) measurements revealed SHG efficiencies of approximately 130 and 150 × α-SiO(2) for Sr(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)) and Pb(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), respectively. Piezoelectric charge constants of 43 and 53 pm/V, and pyroelectric coefficients of -27 and -42 μC/m(2)·K at 70 °C were obtained for Sr(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)) and Pb(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), respectively. Frequency dependent polarization measurements confirmed that the materials are not ferroelectric, that is, the observed polarization cannot be reversed. In addition, the lone-pair on the Se(4+) cation may be considered as stereo-active consistent with calculations. For all of the reported materials, infrared, UV-vis, thermogravimetric, and differential thermal analysis measurements were performed. Crystal data: Ca(2)(VO(2))(2)(SeO(3))(3)(H(2)O)(2), orthorhombic, space group Pnma (No. 62), a = 7.827(4) ?, b = 16.764(5) ?, c = 9.679(5) ?, V = 1270.1(9) ?(3), and Z = 4; Sr(2)(VO(2))(2)(SeO(3))(3), monoclinic, space group P2(1)/c (No. 12), a = 14.739(13) ?, b = 9.788(8) ?, c = 8.440(7) ?, β = 96.881(11)°, V = 1208.8(18) ?(3), and Z = 4; Ba(V(2)O(5))(SeO(3)), orthorhombic, space group Pnma (No. 62), a = 13.9287(7) ?, b = 5.3787(3) ?, c = 8.9853(5) ?, V = 673.16(6) ?(3), and Z = 4; Sr(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), orthorhombic, space group Fdd2 (No. 43), a = 25.161(3) ?, b = 12.1579(15) ?, c = 12.8592(16) ?, V = 3933.7(8) ?(3), and Z = 8; Pb(4)(VO(2))(2)(SeO(3))(4)(Se(2)O(5)), orthorhombic, space group Fdd2 (No. 43), a = 25.029(2) ?, b = 12.2147(10) ?, c = 13.0154(10) ?, V = 3979.1(6) ?(3), and Z = 8.     

Crystal structures of the nickel(II) and copper(II) complexes ofN,N′-bis(dehydroaceto)ethylenediimine

Summary The nickel(II) and copper(II) complexes ofN,N-bis(dehydroaceto) ethylenediimine are monomeric and hydrated. In both compounds, coordination occurs at the C(4) carbonyl of the dehydroacetic acid moiety. The Ni atom has square-planar geometry with a water molecule at a substantial distance away. Both structurally distinct Cu atoms have square-pyramidal geometry, the apical position of one being occupied by an oxygen atom of the C(2) carbonyl group in a neighbouring molecule, and that of the other by a water molecule which participates in hydrogen-bond formation.     

Knoevenagel condensation reaction in a membrane microreactor

A multi-channel membrane microreactor was fabricated and tested for Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate using Cs-exchanged faujasite NaX as the catalyst; the membrane microreactor achieves supra-eqiulibrium conversion at higher product purity.     

Synthesis of novel sulfur containing spirocyclic phosphoranes

The synthesis of new spirocyclic phosphoranes containing both sulfur and oxygen hetero atoms bonded to phosphorus is described.     

A simple method of four-jet analysis ine + e − annihilation

For four-jet events in electron-positron annihilation at center-of-mass energies of 30 GeV or higher, a simple procedure is described to determine all four jet axes and jet energies. The result is insensitive to missing particles such as neutrals and the required computer time is quite moderate.     

The scattering of hydrogen,deuterium, and the rare gases from silver (111) single crystals

The scattering of hydrogen, deuterium, and the rare gases from the (111) face of silver has been studied at ultrahigh vacuum. The surfaces were prepared by argon ion bombardment and high temperature annealing. Incident angles between 20° and 65° and surface temperatures between room temperature and 573°K have been investigated. The scattering data exhibit quasi-elastic scattering (He, H₂, D₂), inelastic scattering (Ne, Ar, Kr), and trapping dominated scattering (Xe). Identification of these scattering regimes correlates with D/kT_g and is consistent with similar data from Pt(111) and W(110). The separate effects of microscopic surface roughness and thermal roughening have been identified and thermal attenuation in the elastic regime correlated with dynamical interactions rather than thermal roughening. Trapping and rotational coupling are discussed. Comparison of the data with scattering from epitaxial (111) silver indicates that the epitaxial surfaces are significantly more disordered than the single crystal surfaces.     

