Octupolar versus Néel Order in Cubic 5d

We report time-of-flight neutron spectroscopy and neutron and x-ray diffraction studies of the 5d^{2} double perovskite magnets, Ba_{2}MOsO_{6} (M=Zn,Mg,Ca). These materials host antiferromagnetically coupled 5d^{2} Os^{6+} ions decorating a face-centered cubic (fcc) lattice and are found to remain cubic down to the lowest temperatures. They all exhibit thermodynamic anomalies consistent with a single phase transition at a temperature T^{*}, and a gapped magnetic excitation spectrum with spectral weight concentrated at wave vectors typical of type-I antiferromagnetic orders. However, while muon spin resonance experiments show clear evidence for time-reversal symmetry breaking below T^{*}, we observe no corresponding magnetic Bragg scattering signal. These results are shown to be consistent with ferro-octupolar symmetry breaking below T^{*}, and are discussed in the context of other 5d double perovskite magnets and theories of exotic orders driven by multipolar interactions.

Inner Coordination Sphere Control of Metal-Metal Superexchange in Ruthenium Dimers.

The dinuclear Ru(III) complexes trans-[{(NH(3))(4)Ru(py)}(2)(&mgr;-L)][PF(6)](4), where py represents pyridine and L represents 1,4-dicyanamidobenzene dianion (dicyd(2)(-)) derivatives dicyd(2)(-) (1), Me(2)dicyd(2)(-) (2), Cl(2)dicyd(2)(-) (3), and Cl(4)dicyd(2)(-) (4), have been prepared and characterized by electronic absorption spectroscopy and cyclic voltammetry. A crystal structure of the complex trans-[{(NH(3))(4)Ru(py)}(2)(&mgr;-dicyd)][PF(6)](4).(1)/(2)H(2)O showed the dicyd(2)(-) ligand to be approximately planar with the cyanamido groups in a syn configuration. Crystal structure data are space group P2(1), with a, b, and c = 7.826(3), 20.455(7), and 14.428(5) Å, respectively, beta = 95.76 (3) degrees, V = 2296.7(14) Å(3), and Z = 2. The structure was refined by using 3292 reflections with I > 2.5sigma(I) to an R factor of 0.069. Solid state magnetic susceptibility measurements of the Ru(III)-Ru(III) dimers showed diamagnetic behavior at room temperature, and this is suggested to be due to strong antiferromagnetic superexchange via the HOMO of the dicyd(2)(-) ligand. The bridging ligand dependence of metal-metal coupling in the Ru(III)-Ru(II) complexes of 1, 2, 3, and 4 in acetonitrile solution was demonstrated by the trend in comproportionation constants, 1.5 x 10(6), 5.7 x 10(6), 1.4 x 10(4), and 1.1 x 10(3), respectively. In addition, comparison to the analogous pentaammineruthenium dimers showed that the magnitude of metal-metal superexchange could be controlled by the nature of the spectator ligand. Spectroelectrochemical methods were used to acquire the absorption spectra of the mixed-valence complexes, and the intervalence band properties were modeled with PKS theory. Metal-metal coupling in the Ru(III)-Ru(II) complexes of 1, 2, 3, and 4 was analyzed by using Hush and CNS theories.

Long-range magnetic order in the 5d(2) double perovskite Ba2CaOsO6: comparison with spin-disordered Ba2YReO6.

