Metal atom dynamics in a charge transfer complex

Temperature-dependent ⁵⁷Fe Mössbauer spectroscopy over the interval 89 < T < 335 K has been used to study the detailed metal atom dynamics in the charge transfer complex (CT) decamethlferrocene-acenaphthenequinone. The quadrupole splitting, area ratio and recoil-free fraction parameters clearly reflect the phase transition (T_pt) at 257 K. The root-mean-square-amplitude of vibrations of the metal atom in the CT complex have been compared to that determined earlier for decamethyl ferrocene. The vibrational amplitudes are isotropic below T_pt but anisotropic above this temperature.     

Plasma and beam facility atomic oxygen erosion of a transition metal complex

Glassy residues of the complex bis(N,N-disalicylidene-1,2-phenylenediamino)zirconium(IV), Zr(dsp)₂, on glass slides were exposed to atomic oxygen in a plasma asher or an atomic beam facility for various amounts of lime in order to study the erosion process, determine the rate of erosion, and learn the chemical identity of the residue. The exposed films were characterized by weight loss, optical photography, profilometry, diffuse reflectance and total transmittance spectroscopy, scanning electron microscopy (SEM) with wavelength dispersive X-ray spectrometry (WDS), X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). Results indicate that these films erode much more slowly polyimide (Kapton) film under identical conditions, that the erosion is very nonuniform, and that zirconium dioxide is the predominant product after extended exposure. This complex is currently being evaluated as a polymer additive.     

Reversible mutarotation in a macrocyclic ytterbium complex

M40 is a four-fold symmetry macrocyclic ligand endowed with axial and central chiral elements, all of R configuration. It promptly binds late lanthanides (Yb(III) and Lu(III) ) yielding a negative helicity, as witnessed by NIR-electronic circular dichroism. In the course of a few hours, a new conformation of the complex takes over, which has opposite helicity and allows for a dynamic free-bound equilibrium. Upon slow solvent evaporation, the original conformation is retrieved and the whole dynamic process can be started again, as in a sandclock, allowing one to envisage applications as a time-marker chiral switch.     

Impedance spectroscopy analysis in a complex system: Sodium dodecyl sulfate solutions

Impedance measurements in the range 10–10⁷ Hz were carried out in water solutions of sodium dodecyl sulfate for concentrations below and above critical micellar concentration (cmc). The results were analysed using a series combination of two Voigt units, describing bulk and interface process and, additionally, an unexpected inductive one, problably due to inertial effects of an adsorbed layer of SDS molecules at the electrode. The interface processes, including the inductive one, show transition at a concentration somewhat below cmc.     

A caged lanthanide complex as a paramagnetic shift agent for protein NMR

A lanthanide complex, named CLaNP (caged lanthanide NMR probe) has been developed for the characterisation of proteins by paramagnetic NMR spectroscopy. The probe consists of a lanthanide chelated by a derivative of DTPA (diethylenetriaminepentaacetic acid) with two thiol reactive functional groups. The CLaNP molecule is attached to a protein by two engineered, surface-exposed, Cys residues in a bidentate manner. This drastically limits the dynamics of the metal relative to the protein and enables measurements of pseudocontact shifts. NMR spectroscopy experiments on a diamagnetic control and the crystal structure of the probe-protein complex demonstrate that the protein structure is not affected by probe attachment. The probe is able to induce pseudocontact shifts to at least 40 A from the metal and causes residual dipolar couplings due to alignment at a high magnetic field. The molecule exists in several isomeric forms with different paramagnetic tensors; this provides a fast way to obtain long-range distance restraints.     

Hydrogenolysis of cycloalkanes on a tantalum hydride complex supported on silica and insight into the deactivation pathway by the combined use of 1D solid-state NMR and EXAFS spectroscopies

Hydrogenolysis of cyclic alkanes is catalysed by [(triple bond)SiO)(2)Ta-H] (1) at 160 degrees C and leads to lower alkanes and cyclic alkanes including cyclopentane. The turnover number is correlated with the number of carbon atoms of the cyclic alkanes, and therefore while cycloheptane is readily transformed, cyclopentane does not give any product (<1 %). The mechanism of ring contraction probably involves carbene de-insertion as a key carbon-carbon bond-cleavage step. The reluctance of cyclopentane to undergo hydrogenolysis was further studied: under the reaction conditions cyclopentane reacts with 1 to give the corresponding cyclopentyl derivative [(triple bond)SiO)(2)Ta-C(5)H(9)] (13), which evolves towards cyclopentadienyl derivative [(triple bond)SiO)(2)Ta(C(5)H(5))] (14) according to both solid-state NMR and EXAFS spectroscopies. This latter complex is inactive in the hydrogenolysis of alkanes, and therefore the formation of cyclopentane in the hydrogenolysis of various cyclic alkanes is probably responsible for the de-activation of the catalyst by formation of cyclopentadienyl complexes.     

The unprecedented role of a Cu<Superscript>II</Superscript> cryptand in the luminescence properties of a Eu<Superscript>III</Superscript> cryptate complex

Abstract  A Eu^III cryptate complex constructed from a Cu^II cryptand with an L ^tBu ligand, [Eu^IIICu₂^II(L ^tBu)₂(NO₃)₃(MeOH)], and the corresponding Ca^II and Na^I cryptates, [Ca^IICu₂^II(L ^tBu)₂(NO₃)₂(MeOH)₂] and [Na^ICu₂^II(L ^tBu)₂(Me₂CO)](BPh₄), have been synthesized and characterized in order to shed light on the essential role of Cu^II in the luminescence of a Eu^III cryptate. The unprecedented role of a Cu^II cryptand makes it possible to produce lanthanide luminescence in a Eu^III cryptate complex and is successfully elucidated by comparison with the corresponding Ca^II and Na^I cryptates. Graphical abstract   Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.