Gregory Morrison

Magnetic and transport properties of single crystal LnRu2Al10 (Ln = Pr, Gd, Yb)

Single crystals of LnRu(2)Al(10) (Ln = Pr, Gd, Yb) have been grown using the self-flux method, their structure has been determined by single crystal x-ray diffraction, and their magnetic and electronic transport properties have been studied. LnRu(2)Al(10) are members of the Y bFe(2)Al(10) structure type with space group Cmcm. PrRu(2)Al(10) displays paramagnetic behaviour down to 13.2 K, at which temperature it enters a non-magnetic singlet ground state, with a large paramagnetic Curie-Weiss temperature of - 49.8(14) K. GdRu(2)Al(10) orders antiferromagnetically at 15.5 K. Y bRu(2)Al(10) is a Pauli paramagnet indicating that the Yb is divalent. The properties of these three analogues are compared with LnM(2)Al(10) (M=Fe, Ru, Os).

Crystal growth of four oxovanadium(IV) tartrates prepared via a mild two-step hydrothermal method: observation of spin-dimer behavior and second harmonic generation.

Four new oxovanadium(IV) tartrates, namely, A2[(VO)2(C4H4O6)(C4H2O6)(H2O)2]·(H2O)2, where A = Cs, 1, Rb, 2; K2[(VO)2(C4H2O6)2(H2O)2]·(H2O)2, 3; and Na2[(VO)2(C4H4O6)(C4H2O6)(H2O)7]·(H2O)2, 4, were prepared utilizing a two-step, mild hydrothermal route involving l-(+)-tartaric acid as the reducing agent. All four compounds were structurally characterized by single-crystal and powder X-ray diffraction methods and were found to crystallize in the non-centrosymmetric orthorhombic space groups P212121 for 1, 2, and 4 and C2221 for 3. The temperature dependence of the magnetic susceptibility of these compounds was measured, and 1, 2, and 4 were found to be paramagnetic down to 2 K, while 3 was found to exhibit spin-dimer behavior. Compounds 1, 2, and 3 were found to be second harmonic generation active. All compounds were further characterized by IR and UV-vis spectroscopies.

Flux Synthesis, Structure, Properties, and Theoretical Magnetic Study of Uranium(IV)-Containing A2USi6O15 (A = K, Rb) with an Intriguing Green-to-Purple, Crystal-to-Crystal Structural Transition in the K Analogue

The flux growth of uranium(IV) oxides presents several challenges, and to the best of our knowledge, only one example has ever been reported. We succeeded in growing two new reduced uranium silicates A2USi6O15 (A = K, Rb) under flux growth conditions in sealed copper tubes. The compounds crystallize in a new structure type with space group C2/c and lattice parameters a = 24.2554(8) Å, b = 7.0916(2) Å, c = 17.0588(6) Å, β = 97.0860(6) ° (K) and a = 24.3902(8) Å, b = 7.1650(2) Å, c = 17.2715(6) Å, β = 96.8600(6) ° (Rb). A2USi6O15 (A = K, Rb) are isocompositional to a previously reported Cs2USi6O15, and the two structures are compared. K2USi6O15 undergoes an interesting crystal-to-crystal structural phase transition at T ≈ 225 K to a triclinic structure, which is accompanied by an intense color change. The magnetic properties of A2USi6O15 (A = K, Rb, Cs) are reported and differ from the magnetism observed in other U(4+) compounds. Calculations are performed on the (UO6)(-8) clusters of K2USi6O15 to study the cause of these unique magnetic properties.

High-Temperature Salt Flux Crystal Growth of New Lanthanide Molybdenum Oxides, Ln5Mo2O12 Ln = Eu, Tb, Dy, Ho, and Er: Magnetic Coupling within Mixed Valent Mo(IV/V) Rutile-Like Chains.

Five new lanthanide molybdenum oxides containing mixed valent Mo(IV/V) rutile-like chains, Ln5Mo2O12 Ln = Eu, Tb, Dy, Ho, and Er, were prepared utilizing a high-temperature molten salt flux synthesis involving an in situ reduction utilizing metallic reducing agents. All five compounds were structurally characterized by single-crystal and powder X-ray diffraction methods and were found to crystallize in the monoclinic space group C2/m. The molybdates all contain rare infinite chains consisting of MoO2O4/2 edge-sharing octahedra. The chains exhibit alternating long and short separations between octahedra caused by the presence of Mo-Mo bonds to form Mo2O10 units containing one unpaired electron. The temperature dependence of the magnetic susceptibility of these compounds was measured, and antiferromagnetic ordering was observed in all cases.

