Nickel(II) meso‐Hydroxyporphyrin Complexes Revisited: Palladium‐Catalysed Synthesis,Electronic Structures of Derived Oxy Radicals,and Oxidative Coupling to a Dioxoporphodimethene Dyad

We report the synthesis and characterisation of new examples of meso‐hydroxynickel(II) porphyrins with 5,15‐diphenyl and 10‐phenyl‐5,15‐diphenyl/diaryl substitution. The OH group was introduced by using carbonate or hydroxide as nucleophile by using palladium/phosphine catalysis. The NiPor?OHs exist in solution in equilibrium with the corresponding oxy radicals NiPor?O^.. The 15‐phenyl group stabilises the radicals, so that the ¹H NMR spectra of {NiPor?OH} are extremely broad due to chemical exchange with the paramagnetic species. The radical concentration for the diphenylporphyrin analogue is only 1 %, and its NMR line‐broadening was able to be studied by variable‐temperature NMR spectroscopy. The EPR signals of NiPor?O^. are consistent with somewhat delocalised porphyrinyloxy radicals, and the spin distributions calculated by using density functional theory match the EPR and NMR spectroscopic observations. Nickel(II) meso‐hydroxy‐10,20‐diphenylporphyrin was oxidatively coupled to a dioxo‐terminated porphodimethene dyad, the strongly red‐shifted electronic spectrum of which was successfully modelled by using time‐dependent DFT calculations.     

Enhanced local density of states at the Fermi level of the surface platinum in carbon-supported platinum particles by Nafion ionomer

¹⁹⁵Pt nuclear magnetic resonance (NMR) was employed to study the influence of Nafion ionomers (NIs), a common ingredient used as a proton conducting mediator and binder in a membrane-electrode-assembly (MEA) for proton exchange membrane fuel cells, on the local density of states at the Fermi surface (E_F-LDOS) of Pt/C catalysts. NIs were observed to increase the surface E_F-LDOS of Pt particles, thereby altering of the catalytic properties of metal particles. This correlates well with the reduction of fuel oxidation rates. Thus, ionomers decreasing the surface E_F-LDOS of Pt particles would be desirable. In addition, a new concept to interpret the surface E_F-LDOS was introduced and validated.     

A H NMR study on the complexation of tetraalkylammonium cations, mono and diprotonated amines, and amino acids with a derivatized cyclotetrachromotropylene in an aqueous solution

The derivatized cyclotetrachromotropylene host forms complexes of 1:1 host to guest stoichiometry with tetraalkylammonium cations and amino acids whereas complexes of 1:2 host to guest stoichiometry are formed with mono and diprotonated amines in an aqueous solution. Both electrostatic and hydrophobic interactions are involved in the complexation.     

Suppression of antiferromagnetic spin fluctuation in Zn-substituted YBa2Cu3O7

We have prepared Zn-substituted YBa₂Cu_3−xZn_xO₇ (YBCO, x=0.0–0.09) and performed ^63,65Cu nuclear quadrupole resonance (NQR) measurements for the plane site at 300 and 100 K as a function of Zn concentration. The substitutional effects are observed in resonant frequencies and linewidths of spectra, and relaxation times as well as in the superconducting transition temperature. The spin–lattice relaxation rate 1/T₁ is reduced for the higher Zn concentration and the reduction is more significant at 100 K. The ratio of ^63,65Cu spin–lattice relaxation rates suggests that a magnetic contribution due to the antiferromagnetic spin fluctuation becomes weak as the Zn concentration increases. These effects confirm that the antiferromagnetic spin fluctuation of Cu 3d spins is suppressed by the Zn substitution due to the absence of local moment at the zinc site.     

Zur Unterscheidung der Citronens?ure von Weinsteins?ure und Aepfels?ure

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Half-sandwich ruthenium(II) complexes containing 4-substituted aniline derivatives: structural characterizations and catalytic properties in transfer hydrogenation of ketones

Transition Metal Chemistry - Four half-sandwich Ru(II) complexes (1)–(4) with the general formulae [Ru(η6-p-cymene)(L)Cl2] were synthesized by the reaction of one equivalent of the...     

Phase transition and relaxation processes by 87Rb and 39K nuclear magnetic measurements of RbKSO4 single crystals

⁸⁷Rb and ³⁹K nuclear magnetic resonance (NMR) spectra of RbKSO₄ single crystals were measured at room temperature. ⁸⁷Rb central line has the angular dependences of second-order quadrupolar shifts. From these results, the quadrupole coupling constant and the asymmetry parameter were determined at room temperature. In addition, the spin–lattice relaxation rate, 1/T₁, and the spin–spin relaxation rate, 1/T₂, were measured as a function of temperature. The values of 1/T₁ for the ⁸⁷Rb and ³⁹K nuclei were found to increase with increasing temperature, and 1/T₁ was determined to be proportional to Tⁿ. Therefore, for the ⁸⁷Rb and ³⁹K nuclei, Raman processes with n=2 are more significantly in nuclear quadrupole relaxation than direct processes.