Electronic, structural, and optical properties of Y2WO6, a host material for inorganic phosphors

Optimization by first principles DFT-based electronic structure methods of the crystal structures for the five polymorphs of Y2WO6 reported in the literature yields results in good agreement with those determined experimentally by X-ray diffraction. The monoclinic P2/c phase appears to be the most stable one at ambient conditions, although high temperature orthorhombic phases with larger molar volumes could be favoured upon replacement of Y3þ cations by larger Ln3þ ones, and hence, provide plausible structures for Y2WO6:Ln3þ phosphors at ambient conditions. For all polymorphs the top of the valence band is dominated by O2p orbitals with a relatively narrow WO6-centred conduction band appearing just below a broad Y4d-centred band. Insertion energies for Eu3þ replacing Y3þ are estimated to be in the range of 3e4eV per cation, with the smaller values corresponding to substitutions into the larger octacoordinated Y3þ sites

Donor-anion interactions in quarter-filled low-dimensional organic conductors

Anions have often been considered to act essentially as electron donors or acceptors in molecular conductors. However there is now growing evidence that they play an essential role in directing the structural and hence electronic properties of many of these systems. After reviewing the basic interactions and different ground states occurring in molecular conductors we consider in detail how anions influence the structure of donor stacks and often guide them toward different types of transitions. Consideration of the Bechgaard and Fabre salts illustrates how anions play a crucial role in directing these salts through complex phase diagrams where different conducting and localized states are in competition. We also emphasize the important role of hydrogen bonding and conformational flexibility of donors related to BEDT-TTF and we discuss how anions have frequently a strong control of the electronic landscape of these materials. Charge ordering, metal to metal and metal to insulator transitions occurring in these salts are considered

'Aggregation-Induced Emission'' of Transition Metal Compounds: Design, Mechanistic Insights, and Applications

In the last decades, compounds with 'Aggregation-Induced Emission' (AIE), which are weakly or non- emissive at all in solution but exhibit a strong luminescence in aggregated states, have emerged as an extraordinary breakthrough in the field of luminescent materials, allowing to circumvent 'Aggre- gation Caused Quenching' (ACQ), which in many cases prevents the development of efficient solid-state materials for optoelectronic applications. Since the discovery of AIE, many AIE-active materials have been developed, most of them composed of organic molecules, and thus fluorescent in nature. Although a wide range of applications such as bioimaging, sensing, multi-stimuli responsive materials, and optoelectronic devices have been proposed for this new class of materials, triplet harvesting phosphorescent materials have much longer lifetimes as compared to their singlet harvesting analogues, and for this particular reason, the development of AIE- active phosphorescent materials seems to be a promising strategy from the applications point of view. In this respect, the synthesis of new AIE-active systems including heavy metals that would facilitate the population of low-lying excited triplet states via spin-orbit coupling (SOC), for which the strength increases as the fourth power of atomic number, i.e. Z4 , is highly desirable. This review covers the design and synthetic strategies used to obtain the AIEgens reported in the literature that contain either d-block metals such as Cu(I), Zn(II), Re(I), Ru(II), Pd(II), Ir(III), Pt(II), Au(I), and Os(IV), describing the mechanisms proposed to explain their AIE. New emerging high-tech applications such as OLEDs, chemical sensors or bioimaging probes proposed for these materials are also discussed in a separate section

Effects of temperature on the shape and symmetry of molecules and solids

Despite its undeniable problems from a philosophical point of view, the concept of molecular structure, with attributes such as shape and symmetry, directly borrowed from the description of macroscopic objects, is nowadays central to most of chemistry. Following this trend, descriptions such as "the tetrahedral" carbon atom are widely used from elementary textbooks to the most up-to-date research articles. The definition of molecular shape is, however, not as simple as it might seem at first sight. Molecules don't behave as macroscopic objects do due to the incessant motion of its constituent particles, nuclei and electrons. How are molecular shape and symmetry affected by this thermal motion? In this review we introduce the language of continuous symmetry measures as a new tool to quantitatively describe the effects of temperature on molecular shape and symmetry

Assessment of Functionals for First-Principle Studies of the Structural and Electronic Properties of -Bi2O3

Fully relativistic full-potential density functional calculations with an all-electron linearized augmented plane waves plus local orbitals method were carried out to perform a comparative study on the structural and electronic properties of the cubic oxide -Bi2O3 phase, which is considered as one of the most promising materials in a variety of applications including fuel cells, sensors, and catalysts. Three different density functionals were used in our calculations, LDA, the GGA scheme in the parametrization of Perdew, Burke, and Ernzerhof (PBE96), and the hybrid scheme of Perdew-Wang B3PW91. The examined properties include lattice parameter, band structure and density of states, and charge density profiles. For this modification the three functionals reveal the characteristics of a metal and the existence of minigaps at high symmetry points of the band structure when spin-orbit coupling is taken into account. Density of states exhibits hybridization of Bi 6s and O 2p orbitals and the calculated charge density profiles exhibit the ionic character in the chemical bonding of this compound. The B3PW91 hybrid functional provided a better agreement with the experimental result for the lattice parameter, revealing the importance of Hartree-Fock exchange in this compound

Fermi surface properties of the bifunctional organic metal κ-(BETS)2Mn[N(CN)2]3 near the metal-insulator transition

We present detailed studies of the high-field magnetoresistance of the layered organic metal κ-(BETS)2Mn- [N(CN)2]3 under a pressure slightly above the insulator-metal transition. The experimental data are analyzed in terms of the Fermi surface properties and compared with the results of first-principles band structure calculations. The calculated size and shape of the in-plane Fermi surface are in very good agreement with those derived from Shubnikov-de Haas oscillations as well as the classical angle-dependent magnetoresistance oscillations. A comparison of the experimentally obtained effective cyclotron masses with the calculated band masses reveals electron correlations significantly dependent on the electron momentum. The momentum- or band-dependent mobility is also reflected in the behavior of the classical magnetoresistance anisotropy in a magnetic field parallel to layers. Other characteristics of the conducting system related to interlayer charge transfer and scattering mechanisms are discussed based on the experimental data. Besides the known high-field effects associated with the Fermi surface geometry, new pronounced features have been found in the angle-dependent magnetoresistance, which might be caused by coupling of the metallic charge transport to a magnetic instability in proximity to the metal-insulator phase boundary

In Search of Chiral Molecular Superconductors: κ-[(S,S)-DM-BEDT-TTF]2ClO4 Revisited

The relationship between chirality and superconductivity is an intriguing question. The two enantiomeric crystalline radical cation salts κ-[(S,S)-DM-BEDT-TTF]2ClO4 and κ-[(R,R)-DM-BEDT-TTF]2ClO4, showing κ-type arrangement of the organic layers, are investigated in search for superconducting chiral molecular materials following a 1992 report indicating the occurrence of a superconducting transition in the former compound. While the initial interpretation is presently challenged through in-depth temperature and pressure dependent single crystal resistivity measurements combined with band structure calculations, the two chiral conductors show metal like behavior with room temperature conductivities of 10-30 S cm−1 at ambient pressure and stabilization of the metallic state down to the lowest temperatures under moderate pressures. Moreover, their structural and theoretical investigations reveal an original feature, namely the existence of two different κ layers with 1D and 2D electronic dimensionality, respectively, as a consequence of an interlayer charge transfer. The resistivity drop observed for one sample below 1 K and insensitive to magnetic field, possibly results from mixing in-plane and out-of-plane contributions to the measured resistance and suggests current induced charge order melting. This feature contradicts the occurrence of superconductivity in these chiral molecular conductors and leaves open the discovery of the first chiral molecular superconductors