Strong Anharmonicity at the Origin of Anomalous Thermal Conductivity in Double Perovskite Cs2 NaYbCl6.

Anomalous thermal transport of Cs2 NaYbCl6 double-halide perovskite above room temperature is reported and rationalized. Calculations of phonon dispersion relations and scattering rates up to the fourth order in lattice anharmonicity have been conducted to determine their effective dependence on temperature. These findings show that specific phonon group velocities and lifetimes increase if the temperature is raised above 500 K. This, in combination with anharmonicity, provides the microscopic mechanism responsible for the increase in lattice thermal conductivity at high temperatures, contrary to the predictions of phonon transport theories based on solely cubic anharmonicity. The model accurately and quantitatively reproduces the experimental thermal conductivity data as a function of temperature.

The Boundary Between Volume and Surface-Driven Magnetic Properties in Spinel Iron Oxide Nanoparticles.

Despite modern preparation techniques offer the opportunity to tailor the composition, size, and shape of magnetic nanoparticles, understanding and hence controlling the magnetic properties of such entities remains a challenging task, due to the complex interplay between the volume-related properties and the phenomena occurring at the particle's surface. The present work investigates spinel iron oxide nanoparticles as a model system to quantitatively analyze the crossover between the bulk and the surface-dominated magnetic regimes. The magnetic properties of ensembles of nanoparticles with an average size in the range of 5-13 nm are compared. The role of surface anisotropy and the effect of oleic acid, one of the most common and versatile organic coatings, are discussed. The structural and morphological properties are investigated by X-ray diffraction and transmission electron microscopy. The size dependence of the surface contribution to the effective particle anisotropy and the magnetic structure are analyzed by magnetization measurements and in-field Mössbauer spectrometry. The structural data combined with magnetometry and Mössbauer spectrometry analysis are used to shed light on this complex scenario revealing a crossover between volume and surface-driven properties in the range of 5-7 nm.

Long-lived electrets and lack of ferroelectricity in methylammonium lead bromide CH3NH3PbBr3 ferroelastic single crystals.

Hybrid lead halides CH3NH3PbX3 (X = I, Br, and Cl) have emerged as a new class of semiconductors for low-cost optoelectronic devices with superior performance. Since their perovskite crystal structure may have lattice instabilities against polar distortions, they are also being considered as potential photo-ferroelectrics. However, so far, research on their ferroelectricity has yielded inconclusive results and the subject is far from being settled. Here, we investigate, using a combined experimental and theoretical approach, the possible presence of electric polarization in tetragonal and orthorhombic CH3NH3PbBr3 (T-MAPB and O-MAPB). We found that T-MAPB does not sustain spontaneous polarization but, under an external electric field, it is projected into a metastable, ionic space-charge electret state. The electret can be frozen on cooling, producing a large and long-lasting polarization in O-MAPB. Molecular dynamics simulations show that the ferroelastic domain boundaries are able to trap charges and segregate ionic point defects, thus playing a favorable role in the stabilization of the electret. At lower temperatures, the lack of ferroelectric behavior is explained using first principles calculations as the result of the tight competition among many metastable states with randomly oriented polarization; this large configurational entropy does not allow a single polar state to dominate at any significant temperature range.

A Platinum-Dithiolene Monoanionic Salt Exhibiting Multiproperties, Including Room-Temperature Proton-Dependent Solution Luminescence.

The platinum salt C[PtL2], where C = [(R)-Ph(Me)HC*-NMe3](+) and [PtL2](-) = radical monoanion based on [4', 5': 5, 6][1, 4]dithiino[2,3-b]quinoxaline-1',3'dithiolato, shows a variety of properties both in solution and in the solid state thanks to the electronic and/or structural features of the ligand. The complex crystallizes in the chiral space group P1 due to the presence of the enantiopure cation (R)-Ph(Me)HC*-NMe3(+), and it shows paramagnetic behavior relatable to the [PtL2](-) radical monoanion. This anionic complex is redox active and shows a strong near-infrared absorbance peak at 1085 nm tunable with the oxidation state of the complex. This complex exhibits a proton-dependent emission at 572 nm in solution at room temperature. The excitation band corresponds to the HOMO-1 (π-orbitals of the S2C2S2 system) → LUMO (π-orbitals of the quinoxaline and benzene-like moieties) transition suggesting that emission is mainly ligand centered in character. The luminescent properties are highly unusual, since the emission falls well above the energy of the lowest energy absorption (anti-Kasha behavior). Joint experimental and density functional theory (DFT) and time-dependent DFT studies are discussed to provide a satisfactory structure/property relationship.

Self-assembly supramolecular architectures of chromium(III) complexes using croconate as building block.

The synthesis, X-ray structure and magnetic properties of polynuclear Cr(III) complexes with the croconate ligand (C5O5(2-)) are reported: [Cr(mu-C5O5)(micro-OH)(OH2)2]2 x 6H2O (, orthorombic, space group Cmca, a = 6.741(7) A, b = 18.841(9) A, c = 16.886(9) A, V = 2145(3) A3) shows a dinuclear structure with two mu-OH hydroxo group and two ligand molecules that are bridging two metal centers with vicinal C[double bond, length as m-dash]O groups (micro-kappa2O,O coordination mode), the octahedral geometry of the Cr atoms being completed by the coordination of the O atom of the water molecule and [Cr(micro-C5O5)(micro-OH)(OH2)2]2[K5(C5O5)2.5] x 7H2O (, monoclinic, space group Cc, a = 15.216(9) A, b = 14.895(8) A, c = 18.503(9) A, beta = 96.77(5) degrees and V = 4164(4) A3), a polymer showing various coordination geometries of the K(I) cations. Magnetic susceptibility measurements, performed on , in the 5-400 K temperature range, show antiferromagnetic interactions with J1/k = -50.2 +/- 0.1 K and J2/k approximately -3 K with J1 and J2 the intradimer and interdimer interaction constants, respectively. DFT calculations, performed to gain insight into the coupling between the two metal centers and characterize their spin and charge distribution in the hydroxo-bridged dinuclear entities, are in good agreement with experimental findings.