Surface plasmons reveal spin crossover in nanometric layers

Nano-objects and thin films displaying molecular spin-crossover phenomena have recently attracted much attention. However, the investigation of spin crossover at reduced sizes is still a big challenge. Here we demonstrate that surface plasmon polariton waves propagating along the interface between a metal and a dielectric layer can be used to detect the spin-state changes in the latter with high sensitivity, even at the nanometer scale.     

Electron Transfer in the Cs⊂{Mn4Fe4} Cubic Switch: A Soluble Molecular Model of the MnFe Prussian‐Blue Analogues

A mixed‐valence {Mn^II₃Mn^IIIFe^II₂Fe^III₂} cyanide‐bridged molecular cube hosting a caesium cation, Cs?{Mn₄Fe₄}, was synthesized and structurally characterized by X‐ray diffraction. Cyclic‐voltammetry measurements show that its electronic state can be switched between five different redox states, which results in a remarkable electrochromic effect. Magnetic measurements on fresh samples point to the occurrence of a spin‐state change near room temperature, which could be ascribed to a metal‐to‐metal electron transfer converting the {Fe^II?CN?Mn^III} pair into a {Fe^III?CN?Mn^II} pair. This feature was only previously observed in the polymeric MnFe Prussian‐blue analogues (PBAs). Moreover, this novel switchable molecule proved to be soluble and stable in organic solvents, paving the way for its integration into advanced materials.     

First dicyanamide-bridged spin-crossover coordination polymer: synthesis, structural, magnetic, and spectroscopic studies

We report here on the synthesis and characterisation of a first iron(II) spin-crossover coordination polymer with the dca spacer ligand, having the formula [Fe(aqin)2(dca)]ClO4.MeOH (aqin=8-aminoquinoline, dca=dicyanamide), which displays a two-step complete spin transition. Variable-temperature magnetic susceptibility measurements and M?ssbauer spectroscopy have revealed that the two relatively gradual steps are centred at 215 and 186 K and are separated by an inflection point at about 201 K, at which 50 % of the complex molecules undergo a spin transition. The two steps are related to the existence of two crystallographically inequivalent metal sites, as confirmed by the structural and M?ssbauer studies. The crystal structure was resolved at 293 K (HS form) and 130 K (LS form). Both spin-state structures belong to the triclinic P1 space group (Z=2). The complex assumes a linear chain structure, in which the active iron(II) sites are linked to each other by anionic dicyanamide ligands acting as chemical bridges. The Fe-Fe distances through the dca ligand are 8.119(1) and 7.835(1) A in the high-spin and low-spin structures, respectively. The polymeric chains extend along a (1, 0, -1) axis and are packed in sheets, between which the perchlorate anions and methanol molecules are inserted. The complex molecules are linked together by pi-stacking interactions and H-bonding between the H-donor aqin ligands and the perchlorate ions. These structural features provide a basis for cooperative interactions in the crystal lattice. Analysis of the two-step spin-crossover character in this compound suggests that covalent interactions through the spacer ligand do not provide the main mechanism of cooperativity.     

Elastic Ising-like model for the nucleation and domain formation in spin crossover molecular solids

We investigate the nucleation, domain formation and propagation mechanisms observed in Spin Crossover materials, in the framework of an Ising-like model taking into account the elastic nature of the interactions. In Spin Crossover materials, the intermolecular coupling originates from a volume difference between the High Spin and the Low Spin molecular states and is simulated by anharmonic interaction potentials whose strengths are molecular-state-dependent. Using Monte Carlo methods, the phase diagram has been established. We show that the model contains both Ising short-range couplings and long-range elastic interactions. In particular, the results of long-range elastic models are reproduced. The introduction of lattice dynamics leads to the existence of spatial distributions of interaction energy and crystal field, corresponding to a local definition of physical properties. The nucleation process becomes highly dependent on the structural inhomogeneities induced by the spin transition. In this approach, connections strength between neighboring molecules are no more equivalent and have different ability to propagate domains. The presence of short-range Ising couplings gives rise to the occurrence of strong bonds forming a volume in which domains of the daughter phase can grow; in this case a macroscopic phase separation appears during the first order transition, even in a system with periodic boundary conditions. By contrast, in the case of a model with only long-range elastic interactions; strong bonds are uniformly spread in the lattice and a homogeneous phase transformation is observed, in good agreement with previous theoretical investigations.     

