Tetrabenzoporphyrin and -mono-, - Cis -di- and tetrabenzotriazaporphyrin derivatives: Electrochemical and spectroscopic implications of meso CH Group replacement with nitrogen

Nonperipherally hexyl-substituted metal-free tetrabenzoporphyrin (2H-TBP, 1a) tetrabenzomonoazaporphyrin (2H-TBMAP, 2a), tetrabenzo-cis-diazaporphyrin (2H-TBDAP, 3a), tetrabenzotriazaporphyrin (2H-TBTAP, 4a), and phthalocyanine (2H-Pc, 5a), as well as their copper complexes (1b-5b), were synthesized. As the number of meso nitrogen atoms increases from zero to four, Îmax of the Q-band absorption peak becomes red-shifted by almost 100 nm, and extinction coefficients increased at least threefold. Simultaneously the blue-shifted Soret (UV) band substantially decreased in intensity. These changes were related to the relative electron-density of each macrocycle expressed as the group electronegativity sum of all meso N and CH atom groups, âχR. X-ray photoelectron spectroscopy differentiated between the three different types of macrocyclic nitrogen atoms (the Ninner, (NH)inner, and Nmeso) in the metal-free complexes. Binding energies of the Nmeso and Ninner,Cu atoms in copper chelates could not be resolved. Copper insertion lowered especially the cathodic redox potentials, while all four observed redox processes occurred at larger potentials as the number of meso nitrogens increased. Computational chemical methods using density functional theory confirmed 1b to exhibit a Cu(II) reduction prior to ring-based reductions, while for 2b, Cu(II) reduction is the first reductive step only if the nonperipheral substituents are hydrogen. When they are methyl groups, it is the second reduction process; when they are ethyl, propyl, or hexyl, it becomes the third reductive process. Spectro-electrochemical measurements showed redox processes were associated with a substantial change in intensity of at least two main absorbances (the Q and Soret bands) in the UV spectra of these compounds

Stabilising solutions to a class of nonlinear optimal state tracking problems using radial basis function networks

A controller architecture for nonlinear systems described by Gaussian RBF neural networks is proposed. The controller is a stabilising solution to a class of nonlinear optimal state tracking problems and consists of a combination of a state feedback stabilising regulator and a feedforward neuro-controller. The state feedback stabilising regulator is computed online by transforming the tracking problem into a more manageable regulation one, which is solved within the framework of a nonlinear predictive control strategy with guaranteed stability. The feedforward neuro-controller has been designed using the concept of inverse mapping. The proposed control scheme is demonstrated on a simulated single-link robotic manipulator

Structural Phase Transitions in EuC2EuC_2

Pure EuC(2), free of EuO impurities, was obtained by the reaction of elemental europium with graphite at 1673 K. By means of synchrotron powder diffraction experiments, the structural behavior was investigated in the temperature range from 10 to 1073 K. In contrast to former results, EuC(2) crystallizes in the ThC(2) type structure (C2/c, Z = 4) at room temperature. A tetragonal modification (I4/mmm, Z = 2) is only observed in a very small temperature range just below the transition to a cubic high-temperature modification (Fm3m, Z = 4) at 648 K. DTA/TG investigations confirm these results. According to Raman spectroscopy, EuC(2) contains C(2)(2-) ions (nu(C[triple bond]C) = 1837 cm(-1)). The divalent character of Eu is confirmed by the results of magnetic susceptibility measurements and (151)Eu Mossbauer spectroscopy. In these measurements a transition to a ferromagnetic state with T(C) = 15 K is observed, which is in reasonable agreement with literature data. Above T(C) EuC(2) is a semiconductor according to measurements of the electric resistivity vs temperature, again in contrast to former results. Around T(C) a sharp maximum of the electric resistivity vs temperature curve was observed, which collapses on applying external magnetic fields. The observed CMR effect (colossal magnetoresistance) is much stronger than that reported for other EuC(2) samples in the literature. These investigations explicitly show the influence of sample purity on the physical and even structural properties of EuC(2)

