Heteropentanuclear {Ru(II)Cu(II)4} Kuratowski Complexes Assembled from a Ruthenium(II) Precursor Complex to Study Competing Exchange Interactions in M(II)(ta)2 Networks [ta(-) = 1,2,3-Triazolate].

We report a directed two-step synthesis toward pentanuclear Kuratowski complexes. First, six 5,6-dimethylbenzo[1,2,3]triazole ligands (Me2btaH) are coordinated to a single Ru(II) ion, providing a topologically ideal template for the addition of further metal ions. The synthesis and crystal structures of [RuCu4X4(Me2bta)6] [X = acetylacetonate (acac) and tris(3,5-dimethyl-1-pyrazolyl)borate (Tp*)] are described. Both represent new members of the family of so-called Kuratowski (K3,3) complexes. The coordination units feature triazolato-bridged metal-centered {MM4} tetrahedra, which are known for frustrated magnetic interactions in both complexes and metal-organic frameworks. The novel Ru(II)-centered complexes were synthesized in order to investigate the influence of the presence or absence of a paramagnetic central metal ion in the Kuratowski complex. Superconducting quantum interference device and electron spin resonance measurements demonstrate that small deviations in bond lengths and valence angles can lead to the formation of pairs of magnetic exchange-coupled Cu(II) ions. Which Cu(II) ions pair up can be predicted in Jahn-Teller active compounds by the overlap of the respective orbitals. These data are compared with those gleaned for M(II)(ta)2 (ta = 1,2,3-triazolate) lattices, in which structurally similar {MM4} tetrahedra constitute the secondary building units.

Cooperative Large-Hysteresis Spin-Crossover Transition in the Iron(II) Triazolate [Fe(ta)2] Metal-Organic Framework.

The metal-organic framework [Fe(ta)2] (Hta = 1H-1,2,3-triazole) containing Fe(II) ions and 1,2,3-triazolate ligands shows a reversible phase transition while retaining the cubic crystal symmetry and space group Fd3m (no. 227). The phase transition between room temperature (RT-[Fe(ta)2]; a = 16.6315(2) Å, V = 4600.39(8) Å3) and high temperature (HT-[Fe(ta)2]; a = 17.7566(4) Å, V = 5598.6(1) Å3) phases occurs at a temperature above 290 °C, whereas the phase transition between HT- and RT-[Fe(ta)2] starts at a temperature below 210 °C. Both [Fe(ta)2] polymorphs have identical bond topologies, but they differ by a large increase of the unit cell's volume of 22% for HT-[Fe(ta)2]. The compounds are characterized by powder X-ray diffraction, differential scanning calorimetry, and thermogravimetric analyses. Additionally, Mössbauer spectroscopy, magnetic studies, and the electronic structure of both phases are discussed in detail with respect to the spin-crossover transition from the low-spin (RT-[Fe(ta)2]) to the high-spin phase (HT-[Fe(ta)2]).

Evidence for Electronically Driven Ferroelectricity in a Strongly Correlated Dimerized BEDT-TTF Molecular Conductor.

By applying measurements of the dielectric constants and relative length changes to the dimerized molecular conductor κ-(BEDT-TTF)_{2}Hg(SCN)_{2}Cl, we provide evidence for order-disorder type electronic ferroelectricity that is driven by the charge order within the (BEDT-TTF)_{2} dimers and stabilized by a coupling to the anions. According to our density functional theory calculations, this material is characterized by a moderate strength of dimerization. This system thus bridges the gap between strongly dimerized materials, often approximated as dimer-Mott systems at 1/2 filling, and nondimerized or weakly dimerized systems at 1/4 filling, exhibiting a charge order. Our results indicate that intradimer charge degrees of freedom are of particular importance in correlated κ-(BEDT-TTF)_{2}X salts and can create novel states, such as electronically driven multiferroicity or charge-order-induced quasi-one-dimensional spin liquids.

[Co5Tp*4(Me2bta)6]: A Highly Symmetrical Pentanuclear Kuratowski Complex Featuring Tris(pyrazolyl)borate and Benzotriazolate Ligands.

