From {Bi22O26} to chiral ligand-protected {Bi38O45}-based bismuth oxido clusters

The reaction of [Bi(22)O(26)(OSiMe(2)tBu)(14)] (1) in THF with salicylic acid gave [Bi(22)O(24)(HSal)(14)] (2) first, which was converted into [Bi(38)O(45)(HSal)(22)(OH)(2)(DMSO)(16.5)]·DMSO·H(2)O (3·DMSO·H(2)O) after dissolution and crystallization from DMSO. Single-crystal X-ray diffraction analysis and ESI mass spectrometry associated with infrared multi-photon dissociation (IRMPD) tandem MS experiments confirm the formation of the large and quite stable bismuth oxido cluster 3. The reaction of compound 2 with the butoxycarbonyl(BOC)-protected amino acids phenylalanine and valine (BOC-PheOH and BOC-ValOH), respectively, resulted in the formation of chiral [Bi(38)O(45)(BOC-AA)(22)(OH)(2)] (AA=deprotonated amino acid), as shown by a combination of different analytical techniques such as elemental analysis, dynamic light scattering, circular dichroism spectroscopy, and ESI mass spectrometry.     

205Tl NMR in the Cuprate Superconductor Tl2Ba2CaCu2O8−δ: Evidence for a pseudo spin gap

²⁰⁵Tl-NMR in Tl₂Ba₂Ca_n-1Cu_nO_8?δ for differentn and δ is reviewed. Forn=2,3 the²⁰⁵Tl spectra consist of two lines. The main line arises from Tl(1) in the TlO-layer whereas the defect line belongs to Tl(2) in the Ca-layers between the CuO₂-layers. The temperature dependent Knight shift of the Tl(2) (defect) line is caused by the hyperfine interaction with the CuO₂-layer and is strongly related to the oxygen content of the sample. We find quasipartticle behavior for the T1(2) line similar to the⁸⁹Y Knight shift in the YBa₂Cu₃O_6+δ system. In contrast the T1(1) line shows strong antiferromagnetic correlations with indication of pseudo spin gap opening above the superconducting transition temperatureT _c.     

Ueber einen neuen Aufsatz zum Gebrauche bei Stickstoffbestimmungen nach der Kjeldahl-Methode

Ohne Zusammenfassung     

Impurity spin dynamics in the classical Kondo system Cu: Fe. NMR relaxation of impurity neighbour nuclei

The correlation time τ_i of the impurity electronic spin in the Kondo system Cu:Fe has been measured over the temperature range 4.2 K?T?300 K (T_K=27.6 K) by means of NMR relaxation of impurity neighbour nuclei. τ_i being in the sub-picosecond region varies with temperatures as predicted by the model calculation of Götze and Schlottmann.     

Magnetic resonance experiments on the radical cation salt (fluoranthenyl)2+ PF6−. Correlation of proton-NMR,fluorine-NMR and ESR

The longitudinal relaxation rates of the protons and the fluorine were determined for the radical cation salt (fluoranthenyl)₂⁺PF₆^? as a function of the temperature. These data are compared with the temperature dependence of the pulsed ESR signal amplitude at the same Larmor frequency (44 MHz). Whereas the fluorines are relaxed mainly by the reorientational motion of the anions and by the interaction with fixed paramagnetic impurities, the protons are relaxed additionally above 150 K predominantly by highly mobile paramagnetic species, whose concentration could be determined directly via the signal amplitudes of the NMR and ESR signals in the same set up. The Pauli susceptibility χ_c^s = 3.1 ×10^?5 cm³/mole which is derived from this experiment and the Korringa relation (T_1H4^?)^?1 = constant of the proton relaxation leads to the assumption of a metal-like behavior of the salt above 183 K. The observation that the protons of the cation stacks, rather than the fluorines on the anions are relaxed by the mobile paramagnetic species favors the assumption of one-dimensional spin transport within the fluoranthenyl stacks, which is further supported by an ω^{$\text{?1}\text{2}$} dependence of T_1H^?1.     

Spinor behaviour of a double quantum transition in three-level systems

4π rotational symmetry (spinor behaviour) of a two-level subsystem, connected by a double quantum transition is demonstrated in the case of a spin-1 nucleus (deuterium).     

Spin-temperature oscillations in the spin-locking experiment

The non-markovian behaviour of coupled nuclear spins in the spin-locking experiment is investigated both experimentally and theoretically.     

Critical slowing down of fluctuations in squaric acid (H2C4O4) at the phase transition observed by 13C spin-lattice relaxation

Spin lattice relaxation T₁ of naturally abundant ¹³C nuclei in squaric acid was measured close to the antiferroelectric-paraelectric phase transition temperature T_c = 373 K. A rapid increase in $\text{1}\text{T}{}_1$ is observed close to T_c coming from above, which follows the power law $\text{1}\text{T}{}_1\text{～ ε}{}^{\mathrm{?1.4}}$ where $\text{ε =}\text{(T ? T}{}_{\mathrm{c}}\text{)}\text{T}{}_{\mathrm{c}}$. This behaviour is explained on the basis of the two-dimensional character of the fluctuations.