Magnetic order induced by Fe substitution of Al site in the heavy-fermion systems α-YbAlB4 and β-YbAlB4

beta-YbAlB4 is a heavy fermion superconductor that exhibits a quantum criticality without tuning at zero field and under ambient pressure. We have succeeded in substituting Fe for Al in beta-YbAlB4 as well as the polymorphous compound alpha-YbAlB4, which in contrast has a heavy Fermi liquid ground state. Full structure determination by single crystal X-ray diffraction confirmed no change in crystal structure for both alpha- and beta-YbAlB4, in addition to volume contraction with Fe substitution. Our measurements of the magnetization and specific heat indicate that both alpha-YbAl0.93Fe0.07B4 and beta-YbAl0.94Fe0.06B4 exhibit a magnetic order, most likely of a canted antiferromagnetic type, at

Synthesis and structure of the new pentanary uranium(VI) silicate, K4CaUSi4O14, a member of a structural family related to fresnoite

7\sim 9

New Lanthanide Mixed-Valent Vanadium(III/IV) Oxosilicates, Ln4V5–xZnxSi4O22 (Ln = La, Ce, Pr, and Nd), Crystallizing in a Quasi Two-Dimensional Rutile-Based Structure

K. The increase in the entropy as well as the decrease in the antiferromagnetic Weiss temperature with the Fe substitution in both systems indicates that the chemical pressure due to the Fe substitution suppresses the Kondo temperature and induces the magnetism.

A5RE4X[TO4]4 crystal growth and photoluminescence. Hydroflux synthesis of sodium rare earth silicate hydroxides

Single crystals of K4CaUSi4O14 have been grown from a eutectic CaF2–KF flux. K4CaUSi4O14 crystallizes in a new structure which exhibits a 49-fold superstructure believed to be due to a modulation of the uranium and silicon polyhedra. We report the sub-cell of the structure which adopts the tetragonal space group Pn2 with lattice parameters a = 9.2862(2) A, c = 8.3796(4) A, and V = 722.60(5) A3. K4CaUSi4O14 is a member of a structural family related to the mineral fresnoite which we describe here. Finally, we report UV-vis absorbance and SHG measurements on the compound, which is non-centrosymmetric.

Synthetic strategies for new vanadium oxyfluorides containing novel building blocks: structures of V(IV) and V(V) containing Sr4V3O5F13, Pb7V4O8F18, Pb2VO2F5, and Pb2VOF6

A family of lanthanide mixed-valent vanadium(III/IV) oxosilicates Ln4V(5-x)Zn(x)Si4O22 (Ln = La, Ce, Pr, and Nd) was synthesized as high-quality single crystals via a high-temperature molten salt method. An in situ reduction of V(V) to V(III/IV) as well as of Ce(IV) to Ce(III) was achieved utilizing Zn metal as the reducing agent, some of which is incorporated into the crystal structure. Ce4V(4.77)Zn(0.23)Si4O22, to the best of our knowledge, is the first example of a cerium-containing mixed-valent vanadium silicate. The crystal structures were determined by single-crystal X-ray diffraction, and the four isostructural oxosilicates were determined to crystallize in the chevkinite-structure type in the monoclinic space group I2/a. The unit cells of the Ln4V(5-x)Zn(x)Si4O22 (Ln = La, Ce, Pr, and Nd) series are related to the reported C2/m phases Ln4V5Si4O22 (Ln = La, Pr, and Nd) by a doubling of the c-axis and a loss of a mirror plane. The three-dimensional crystal structure consist of two-dimensional rutile-based vanadium oxide and lanthanide oxide layers linked via Si2O7 groups. The temperature dependence of the magnetic susceptibility of these compounds was measured, and only the Nd analogue exhibited a magnetic transition at 5 K; all samples displayed a discontinuity or deviation from linearity at ca. 130-150 K.

Surface-Directed Synthesis of Erbium-Doped Yttrium Oxide Nanoparticles within Organosilane Zeptoliter Containers

Single crystals of Na5RE4(OH)[SiO4]4 (RE = Pr, Nd, Sm, Eu, Tb–Yb, Y) were grown using the hydroflux synthetic method. All compositions adopt the tetragonal I space group with lattice parameter ranges of a = 11.5275(4)–12.0588(3) A and c = 5.3951(4)–5.4846(13) A. Intense photoluminescent properties were observed for Na5Eu4(OH)[SiO4]4, Na5Gd4(OH)[SiO4]4, and Na5Tb4(OH)[SiO4]4. The magnetic susceptibility was measured for the magnetic rare earth containing compositions, where the terbium analogue displayed antiferromagnetic order at T = 2.8 K.