Charge fluctuations across the pressure-induced quantum phase transition in EuCu₂(Ge_1-xSi_x)₂

Pressurizing strategically selected compositions of the EuCu2(Ge1-xSix)(2) series affords an opportunity for gaining microscopic insight into the ground-state properties and interplay between magnetism and valence fluctuations across a quantum critical point. This is investigated by way of systematic Eu-151 Mossbauer spectroscopy measurements on x = 0 and x = 0.5 compositions in the series, pressurized up to 7 GPa including variable temperature scans in the range 300-4.2 K. In EuCu2Ge2 the temperature and pressure dependences of the hyperfine interaction parameters indicate that both the magnetic and divalent state, Eu nu+ where nu = 2, are stable up to 6-7 GPa, thus serving as a useful reference. Whereas in the x = 0.5 composition which initially involves Eu2+, collapse of the magnetically ordered state is onset at similar to 1.3 GPa and there is emergence of a nonmagnetic intermediate valence state coexisting with the magnetically ordered state. This regime of mixed states is a precursor of a quantum phase transition to a nonmagnetic homogeneous intermediate valence state nu similar to 2.45, across a quantum critical point at 3.6 GPa, suggesting a first-order phase transition. X-ray-diffraction pressure studies at 300 K up to 6 GPa of the x = 0.5 composition indicate there is no change in lattice symmetry from the tetragonal ThCr2Si2-type structure. There are also no obvious discontinuities in pressure dependences of the lattice parameters upon evolving through the quantum critical point at 3.6 GPa. Increasing pressure changes the starting Eu2+ valence monotonically, until the mean valence attains its largest value nu similar to 2.45 indicative of enhanced charge fluctuations at the quantum critical point and plateaus thereafter. High-pressure resistance measurements at low temperatures down to 40 mK near the quantum critical point reveal no evidence for superconductivity

Valence fluctuations of europium in the boride Eu₄Pd_29+xB₈

We synthesized a high-quality sample of the boride Eu4Pd29+xB8 (x = 0.76) and studied its structural and physical properties. Its tetragonal structure was solved by direct methods and confirmed to belong to the Eu4Pd29B8 type. All studied physical properties indicate a valence fluctuating Eu state, with a valence decreasing continuously from about 2.9 at 5 K to 2.7 at 300 K. Maxima in the T dependence of the susceptibility and thermopower at around 135 K and 120 K, respectively, indicate a valence fluctuation energy scale on the order of 300 K. Analysis of the magnetic susceptibility evidences some inconsistencies when using the ionic interconfigurational fluctuation (ICF) model, thus suggesting a stronger relevance of hybridization between 4f and valence electrons compared to standard valence-fluctuating Eu systems

Analyzing the Total Structural Intensity in Beams Using a Homodyne Laser Doppler Vibrometer

The total structural intensity in beams can be considered as composed of three types of waves: bending, longitudinal, and torsional. In passive and active control applications, it is useful to separate each of these components in order to evaluate their contribution to the total structural power flowing through the beam. In this paper, a twisted z-shaped beam is used in order to allow the three types of waves to propagate. The contributions of the structural intensity, due to these waves, are computed from measurements taken over the surface of the beam with a simple homodyne interferometric laser vibrometer. The optical sensor incorporates some polarizing optics, additional to a Michelson type interferometer, to generate two optical signals in quadrature, which are processed to display velocities and/or displacements. This optical processing scheme is used to remove the directional ambiguity from the velocity measurement and allows nearly all back-scattered light collected from the object to be detect. This paper investigates the performance of the laser vibrometer in the estimation of the different wave components. The results are validated by comparing the total structural intensity computed from the laser measurements, with the measured input power. Results computed from measurements using PVDF sensors are also shown, and compared with the non-intrusive laser measurements