When high voltage is applied to distilled water filled into two glass beakers which are in contact, a stable water connection forms spontaneously, giving the impression of a floating water bridge. A detailed experimental analysis reveals static and dynamic structures as well as heat and mass transfer through this bridge.
Heating of 6-methylpyridazine-3-thione (HPn(Me)) and 6-tert-butylpyridazine-3-thione (HPn(tBu)) with potassium borohydride in diphenylmethane in a 3:1 ratio gave two new scorpionate ligands K[HB(Pn(Me))(3)] and K[HB(Pn(tBu))(3)]. Single crystal X-ray diffraction analysis of the methyl derivative K[HB(Pn(Me))(3)] revealed a dimeric species with one potassium atom coordinated by six sulfur atoms of two scorpionate ligands and a second potassium atom coordinated by three nitrogen atoms of one of the two ligands as well as by three water molecules. The reaction of K[HB(Pn(tBu))(3)] with nickel(II) chloride or cobalt(II) chloride in CH(2)Cl(2) led to the new boratrane compounds [M{B(Pn(tBu))(3)}Cl] (M = Ni 1, Co 3) where a formal reduction of the metal ions to Ni(I) and Co(I), respectively, and activation of the B-H bond occurred. Similar reactivity was observed by employing K[HB(Pn(R))(3)] (R = Me, tBu) and nickel(II) chloride in water. Reaction with cobalt(II) chloride in water also gave boratrane compounds [Co{B(Pn(R))(3)}(Pn(R))] (R = tBu 4, Ph 5), but instead of a chloride a bidentate pyridazinethionate ligand from a defragmentated scorpionate is found in the molecules. The molecular structures of all nickel and cobalt compounds were determined by single crystal X-ray diffraction analyses confirming the formation of boratranes in compounds 1-5. Magnetic measurements confirm the reduced oxidation states and the paramagnetic character of the Ni(I) and Co(I) complexes. Supportive DFT studies were carried out for a better understanding of the electronic nature of the metal-boron bond of the boratrane complexes.
When high voltage is applied to distilled water filled into two beakers close to each other, a water connection forms spontaneously, giving the impression of a floating water bridge (Fuchs et al 2007 J. Phys. D: Appl. Phys. 40 6112–4). This phenomenon is of special interest, since it comprises a number of phenomena currently tackled in modern water science. The build-up mechanism, the chemical properties and the dynamics of this bridge as well as related additional phenomena are presented and discussed.
Complexes featuring lanthanide silicon
bonds represent a research area still in its infancy. Herein, we report
a series of Cp-free lanthanide (+II) complexes bearing σ-bonded
silyl ligands. By reactions of LnI2 (Ln = Yb, Eu, Sm) either
with a 1,4-oligosilanyl dianion [K-Si(SiMe3)2SiMe2SiMe2Si(SiMe3)2-K)] (1) or with 2 (Me3Si)3SiK (3) the corresponding neutral metallacyclopentasilanes
({Me2Si(Me3Si)2Si}2)Ln·(THF)4 (Ln = Yb (2a), Eu (2b), Sm (2c)), or the disilylated complexes ({Me3Si}3Si)2Ln·(THF)3 (Ln = Yb (4a), Eu (4b), Sm (4c)), were selectively
obtained. Complexes 2b, 2c, 4b, and 4c represent the first examples of structurally
characterized Cp-free Eu and Sm complexes with silyl ligands. In both
series, a linear correlation was observed between the Ln–Si
bond lengths and the covalent radii of the corresponding lanthanide
metals. Density functional theory calculations were also carried out
for complexes 2a–c and 4a–c to elucidate the bonding situation between
the Ln(+II) centers and Si.
A new thermographic phosphor based on chromium(III)-doped yttrium aluminum borate (YAB) is obtained as single crystals by high temperature flux growth and as a microcrystalline powder via solution combustion synthesis. The phosphor is excitable both in the blue (λmax 422 nm) and in the red part of the spectrum (λmax 600 nm) and shows bright NIR emission. The brightness of the phosphor is comparable to that of a well-known lamp phosphor Mn(IV)-doped magnesium fluorogermanate. At ambient temperatures, the Cr(III)-doped YAB shows high temperature dependence of the luminescence decay time, which approaches 1% per deg. The material shows no decrease in luminescence intensity at higher temperatures. The new phosphor is particularly promising for applications in temperature-compensated optical chemosensors (including those based on NIR-emitting indicators) and in pressure-sensitive paints.
Glasses of composition (x − 1)PbOؒ(100 − x)GeO 2 ؒ1Ln 2 O 3 , with x = 30 mol% (Ln = Nd, Eu, Er), 40 mol% (Ln = Pr, Nd, Sm, Eu, Dy, Ho, Er, Tm), and 50 mol% (Ln = Eu, Er), have been prepared by quenching the oxidic melts. From the optical absorption and emission spectra in the ultravioletvisible-near-infrared (UV-VIS-NIR) region, the intensity parameters, spontaneous emission probabilities, branching ratios, radiative lifetimes, and, for selected NIR transitions, peak stimulated emission cross sections have been obtained. The trends observed in the intensity parameters have been discussed, as a function of the number of f electrons as well as a function of the lead content. As the amount of lead increases, the covalency of the Ln−O bond increases, the symmetry of the rare-earth site increases, and the dopant site distribution narrows. The peak stimulated emission cross sections rank among the highest found for oxide glasses.
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