The B-site ordered double perovskite Ba2CaOsO6 was studied by dc magnetic susceptibility, powder neutron diffraction and muon spin relaxation methods. The lattice parameter is a = 8.3619(6) Å at 280 K and cubic symmetry [Formula: see text] is retained to 3.5 K with a = 8.3462(7) Å. Curie-Weiss susceptibility behaviour is observed for T > 100 K and the derived constants are C = 0.3361(3) emu K mol(-1) and ΘCW = -156.2(3) K, in excellent agreement with literature values. This Curie constant is much smaller than the spin-only value of 1.00 emu K mol(-1) for a 5d(2) Os(6+) configuration, indicating a major influence of spin-orbit coupling. Previous studies had detected both susceptibility and heat capacity anomalies near 50 K but no definitive conclusion was drawn concerning the nature of the ground state. While no ordered Os moment could be detected by powder neutron diffraction, muon spin relaxation (µSR) data show clear long-lived oscillations indicative of a continuous transition to long-range magnetic order below TC = 50 K. An estimate of the ordered moment on Os(6+) is ∼ 0.2 µB, based upon a comparison with µSR data for Ba2YRuO6 with a known ordered moment of 2.2 µB. These results are compared with those for isostructural Ba2YReO6 which contains Re(5+), also 5d(2), and has a nearly identical unit cell constant, a = 8.36278(2) Å-a structural doppelgänger. In contrast, Ba2YReO6 shows ΘCW = - 616 K, and a complex spin-disordered and, ultimately, spin-frozen ground state below 50 K, indicating a much higher level of geometric frustration than in Ba2CaOsO6. The results on these 5d(2) systems are compared to recent theory, which predicts a variety of ferromagnetic and antiferromagnetic ground states. In the case of Ba2CaOsO6, our data indicate that a complex four-sublattice magnetic structure is likely. This is in contrast to the spin-disordered ground state in Ba2YReO6, despite a lack of evidence for structural disorder, for which theory currently provides no clear explanation.

A search for disorder in the spin glass double perovskites Sr(2)CaReO(6) and Sr(2)MgReO(6) using neutron diffraction and neutron pair distribution function analysis.

The geometrically frustrated, B-site ordered, S = 1/2, double perovskites Sr(2)CaReO(6) and Sr(2)MgReO(6), which show spin frozen magnetic ground states, have been investigated using neutron powder diffraction (ND) and neutron pair distribution function (NPDF) analysis in a search for evidence for atomic positional disorder. For both materials, data were taken above and below the spin freezing temperatures of ∼ 14 K and ∼ 45 K for the CaRe and MgRe phases, respectively. In both cases the fully B-site ordered model was in excellent agreement with the data, both ND and NPDF, at all temperatures studied. Thus, the structure of these materials, from the average and the local perspectives, is very well described by the fully B-site ordered model, which raises questions concerning the origin of the spin glass ground state. These results are compared with those for the spin glass pyrochlore Y(2)Mo(2)O(7) and other B-site ordered double perovskites.

A reinterpretation of the magnetic properties of the mixed-valence (Nb(V)/Nb(IV)) Zintl phase, Cs(9)Nb(2)As(6).

A new mixed-valent (Nb(V)/Nb(IV)) Zintl phase, Cs(9)Nb(2)As(6), has been prepared and characterized, recently (Gascoin, F.; Sevov, S. C. Inorg. Chem. 2002, 41, 5920). Niobium is present in the form of isolated, edge-sharing tetrahedral, Nb(2)As(6)(9)(-) dimers. The reported magnetic susceptibility features a broad maximum at approximately 36 K which has been interpreted as the onset of long-range antiferromagnetic order. Such a high transition temperature is difficult to understand as the compound is insulating and the interdimer Nb-Nb distance is 7.2 A. It is shown here that the observed magnetic properties follow straightforwardly from a statistical occupation of the equivalent intradimer Nb sites by equal concentrations of Nb(IV)(4d(1), S = (1)/(2)) and Nb(V)(4d(0)). From this analysis the broad maximum arises from intradimer antiferromagnetic exchange with an exchange constant, J/k = -40 K, and there is no long-range magnetic order except, possibly, below 5 K.

Solid-state coordination chemistry: structural influences of copper-phenanthroline subunits on oxovanadium organophosphonate phases. hydrothermal synthesis and structural characterization of the two-dimensional materials [Cu(phen)(VO)(O3PCH2PO3)(H2O)], [[Cu(phen)]2(V2O5)(O3PCH2CH2PO3)], and [[Cu(phen)]2(V3O5)(O3PCH2CH2CH2PO3)2(H2O)] and the three-dimensional phase [[Cu(phen)]2(V3O5)(O3PCH2PO3)2(H2O)].

