Raman scattering spectra of boron imidazolate frameworks containing different magnetic ions.

We present a Raman scattering spectroscopic study of boron imidazolate metal-organic frameworks (BIFs) with three different magnetic metal ions and one non-magnetic in a wide frequency range from 25 to 1700 cm-1, which covers local vibrations of the imidazolate linkers as well as collective lattice vibrations. We show that the spectral region above 800 cm-1 belongs to the local vibrations of the linkers, which have the same frequencies for the studied BIFs without any dependence on the structure of the BIFs and are easily interpreted based on the spectra of imidazolate linkers. In contrast, collective lattice vibrations, observed below 100 cm-1, show a distinction between cage and two-dimensional BIFs structures, with a weak dependence on the metal node. We identify the range of vibrations around 200 cm-1, which are distinct for each metal-organic framework, depending on a metal node. Our work demonstrates the energy hierarchy in the vibrational response of BIFs.

Anomalously field-susceptible spin clusters emerging in the electric-dipole liquid candidate κ-(ET)2Hg(SCN)2Br.

Mutual interactions in many-body systems bring about various exotic phases, among which liquid-like states failing to order due to frustration are of keen interest. The organic system with an anisotropic triangular lattice of molecular dimers, κ-(ET)2Hg(SCN)2Br, has been suggested to host a dipole liquid arising from intradimer charge-imbalance instability, possibly offering an unprecedented stage for the spin degrees of freedom. Here, we show that an extraordinary unordered/unfrozen spin state having soft matter-like spatiotemporal characteristics emerges in this system. 1H nuclear magnetic resonance (NMR) spectra and magnetization measurements indicate that gigantic, staggered moments are nonlinearly and inhomogeneously induced by a magnetic field, whereas the moments vanish in the zero-field limit. The analysis of the NMR relaxation rate signifies that the moments fluctuate at a characteristic frequency slowing down to below megahertz at low temperatures. The inhomogeneity, local correlation, and slow dynamics indicative of middle-scale dynamical correlation length of several nanometers suggest novel frustration-driven spin clusterization.

A Gold(I) Oxide Double Perovskite: Ba2AuIO6.

Oxide perovskites offer improved stability compared to halide perovskite compounds for optoelectronic applications. Here, we report the first gold-containing double perovskite, Ba2AuIO6, and compare it to Ba2AgIO6 and Ba2NaIO6. Ba2AuIO6 and Ba2AgIO6 exhibit a monoclinic distortion from the cubic perovskite structure possessed by Ba2NaIO6 and have similar lattice constants despite the nominally larger size of Au+ compared to Ag+. Ba2AgIO6 shows photoluminescence (PL) at 2.10 eV, and Ba2AuIO6 exhibits PL at 1.30 and 1.47 eV. As prepared, both compounds appear stable under visible light at room temperature but decompose when subjected to gentle heating followed by illumination. Our data suggest that this behavior is due to the presence of -OH defects in the crystal structures. This discovery provides a new route to semiconductors with a near-IR band gap and identifies engineering challenges that must be addressed to use oxide perovskites for optoelectronic devices.

Impact of the Lattice on Magnetic Properties and Possible Spin Nematicity in the S=1 Triangular Antiferromagnet NiGa_{2}S_{4}.

NiGa_{2}S_{4} is a triangular lattice S=1 system with strong two dimensionality of the lattice, actively discussed as a candidate to host spin-nematic order brought about by strong quadrupole coupling. Using Raman scattering spectroscopy we identify a phonon of E_{g} symmetry which can modulate magnetic exchange J_{1} and produce quadrupole coupling. Additionally, our Raman scattering results demonstrate a loss of local inversion symmetry on cooling, which we associate with sulfur vacancies. This will lead to disordered Dzyaloshinskii-Moriya interactions, which can prevent long-range magnetic order. Using magnetic Raman scattering response we identify 160 K as a temperature of an upturn of magnetic correlations. The temperature range below 160 K, but above 50 K where antiferromagnetic correlations start to increase, is a candidate for spin-nematic regime.

