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.     

Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

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.     

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.     

Multi-scale Young measures

We introduce multi-scale Young measures to deal with problems where multi-scale phenomena are relevant. We prove some interesting representation results that allow the use of these families of measures in practice, and illustrate its applicability by treating, from this perspective, multi-scale convergence and homogenization of multiple integrals.