Seeded high yield synthesis of short Au nanorods in aqueous solution

Short gold nanorods of average lengths ranging between 20 and 100 nm (with corresponding aspect ratios of 2 and 4) were synthesized in excellent yield (approximately 97%). These nanorods were characterized by dark-field microscopy, UV-visible spectrophotometry, and transmission electron microscopy. Temporal evolution of rod shape had also been followed by UV-visible spectrophotometry and transmission electron microscopy and indicates that the nanorods briefly increase in length, then increase slightly in width, as they grow. The effect of the synthetic parameters on the rod dimension and yield was explored to find out suitable conditions to produce short nanorods; short nanorods have both plasmon bands in the visible region of the spectrum, which is a valuable property for sensor applications.     

Self-assembly patterns formed upon solvent evaporation of aqueous cetyltrimethylammonium bromide-coated gold nanoparticles of various shapes

Gold nanocrystals of various shapes, which were produced in high yield in the presence of cetyltrimethylammonium bromide (CTAB), showed a range of two-dimensional self-assembly patterns upon drying from aqueous solution. The interparticle spacings were independent of the size and shape of the gold nanocrystals. Energy-dispersive X-ray analysis (EDAX) and Fourier-transform infrared (FTIR) spectroscopic studies revealed that the CTAB molecules adsorb onto surfaces of the gold nanocrystals in a bilayer or multilayer fashion, consistent with other groups' results. Zeta potential measurements showed that CTAB-coated nanocrystals were positively charged and the zeta potential remained almost the same upon two centrifugations and redispersion of the nanocrystals in deionized water, confirming the high stability of the surfactant-nanoparticle interaction. The nanocrystal shape strongly influenced the nature of the self-assembly patterns, in some cases in accord with theoretical predictions. CTAB is proposed as the medium for self-assembly, via interdigitation of its hydrophobic chains from adjacent nanocrystals for close contact, or via sharing a layer of counterions for larger inter-nanocrystal spacings.     

Harnessing sulfur and nitrogen in the cobalt(iii)-catalyzed unsymmetrical double annulation of thioamides: probing the origin of chemo- and regio-selectivity

An unconventional cobalt(iii)-catalyzed one-pot domino double annulation of aryl thioamides with unactivated alkynes is presented. Sulfur (S), nitrogen (N), and o,o′-C–H bonds of aryl thioamides are involved in this reaction, enabling access to rare 6,6-fused thiopyrano-isoquinoline derivatives. A reverse ‘S’ coordination over a more conventional ‘N’ coordination of thioamides to the Co-catalyst specifically regulates the formation of four [C–C and C–S at first and then C–N and C–C] bonds in a single operation, a concept which is uncovered for the first time. The power of the N-masked methyl phenyl sulfoximine (MPS) directing group in this annulation sequence is established. The transformation is successfully developed, building a novel chemical space of structural diversity (56 examples). In addition, the late-stage annulation of biologically relevant motifs and drug candidates is disclosed (17 examples). The preliminary photophysical properties of thiopyrano-isoquinoline derivatives are discussed. Density functional theory (DFT) studies authenticate the participation of a unique 6π-electrocyclization of a 7-membered S-chelated cobaltacycle in the annulation process.

A Co-catalyzed one-pot double annulation of sulfoximine bearing thioamides with alkynes for the synthesis of [6,6]-fused thiopyrano-isoquinolines is disclosed. The annulation involves a 6π-electrocyclization of 7-membered S-chelated cobaltacycle.