Dynamical Bonding Driving Mixed Valency in a Metal Boride.

Samarium hexaboride is an anomaly, having many exotic and seemingly mutually incompatible properties. It was proposed to be a mixed-valent semiconductor, and later a topological Kondo insulator, and yet has a Fermi surface despite being an insulator. We propose a new and unified understanding of SmB6 centered on the hitherto unrecognized dynamical bonding effect: the coexistence of two Sm-B bonding modes within SmB6 , corresponding to different oxidation states of the Sm. The mixed valency arises in SmB6 from thermal population of these distinct minima enabled by motion of B. Our model simultaneously explains the thermal valence fluctuations, appearance of magnetic Fermi surface, excess entropy at low temperatures, pressure-induced phase transitions, and related features in Raman spectra and their unexpected dependence on temperature and boron isotope.

Substrate-directed synthesis of MoS2 nanocrystals with tunable dimensionality and optical properties.

Two-dimensional transition-metal dichalcogenide (TMD) crystals are a versatile platform for optoelectronic, catalytic and quantum device studies. However, the ability to tailor their physical properties through explicit synthetic control of their morphology and dimensionality is a major challenge. Here we demonstrate a gas-phase synthesis method that substantially transforms the structure and dimensionality of TMD crystals without lithography. Synthesis of MoS2 on Si(001) surfaces pre-treated with phosphine yields high-aspect-ratio nanoribbons of uniform width. We systematically control the width of these nanoribbons between 50 and 430 nm by varying the total phosphine dosage during the surface treatment step. Aberration-corrected electron microscopy reveals that the nanoribbons are predominantly 2H phase with zig-zag edges and an edge quality that is comparable to, or better than, that of graphene and TMD nanoribbons prepared through conventional top-down processing. Owing to their restricted dimensionality, the nominally one-dimensional MoS2 nanocrystals exhibit photoluminescence 50 meV higher in energy than that from two-dimensional MoS2 crystals. Moreover, this emission is precisely tunable through synthetic control of crystal width. Directed crystal growth on designer substrates has the potential to enable the preparation of low-dimensional materials with prescribed morphologies and tunable or emergent optoelectronic properties.

Evidence for a quantum dipole liquid state in an organic quasi-two-dimensional material.

Mott insulators are commonly pictured with electrons localized on lattice sites, with their low-energy degrees of freedom involving spins only. Here, we observe emergent charge degrees of freedom in a molecule-based Mott insulator κ-(BEDT-TTF)2Hg(SCN)2Br, resulting in a quantum dipole liquid state. Electrons localized on molecular dimer lattice sites form electric dipoles that do not order at low temperatures and fluctuate with frequency detected experimentally in our Raman spectroscopy experiments. The heat capacity and Raman scattering response are consistent with a scenario in which the composite spin and electric dipole degrees of freedom remain fluctuating down to the lowest measured temperatures.

Patterning Superconductivity in a Topological Insulator.

Topologically protected states in combination with superconductivity hold great promise for quantum computing applications, but the progress on electrical transport measurements in such systems has been impeded by the difficulty of fabricating devices with reliable electrical contacts. We find that superconductivity can be patterned directly into Bi2Se3 nanostructures by local doping with palladium. Superconducting regions are defined by depositing palladium on top of the nanostructures using electron beam lithography followed by in situ annealing. Electrical transport measurements at low temperatures show either partial or full superconducting transition, depending on the doping conditions. Structural characterization techniques indicate that palladium remains localized in the targeted areas, making it possible to pattern superconducting circuits of arbitrary shapes in this topological material.

Absence of Jahn-Teller transition in the hexagonal Ba3CuSb2O9 single crystal.