Antagonism between extreme negative linear compression and spin crossover in [Fe(dpp)(2)(NCS)(2)]⋅py

A scissor-like geometric mechanism is responsible for the strongest negative linear compression effect yet observed in a molecular material, [Fe(dpp)(2)(NCS)(2)]?py (see picture; dpp=dipyrido[3,2-a:2'3'-c]phenazine), C gray, N blue, S yellow, Fe red). The same mechanism is also responsible for suppressing the high-spin to low-spin transition under pressure.     

Simultaneous collinear and non-collinear parametric generation in 1D single grating periodically poled lithium tantalate

We report a detailed study of multiple wavelengths optical parametric generation in a single grating one-dimensional periodically poled lithium tantalate crystal. Simultaneous collinear and non-collinear generations are observed around the pump collinear direction. Similar spectra are found in continuous spatial positions symmetrical to the collinear direction, with decreasing signal and increasing idler wavelengths, associated with decreasing powers when the far-field angle increases. A phase matching scheme is proposed to describe these interactions. Numerical simulations emphasize the agreement of our phase matching scheme with the experimental results. Single-pass gain and high pump power density are very likely at the origin of the simultaneous collinear and non-collinear QPM interactions.     

One dimensional study of a module for active/passive control of both absorption and transmission

Hybrid active/passive absorbers have proven to be efficient over a large frequency range. The next step consists in building up a system which can exhibit good absorption and insulation properties. To simulate such hybrid cell, active and passive behaviors of an electroacoustic loudspeaker have been modelized by using a one-dimensional approach. The rear acoustic load at the back of the membrane has been taken into account to obtain a reliable model. The proposed model has been validated with measurements performed in a 7 cm diameter tube. Then, a hybrid cell composed of a porous plate and a small thickness loudspeaker has been designed and numerically tested. It is shown that, when driving the loudspeaker for total absorption, the transmission losses are suppressed at lower frequencies. To overcome this problem, a dual actuator cell is designed to deal with both absorption and transmission. Simulations shows that this solution can lead to good results. It is also shown that interaction of the loudspeakers can be significantly reduced by using directive sources, thus lowering supplying voltages and condition number of the matrix inversion required by the control process.     

Analysis of polarization mode dispersion fluctuations in single mode fibres due to temperature

We have studied the effect of temperature on the birefringence and polarization mode dispersion PMD in standard single mode fibre (SSMF) with elliptical core cross section by using numerical computations. On the basis of simulation we have concluded that PMD fluctuates more rapidly than the stress-induced birefringence. In addition, DGD is inversely proportional to temperature.     

High-pressure spin-crossover in a dinuclear Fe(II) complex

The effect of pressure on the dinuclear spin crossover material [{Fe(bpp)(NCS)(2)}(2)(4,4'-bipy)]·2MeOH (where bpp = 2,6-bis(pyrazol-3-yl)pyridine and 4,4'-bipy = 4,4'-bipyridine, 1) has been investigated with single crystal X-ray diffraction and Raman spectroscopy using diamond anvil cell techniques. The very gradual pressure-induced spin crossover occurs between 7 and 25 kbar, and shows no evidence of crystallographic phase transitions. The pressure-induced spin transition leads to a complete LS state which is not thermally accessible. This structural evolution under pressure is in stark contrast to the previously reported thermal spin crossover behaviour, in which a symmetry-breaking, purely structural phase transition results in only partial conversion to the low spin state. This observation is attributed to the symmetry-breaking phase transition becoming unfavourable under pressure.     

Non-isothermal crystallization kinetics and nucleation behavior of isotactic polypropylene composites with micro-talc

Journal of Thermal Analysis and Calorimetry - The current investigation has presented a new synthesis technique to prepare pentaethylene glycol-treated graphene nanoplatelets (PEG-GnP) and...