Structures, relative stability and dissociation of [Si,N,C,O]2+ isomers

Fifteen isomers of [Si,N,C,O]²⁺ system are obtained at UB3LYP/6-311G(d) and UCCSD(T)/6-311+G(2df) (single-point) levels. The analyses are made for predicting the structures of optimized isomers, while ionic fragments with lower energies are suggested. The calculated results indicate that linear isomer SiNCO²⁺(²Π) is thermodynamically the most stable species in [Si,N,C,O]²⁺ system, followed by linear SiOCN²⁺ (²Π), SiCNO²⁺ (²Π), and SiC(NO) (²A) with NCO three-membered ring. The order of stability of several kinetically stable isomers is SiNCO²> SiCNO²⁺ (²Π)>SiOCN²⁺>SiC(NO)²⁺>OSiNC²⁺ (²Π). The obtained results by analyzing the isomerizations and ionic fragment patterns show that the signal peaks of [Si,N,C,O]²⁺ are attributed to the contribution of linear SiNCO²⁺ species, which is metastable and can dissociate to the ionic fragments in the mass spectrometry experiments.     

具有双螺旋链的新型二维无机-有机骨架晶体材料Ni(PDC)(H2O)2的合成与结构

本文报道由H2PDC合成的新型维层状无机-有机骨架晶体Ni(PDC)(H2O)2(H2PDC=吡啶-2,5-二羧酸), 该化合物的一层是由右手螺旋Ni—O—C链与左手螺旋Ni-pdc链组成, 而邻近的一层则是由左手螺旋Ni—O—C链与右手螺旋Ni-pdc链组成, 层与层之间通过氢键作用形成了三维超分子结构. 用ICP、TG、IR和X射线单晶衍射分析等手段对其结构进行表征.     

化学计量一级站量值传递工作及经验

介绍了国防科工委化学计量一级站为保证化学量值的准确与统一,在计量标准建立、标准物质研制、测量方法研究等方面所做的工作和经验。     

Tricarbonyl(dialkylamidocyclohexa-1,3-diene)iron: Preparation,Isomerization and Stereochemistry

The direct reaction of iron pentacarbonyl with diethylamidocyclohexadiene gave three isomeric tricarbonyliron complexes, 1, 2 and 3. Only 1 isomerized to give 2 under acidic conditions, whereas 3 remained unchanged. The chemical properties of the tricarbonyl(amidocyclohexadiene)iron complexes differed from those of the tricarbonyl(carboxycyclohexadiene)iron complexes. Complex 3 which underwent no hydride abstraction with triphenylmethyl hexafluorophosphate, has an exo stereochemistry.     

Interlayer Energy Transfer from Naphthalene to Anthracene Chromophores Organized in Langmuir—Blodgett Films

Interlayer energy transfer between 2,3-naphthol-10-hexadecylaza-15-crown-5(NC16) and N-[1-(9-methoxyanthryl)] decylaza-15-crown-5(A10C) within multilayer Langmuir-Blodgett films has been studied by steady-state fluorescence spectra. The donor and acceptor could be separated precisely by inserting stearic acid (SA) spacers. The efficiency of the energy transfer increases with the decrease in the donor-acceptor distance by a quadratic manner, suggesting the donor excitations are delocalized in the layer.     

Synthesis and Characterization of (βDiketonate)(7-norbornadienyl acetate)Copper(l) Complexes,Single-Crystal Structure of (hfac)Cu(7-AcO-NBD)

Copper(I) complexes of general formula (β-diketonate)Cu(7-AcO-NBD), where 7-AcO-NBD = 7-norbornadienyl acetate and β-diketonate = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate (1), 1,1,1-trifluoro-2,4-pentanedionate (2), 2,4-pentanedionate (3), 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate (4), 4,4,4-trifluoro-1-phenyl-1,3-butanedionate (5), were prepared from reactions of CuCl with Na(β-diketonate) in the presence of 7-AcO-NBD. AH compounds were characterized by elemental analyses, ¹H, ¹³C, ¹⁹F NMR and IR spectra. Single-crystal strucutre of compound 1 was determined by X-ray diffraction analysis that showed a mononuclear copper species with coordination of a chelating β-diketonate ligand through two oxygen atoms and the 7-AcO-NBD through its C? C double bond and an oxygen atom in the solid state. For compound 1, the crystal data are: triclinic, space group $ {\rm P}\bar 1 $, a= 5.4519(14) Å, b= 11.852(3) Å, c= 13.304(3) Å, α = 74.721(20)° β = 80.220(20)°, γ= 76.848(19)°, Z = 2, R_F = 0.060 and R_w = 0.064. Hot-wall chemical vapor deposition experiments revealed that compound 1 is suitable as a precursor for deposition of copper films in the temperature range 170–260 °C.     

Palladium complexes with ethylene-bridged bis(N-heterocyclic carbene) for C-C coupling reactions

A series of new ethylene-bridged bis(imidazolium) halides with various N-substitutions were synthesized. Complexation of these imidazolium halides with Pd(OAc)₂ produced new Pd(II) ethylene-bridged bis(carbene) complexes. Crystallographic analyses of some of the new imidazolium salts and Pd(II) complexes were determined. Applications of these seven-member palladacycles in Suzuki and Heck coupling reactions produced comparable catalytic activities to those of six-member analogs.     

DIFFUSION OF LONG CHAINS THROUGH A POROUS THIN GEL NETWORK

Using a core(142 nm)made of linear polystyrene(PS)chains as a seed,we further polymerized a thin layer of cross-linked PS shell(7 nm)on it in water to form a core-shell particle.Such a particle swells in toluene,which enables linear PS chains inside the core to gradually diffuse out through the porous shell.Using a combination of static and dynamic laser light scattering,we examined the chain diffusion process by following the change of the scattering intensity(i.e.the average molar mass of the particles).For the first time,we have revealed that the diffusion exhibits three stages.In the first stage,the chain diffusion through the shell is even faster than their translational diffusion in a dilute solution.The three stages respectively correspond to the change of the solution in the core from concentrated to semidilute and then from semidilute to dilute.