ChemInform Abstract: Synthesis and Single Crystal Structure of Sodium Octahydrotriborate,NaB3H8.

The title compound is prepared by a modified synthesis involving the reduction of BH₃·THF with Na dispersed on silica gel (-10 °C), removal of THF, and extraction by Et₂O.     

Solid-state coordination chemistry of the Cu/triazolate/X system (X = F-, Cl-, Br-, I-, OH-, and SO4(2-))

Hydrothermal reactions of 1,2,4-triazole with the appropriate copper salt have provided eight structurally unique members of the Cu/triazolate/X system, with X = F-, Cl-, Br-, I-, OH-, and SO4(2-). The anionic components X of [Cu3(trz)4(H2O)3]F2 (1) and [Cu6(trz)4Br]Cu4Br4(OH) (4) do not participate in the framework connectivity, acting as isolated charge-compensating counterions. In contrast, the anionic subunits X of [Cu(II)Cu(I)(trz)Cl2] (2), [Cu6(trz)4Br2] (3), [Cu(II)Cu(I)(trz)Br2] (5), [Cu3(trz)I2] (6), [Cu6(II)Cu2(I)(trz)6(SO4)3(OH)2(H2O)] (8), and [Cu4(trz)3]OH.7.5H2O (9.7.5H2O) are intimately involved in the three-dimensional connectivities. The structure of [Cu(II)Cu(I)(trz)2][Cu3(I)I4] (7) is constructed from two independent substructures: a three-dimensional cationic {Cu2(trz)2}n(n+) component and {Cu3I4}n(n-) chains. Curiously, four of the structures are mixed-valence Cu(I)/Cu(II) materials: 2, 5, 7, and 8. The only Cu(II) species is 1, while 3, 4, 6, and 9.7.5H2O exhibit exclusively Cu(I) sites. The magnetic properties of the Cu(II) species 1 and of the mixed-valence materials 5, 7, 8, and the previously reported [Cu3(trz)3OH][Cu2Br4] have been studied. The temperature-dependent magnetic susceptibility of 1 conforms to a simple isotropic model above 13 K, while below this temperature, there is weak ferromagnetic ordering due to spin canting of the antiferromagnetically coupled trimer units. Compounds 5 and 7 exhibit magnetic properties consistent with a one-dimensional chain model. The magnetic data for 8 were fit over the temperature range 2-300 K using the molecular field approximation with J = 204 cm(-1), g = 2.25, and zJ' = -38 cm(-1). The magnetic properties of [Cu3(trz)3OH][Cu2Br4] are similar to those of 8, as anticipated from the presence of similar triangular {Cu3(trz)3(mu3-OH)}(2+) building blocks. The Cu(I) species 3, 4, 6, and 9 as well as the previously reported [Cu(5)(trz)3Cl2] exhibit luminescence thermochromism. The spectra are characterized by broad emissions, long lifetimes, and significant Stokes' shifts, characteristic of phosphorescence.     

Superconductivity at Tc = 44 K in LixFe2Se2(NH3)y

We report a new approach to measuring the dielectric behavior of thin films by means of differential interdigitated electrode (IDE) cells coupled with a dual-channel impedance measurement setup. The differential IDE cell consists of two identical IDE??s on a common substrate. With one IDE loaded with sample and the other one empty, the complex permittivities of both capacitors are measured simultaneously by means of a dual-channel impedance measurement setup. The net dielectric response of the material under study is then obtained by the difference of the two permittivities, which corrects for the substrate contribution. The applicability of this approach is examined with bulk glycerol and a 600 nm indomethacin film and is evidenced by the results being consistent with those measured by conventional methods. The main advantages of this new approach include a simplified preparation technique for thin film samples and a straightforward correction for the substrate contribution by subtracting the empty IDE signal obtained at the same temperature and thermal history.     

Crystal-to-Crystal Transformation of Magnets Based on Heptacyanomolybdate(III) Involving Dramatic Changes in Coordination Mode and Ordering Temperature

Two for one: Two unusual magnets based on the [Mo(CN)(7) ](4-) building block with Mn(II) linkers have been prepared with different topological 3D networks. Conversion of one into the other is triggered by dehydration during a single-crystal to single-crystal event (see picture; Mn:?dark red, Mo:?pink, C:?green, N:?blue, O:?red).     

IR-spectroscopic characterization of acetophenone complexes with Fe+, Co+, and Ni+ using free-electron-laser IRMPD

The gas-phase complexes M(+)(acet)(2), where M is Fe, Co, or Ni and acet is acetophenone, were studied spectroscopically by infrared multiple-photon dissociation (IRMPD) supported by density functional (DFT) computations. The FELIX free electron laser was used to give tunable radiation from approximately 500 to 2200 cm(-1). The spectra were interpreted to determine the metal-ion binding sites on the ligands (oxygen (O) or ring (R)) and to see if rearrangement of the ligand(s) to toluene plus CO occurred. For Ni(+), O binding was found to predominate (similar to the previously studied Cr(+) case), with less than approximately 10% of R-bound ligands in the population. For Co(+), a roughly equal mixture of R-bound and O-bound ligands was present; based on the computed thermochemistry, the OR complex was considered likely to predominate. Fe(+) complexes appeared largely O-bound, but with clear evidence for some R-binding. The exceptionally large extent of R binding for Co(+) highlights the special affinity of this metal ion for aromatic ring ligands. In contrast, the predominant O binding for Ni(+) emphasizes the especially high metal-ion affinity of the O site of acetophenone compared with other ligands such as anisole where R binding of Ni(+) predominates. The spectra did not indicate significant intracomplex rearrangement of ligands to toluene plus CO, and in particular for the Co(+) case the absence of a metal-bound C triple bond O stretching peak near 2100 cm(-1) strongly ruled out such a rearrangement.     

乙酸铵离心交换法和乙酸钙离心交换法测定土壤阳离子交换量

土壤阳离子交换量(CEC)的测定在农业中有重要的意义,对农业行业标准NY/T295—1995和NY/T1121.5—2006中的离心交换法测定土壤中CEC值的方法进行了优化,讨论了不同pH值的土壤样品对两种方法的选择依据,分析了CEC值测定重现性较差的原因。结果表明,pH值的范围是方法选择的重要依据,pH7.0的样品适合用乙酸铵离心交换法,pH≥7.0的样品则适用乙酸钙离心交换法。优化后方法的准确度和精密度有了较大的改善,实验中对各步骤的优化缩短了约40%的操作时间,减少工作量,适合于批量样品的准确测定。