Lanthanide SMMs Based on Belt Macrocycles: Recent Advances and General Trends

Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed.     

A constructive characterization of the split closure of a mixed integer linear program

Two independent proofs of the polyhedrality of the split closure of mixed integer linear program have been previously presented. Unfortunately neither of these proofs is constructive. In this paper, we present a constructive version of this proof. We also show that split cuts dominate a family of inequalities introduced by Köppe and Weismantel.     

Structural manipulation of pyrochlores: Thermal evolution of metastable Gd2(Ti1−yZry)2O7 powders prepared by mechanical milling

The structural and microstructural characteristics of metastable Gd₂(Ti_1−yZr_y)₂O₇ powders prepared by mechanical milling have been studied by a combination of XRD and Raman spectroscopy. Irrespective of their Zr content, as-prepared powder phases present an anion-deficient fluorite-type of structure as opposed to the pyrochlore equilibrium configuration obtained for the same solid solution by other synthetic routes. These fluorites are stable versus thermal activation, at least up to temperatures of 800 °C. For the Ti-rich compositions, thermal treatments at higher temperatures facilitate the rearrangement of the cation and anion substructures and the relaxation of mechanochemically induced defects whereas for compositions with high Zr content, the fluorite crystal structure is retained even at temperatures as high as 1200 °C. Interestingly enough, transient pyrochlores showing a very unusual cation distribution were observed during the thermally induced defect-recovery process.     

An alternative approach for non-linear optimal control problems based on the method of moments

We propose an alternative method for computing effectively the solution of non-linear, fixed-terminal-time, optimal control problems when they are given in Lagrange, Bolza or Mayer forms. This method works well when the nonlinearities in the control variable can be expressed as polynomials. The essential of this proposal is the transformation of a non-linear, non-convex optimal control problem into an equivalent optimal control problem with linear and convex structure. The method is based on global optimization of polynomials by the method of moments. With this method we can determine either the existence or lacking of minimizers. In addition, we can calculate generalized solutions when the original problem lacks of minimizers. We also present the numerical schemes to solve several examples arising in science and technology.     

Birefringent filter with amplitude beats

In this work, we show a very simple birefringent filter useful to modulate a broadband light spectrum. We first show the generation of various oscillating spectra using two identical multiple-order waveplates. In particular a sinusoidal broadband spectrum with a rapid oscillation is obtained. This spectrum is amplitude modulated by adding another waveplate to the system. This waveplate has a small phase shift, and with the proper orientation generates amplitude beats on the broadband spectrum. Finally, we show how this system can be voltage controlled by means of a ferroelectric liquid crystal modulator. We experimentally demonstrate this behavior with the aid of a portable spectrophotometer, and we provide a theoretical explanation on the basis of the Jones matrix formalism.