The pentanuclear Co(II) complex [Co5Tp*4(Me2bta)6] containing N-donor ligands (5,6-dimethyl benzotriazolate; Me2bta6) and N-donor capping ligands (tris(3,5-dimethyl-1-pyrazolyl)borate; Tp*) was prepared by a simple and efficient ligand exchange reaction from [Co5Cl4(Me2bta)6] and tetra-n-butyl ammonium tris(3,5-dimethyl-1-pyrazolyl)borate. Compared to the precursor complex [Co5Cl4(Me2bta)6], which contains one Co(II) ion in octahedral and four Co(II) ions in tetrahedral coordination geometry, the title compound features all five Co(II) ions in an octahedral coordination environment while keeping a high complex symmetry. This results in modified properties including improved solubility and distinct magnetic behavior as compared to the precursor complex. The molecular structure and phase purity of the compound was verified by XRPD, UV-vis, ESI-MS, IR, and NMR measurements. Thermal stability of the compound was determined via TGA. The magnetic properties of here reported novel complex [Co5Tp*4(Me2bta)6] as well as its precursor [Co5Cl4(Me2bta)6] were examined in detail via ESR and SQUID measurements, which indicated weak anti-ferromagnetic exchange interactions between high-spin Co(II) centers at T < 20 and 50 K, respectively.

Sub-gap optical response in the Kitaev spin-liquid candidate α-RuCl3.

We report detailed optical experiments on the layered compound α-RuCl3 focusing on the THz and sub-gap optical response across the structural phase transition from the monoclinic high-temperature to the rhombohedral low-temperature structure, where the stacking sequence of the molecular layers is changed. This type of phase transition is characteristic for a variety of tri-halides crystallizing in a layered honeycomb-type structure and so far is unique, as the low-temperature phase exhibits the higher symmetry. One motivation is to unravel the microscopic nature of THz and spin-orbital excitations via a study of temperature and symmetry-induced changes. The optical studies are complemented by thermal expansion experiments. We document a number of highly unusual findings: A characteristic two-step hysteresis of the structural phase transition, accompanied by a dramatic change of the reflectivity. A complex dielectric loss spectrum in the THz regime, which could indicate remnants of Kitaev physics. Orbital excitations, which cannot be explained based on recent models, and an electronic excitation, which appears in a narrow temperature range just across the structural phase transition. Despite significant symmetry changes across the monoclinic to rhombohedral phase transition and a change of the stacking sequence, phonon eigenfrequencies and the majority of spin-orbital excitations are not strongly influenced. Obviously, the symmetry of a single molecular layer determines the eigenfrequencies of most of these excitations. Only one mode at THz frequencies, which becomes suppressed in the high-temperature monoclinic phase and one phonon mode experience changes in symmetry and stacking. Finally, from this combined terahertz, far- and mid-infrared study we try to shed some light on the so far unsolved low energy (<1 eV) electronic structure of the ruthenium 4d 5 electrons in α-RuCl3.

Ultra-robust high-field magnetization plateau and supersolidity in bond-frustrated MnCr2S4.

Frustrated magnets provide a promising avenue for realizing exotic quantum states of matter, such as spin liquids and spin ice or complex spin molecules. Under an external magnetic field, frustrated magnets can exhibit fractional magnetization plateaus related to definite spin patterns stabilized by field-induced lattice distortions. Magnetization and ultrasound experiments in MnCr2S4 up to 60 T reveal two fascinating features: (i) an extremely robust magnetization plateau with an unusual spin structure and (ii) two intermediate phases, indicating possible realizations of supersolid phases. The magnetization plateau characterizes fully polarized chromium moments, without any contributions from manganese spins. At 40 T, the middle of the plateau, a regime evolves, where sound waves propagate almost without dissipation. The external magnetic field exactly compensates the Cr-Mn exchange field and decouples Mn and Cr sublattices. In analogy to predictions of quantum lattice-gas models, the changes of the spin order of the manganese ions at the phase boundaries of the magnetization plateau are interpreted as transitions to supersolid phases.

An organometallic chimie douce approach to new Re(x)W(1-x)O3 phases.

Re(x)W(1-x)O3.H2O and Re(x)W(1-x)O3 phases are prepared by a new organometallic chimie douce concept employing the organometallic precursor methyltrioxorhenium.

A U(V) chalcogenide: synthesis, structure, and characterization of K2Cu3US5.

The compound K2Cu3US5 was obtained by the reaction of K2S, UCl4, CuCl, and S at 973 K. K2Cu3US5 crystallizes in a new structure type in space group Cmcm of the orthorhombic system in a cell of dimensions a = 3.9374(6) A, b = 13.813(2) A, c = 17.500(3) A, and V = 951.8(2) A3 at 153 K. The structure comprises (2)(infinity)[UCu3S52-] slabs separated by K+ cations. The slabs are built from CuS4 tetrahedra and US6 octahedra. Their connectivity differs from other known octahedral/tetrahedral packing patterns. In the temperature range 130-300 K the compound exhibits Curie-Weiss magnetic behavior with mu(eff) = 2.45(8) mu(B). This result together with both the bond distances and bond valence calculations and the absence of a Cu2+ ESR signal support the formulation of the above compound as K+2Cu+3U5+S2-5.