Caging the mercurous ion: a tetradentate tripodal nitrogen ligand enhances stability and J(1H199Hg)

The dimeric mercurous ion has been encapsulated by a pair of the tetradentate tripodal nitrogen ligands tris[(2-(6-methylpyridyl))methyl]amine (TLA). The complex [Hg₂(TLA)₂](ClO₄)₂ (1) was isolated directly from an acetonitrile solution of Hg(ClO₄)₂ 3H₂O and TLA. Complex 1 crystallizes in the triclinic space group with a = 10.537(2) Å, b = 10.751(2) Å, c = 10.907(2) Å, = 75.20(3), = 73.73(3), = 75.73(3), and Z = 1. The cation is located an inversion center. The Hg–Hg and Hg–N_amine bond distances are 2.5469(8) and 2.297(6) Å, respectively, and the average Hg–N_pyridyl bond length is 2.75(7) Å. Complex 1 was stable indefinitely in acetonitrile-d ₃ solution, permitting detection of 13 and 22 Hz heteronuclear couplings between the Hg(I) ions and the methylene protons of the ligand. Comparisons with the structures and spectroscopic properties of related mercuric and mercurous complexes are made.     

The ESR spectra of Mn<Superscript>2+</Superscript> ions and the low-temperature NQR spectra of <Superscript>175</Superscript>Lu in LuNbO<Subscript>4</Subscript> crystals

The electron-spin resonance spectra of Mn²⁺ ions and nuclear-quadrupole resonance spectra of ¹⁷⁵Lu are investigated to find out the possibility of implementing the technique of dynamic alignment of nuclei using LuNbO₄ single crystals doped with Mn²⁺. An estimate for the electron-spin resonance frequency of Mn²⁺ ions is obtained, and the temperature dependences of the quadrupole coupling constant eQq and the anisotropy parameter that characterizes the asymmetry of the electric field gradient at ¹⁷⁵Lu nuclei are studied. It is demonstrated that LuNbO₄ single crystals doped with Mn²⁺ ions can be used as working media in experiments on dynamic alignment of nuclei.     

Effects of alkaline earth metal ion complexation on amino acid zwitterion stability: results from infrared action spectroscopy

The structures of isolated alkaline earth metal cationized amino acids are investigated using infrared multiple photon dissociation (IRMPD) spectroscopy and theory. These results indicate that arginine, glutamine, proline, serine, and valine all adopt zwitterionic structures when complexed with divalent barium. The IRMPD spectra for these ions exhibit bands assigned to carboxylate stretching modes, spectral signatures for zwitterionic amino acids, and lack bands attributable to the carbonyl stretch of a carboxylic acid functional group. Structural and spectral assignments are strengthened through comparisons with absorbance spectra calculated for low-energy structures and the IRMPD spectra of analogous ions containing monovalent alkali metals. Many bands are significantly red-shifted from the corresponding bands for amino acids complexed with monovalent metal ions, owing to increased charge transfer to divalent metal ions. The IRMPD spectra of arginine complexed with divalent strontium and barium are very similar and indicate that arginine adopts a zwitterionic form in both ions. Calculations indicate that nonzwitterionic forms of arginine are lowest in free energy in complexes with smaller alkaline earth metal cations and that zwitterionic forms are preferentially stabilized with increasing metal ion size. B3LYP and MP2 calculations indicate that zwitterionic forms of arginine are lowest in free energy for M = Ca, Sr, and Ba.     

Nonergodicity in electron capture dissociation investigated using hydrated ion nanocalorimetry

Hydrated divalent magnesium and calcium clusters are used as nanocalorimeters to measure the internal energy deposited into size-selected clusters upon capture of a thermally generated electron. The infrared radiation emitted from the cell and vacuum chamber surfaces as well as from the heated cathode results in some activation of these clusters, but this activation is minimal. No measurable excitation due to inelastic collisions occurs with the low-energy electrons used under these conditions. Two different dissociation pathways are observed for the divalent clusters that capture an electron: loss of water molecules (Pathway I) and loss of an H atom and water molecules (Pathway II). For Ca(H(2)O)(n)(2+), Pathway I occurs exclusively for n >or= 30 whereas Pathway II occurs exclusively for n 相似文献   

昆虫信息素研究III: 拟蚜虫警戒素的研究

合成了一系列碳数为十五和十四的倍半萜类蚜虫警戒素,并进行了生物活性测定,从中筛选有效化合物.