With decreasing temperature, liquids generally freeze into a solid state, losing entropy in the process. However, exceptions to this trend exist, such as quantum liquids, which may remain unfrozen down to absolute zero owing to strong quantum entanglement effects that stabilize a disordered state with zero entropy. Examples of such liquids include Bose-Einstein condensation of cold atoms, superconductivity, quantum Hall state of electron systems, and quantum spin liquid state in the frustrated magnets. Moreover, recent studies have clarified the possibility of another exotic quantum liquid state based on the spin-orbital entanglement in FeSc2S4. To confirm this exotic ground state, experiments based on single-crystalline samples are essential. However, no such single-crystal study has been reported to date. Here, we report, to our knowledge, the first single-crystal study on the spin-orbital liquid candidate, 6H-Ba3CuSb2O9, and we have confirmed the absence of an orbital frozen state. In strongly correlated electron systems, orbital ordering usually appears at high temperatures in a process accompanied by a lattice deformation, called a static Jahn-Teller distortion. By combining synchrotron X-ray diffraction, electron spin resonance, Raman spectroscopy, and ultrasound measurements, we find that the static Jahn-Teller distortion is absent in the present material, which indicates that orbital ordering is suppressed down to the lowest temperatures measured. We discuss how such an unusual feature is realized with the help of spin degree of freedom, leading to a spin-orbital entangled quantum liquid state.

Characterization of the quasi-one-dimensional compounds δ-(EDT-TTF-CONMe2)2X, X=AsF6 and Br by vibrational spectroscopy and density functional theory calculations.

We have investigated the infrared spectra of the quarter-filled charge-ordered insulators δ-(EDT-TTF-CONMe2)2X (X= AsF6, Br) along all three crystallographic directions in the temperature range from 300 to 10 K. DFT-assisted normal mode analysis of the neutral and ionic EDT-TTF-CONMe2 molecule allows us to assign the experimentally observed intramolecular modes and to obtain relevant information on the charge ordering and intramolecular interactions. From frequencies of charge-sensitive vibrations we deduce that the charge-ordered state is already present at room temperature and does not change on cooling, in agreement with previous NMR measurements. The spectra taken along the stacking direction clearly show features of vibrational overtones excited due to the anharmonic electronic molecule potential caused by the large charge disproportionation between the molecular sites. The shift of certain vibrational modes indicates the onset of the structural transition below 200 K.

Coordination chemistry and reactivity of a cupric hydroperoxide species featuring a proximal H-bonding substituent.

At -90 °C in acetone, a stable hydroperoxo complex [(BA)Cu(II)OOH](+) (2) (BA, a tetradentate N(4) ligand possessing a pendant -N(H)CH(2)C(6)H(5) group) is generated by reacting [(BA)Cu(II)(CH(3)COCH(3))](2+) with only 1 equiv of H(2)O(2)/Et(3)N. The exceptional stability of 2 is ascribed to internal H-bonding. Species 2 is also generated in a manner not previously known in copper chemistry, by adding 1.5 equiv of H(2)O(2) (no base) to the cuprous complex [(BA)Cu(I)](+). The broad implications for this finding are discussed. Species 2 slowly converts to a µ-1,2-peroxodicopper(II) analogue (3) characterized by UV-vis and resonance Raman spectroscopies. Unlike a close analogue not possessing internal H-bonding, 2 affords no oxidative reactivity with internal or external substrates. However, 2 can be protonated to release H(2)O(2), but only with HClO(4), while 1 equiv Et(3)N restores 2.

Two alternating BEDT-TTF packing motifs in alpha-kappa-(BEDT-TTF)2Hg(SCN)3.

The first BEDT-TTF charge transfer salt in which alternating electron-donor layers possess alpha- and kappa-type packing motifs has been synthesized. The crystal structure and physical properties of the organic conductor alpha-kappa-(BEDT-TTF)2Hg(SCN)3 are described, including a detailed description of its optical properties. The electronic behavior is dominated by a sharp metal-to-insulator transition at T = 176 K which is due to a first-order structural phase transition. The optical properties in the metallic regime are a superposition of those of the alpha- and kappa-phases, while in the insulating state the spectra become more anisotropic in the conducting plane, and the features of the two layers cannot be distinguished.