The hydrothermal reactions of CuCl2*2H2O, Na3VO4, 1,10-phenanthroline, and the appropriate organodiphosphonate ligand yield [Cu(phen)(VO)(O3PCH2PO3)(H2O)] (1), [[Cu(phen)]2(V2O5)(O3PCH2CH2PO3)] (2), [[Cu(phen)]2(V3O5)(O3PCH2CH2CH2PO3)2 (H2O)] (3), and [[Cu(phen)]2(V3O5)(O3PCH2PO3)2(H2O)] (4). Compounds 1-3 exhibit two-dimensional structures. The structures exhibit distinct vanadium building blocks: square pyramidal, mononuclear V(IV) sites in 1, a binuclear unit of corner-sharing V(V) tetrahedra in 2, and a trinuclear unit of corner-sharing V(V) square pyramids and a V(IV) octahedron in 3. The network structures of 1 and 2 are constructed from one-dimensional oxovanadium-diphosphonate chains linked by Cu(II) square pyramids into two-dimensional layers. In contrast, compound 3 exhibits a two-dimensional oxovanadium-organodiphosphonate network, with Cu(II) sites decorating the surfaces. Compound 4 is unique in exhibiting a framework structure, which may be described as a three-dimensional oxovanadium-organodiphosphonate substructure with [Cu(phen)]2+ subunits covalently attached to the surface of channels running parallel to the a-axis. The magnetic properties of 1-4 are also correlated to the structural characteristics. The magnetic behavior of 2 is thus dominated by antiferromagnetic interactions. The magnetic behavior of 1 and 4 is consistent with the presence of two distinct paramagnetic metal ions, Cu(II) and V(IV). In contrast, 3 does not exhibit ferrimagnetic behavior, but rather weak antiferromagnetic coupling. Crystal data: 1, C13H10N2CuP2VO8, monoclinic P2(1)/c, a = 9.0656(5) A, b = 8.6584(5) A, c = 20.934(1) A, beta = 97.306(1) degrees, Z = 4; 2, C26H20N4Cu2P2V2O11, triclinic P1, a = 10.6096(5) A, b = 11.6951(5) A, c = 13.1796(6) A, alpha = 71.369(1) degrees, beta = 70.790(1) degrees, gamma = 80.738(1) degrees, Z = 2; 3, C30H28N4Cu2P4V3O18, triclinic P1, a = 9.4356(6) A, b = 10.6556(6) A, c = 11.0354(7) A, alpha = 118.187(1) degrees, beta = 91.416(1) degrees, gamma = 107.821(1) degrees, Z = 1; 4, C26H20N4Cu2P4V3O18, monoclinic, P2(1)/c a = 8.3947(3) A, b = 16.8401(7) A, c = 11.9144(5) A, beta = 93.903(1) degrees, Z = 2.

(Li0.91Mn0.09)Mn2O4.

Lithium manganese oxide crystals with composition (Li(0.91)Mn(0.09))Mn(2)O(4) were synthesized by a flux method. The crystals have a structure closely related to that of the cubic spinel LiMn(2)O(4), but 9% of the lithium ions in the tetrahedral 4a site are substituted by Mn(2+) ions. This substitution lowers the average Mn oxidation state below 3.5+, resulting in a Jahn-Teller distortion of the MnO(6) octahedron.

Magnetic ordering in the spin-ice candidate Ho2Ru2O7.

Neutron scattering measurements on the spin-ice candidate material Ho2Ru2O7 have revealed two magnetic transitions at T approximately 95 and approximately 1.4 K to long-range ordered states involving the Ru and Ho sublattices, respectively. Between these transitions, the Ho3+ moments form short-ranged ordered spin clusters. The internal field provided by the ordered S=1 Ru4+ moments disrupts the fragile spin-ice state and drives the Ho3+ moments to order. We have directly measured a slight shift in the Ho3+ crystal field levels at 95 K from the Ru ordering.