Metal–organic frameworks (MOFs) containing redox active linkers have led to hybrid compounds exhibiting high electrical conductivity, which enables their use in applications in electronics and ...electrocatalysis. While many computational studies predict two-dimensional (2D) MOFs to be metallic, the majority of experiments show decreasing conductivity on cooling, indicative of a gap in the electronic band structure. To date, only a handful of MOFs have been reported that exhibit increased electrical conductivity upon cooling indicative of a metallic character, which highlights the need for a better understanding of the origin of the conductivity. A 2D MOF containing iron bis(dithiolene) motifs was recently reported to exhibit semiconducting behavior with record carrier mobility. Herein, we report that high crystallinity and the elimination of guest species results in an iron 2,3,6,7,10,11-tripheylenehexathiolate (THT) MOF, FeTHT, exhibiting a complex transition from semiconducting to metallic upon cooling, similar to what was shown for the analogous CoTHT. Remarkably, exposing the FeTHT to air significantly influences the semiconducting-to-metallic transition temperature (100 to 300 K) and ultimately results in a material showing metallic-like character at, and above, room temperature. This study indicates these materials can tolerate a substantial degree of doping that ultimately results in charge delocalization and metallic-like conductivity, an important step toward enabling their use in chemiresistive sensing and optoelectronics.
Two new transition metal oxides with the nominal chemical compositions of Li4NiOsO6 and Li3Ni2OsO6 were successfully synthesized. Both compounds crystallize in an ordered rock salt structure type in ...the monoclinic C2/m space group. The crystal structures were determined using both synchrotron X-ray and time-of-flight neutron, powder diffraction data. In both phases, Ni2+ ions are present while oxidation states of osmium are +6 and +5 in Li4NiOsO6 and Li3Ni2OsO6, respectively. Ni2+ ions in the hypothetical fully ordered phase form a honeycomb arrangement in the ab crystallographic plane and these hexagons are centered by osmium ions. Furthermore, the magnetic layers are separated along the c axis by the octahedra, which are centered by Li+ (or Li+/Ni2+, depending on the chemical compositions). Crystal structure refinements reveal that there is some degree of mixed occupancy in cationic positions. Temperature dependent magnetic susceptibility data for both phases show ferrimagnetic transitions with predominant antiferromagnetic (AFM) interactions among 3d electrons of nickel and Sd electrons of osmium. Iso-thermal magnetization loops as a function of the applied magnetic field below the transition temperatures confirm the ferrimagnetic nature in magnetic transitions. Temperature dependent heat capacity data, however, did not exhibit any anomaly in either phase, indicating the absence of long-range magnetic ordering. The lack of long-range order for both Os5+ and Os6+-based compounds was also confirmed by low temperature neutron diffraction data down to 10 K. Temperature dependent AC magnetic susceptibility data in various frequencies for both samples indicate that Li4NiOsO6 exhibits spin-glass-like behavior, while the transition temperature for Li3Ni2OsO6 is nearly frequency independent.
A new Os-based B-site ordered double perovskite with the chemical composition of Ca2ScOsO6 was successfully synthesized. The crystal structure of the title compound was determined by employing the ...powder X-ray diffraction method and was found to crystallize in the monoclinic P21/n space group with the cell constants of a = 5.4716(1) Å, b = 5.6165(1) Å, c = 7.8168 (1) Å, and β = 89.889 (2)°. The temperature-dependent magnetic susceptibility data suggest that this novel S = 3/2 compound undergoes an antiferromagnetic transition at ∼69 K. Fitting the high-temperature susceptibility data (100–300 K) to Currie–Weisse behavior showed C = 1.734 emu·K/mol (μeff = 3.72 bohr magnetons) and θ = −341 K, which is indicative of dominant antiferromagnetic interactions. Temperature-dependent specific heat measurements exhibit a λ shape anomaly at 69 K, which is consistent with a long-range ordering of the spins. Because of a triangular arrangement of antiferromagnetically ordered magnetic ions, the system exhibits some degree of geometric magnetic frustration (GMF), but not strongly. Spin-dimer analysis, employing extended Hückel theory, reveals that a dominant exchange interaction exists (along the a crystallographic axis in perovskite layer), which violates the perfect condition for GMF.
Here we present a comparative study of the magnetic and crystal chemical properties of two Co2+ containing garnets. CaY2Co2Ge3O12 (which has been reported previously) and NaCa2Co2V3O12 both exhibit ...the onset of antiferromagnetic order around 6 K as well as field-induced transitions around 7 and 10 T, respectively, that manifest as anomalies in the dielectric properties of the material. We perform detailed crystal-chemistry analyses and complementary density functional theory calculations to show that very minor changes in the local environment of the Co ions explain the differences in the two magnetic structures and their respective properties.
Two new transition metal oxides with the nominal chemical compositions of Li
NiOsO
and Li
Ni
OsO
were successfully synthesized. Both compounds crystallize in an ordered rock salt structure type in ...the monoclinic
2/
space group. The crystal structures were determined using both synchrotron X-ray and time-of-flight neutron, powder diffraction data. In both phases, Ni
ions are present while oxidation states of osmium are +6 and +5 in Li
NiOsO
and Li
Ni
OsO
, respectively. Ni
ions in the hypothetical fully ordered phase form a honeycomb arrangement in the
crystallographic plane and these hexagons are centered by osmium ions. The magnetic layers are separated along the
axis by the octahedra, which are centered by Li
(or Li
/Ni
, depending on the chemical compositions). Crystal structure refinements reveal that there is some degree of mixed occupancy in cationic positions. Temperature dependent magnetic susceptibility data for both phases show ferrimagnetic transitions with predominant antiferromagnetic (AFM) interactions among 3d electrons of nickel and 5d electrons of osmium. Iso-thermal magnetization loops as a function of the applied magnetic field below the transition temperatures confirm the ferrimagnetic nature in magnetic transitions. Temperature dependent heat capacity data, however, did not exhibit any anomaly in either phase, indicating the absence of long-range magnetic ordering. The lack of long-range order for both Os
and Os
-based compounds was also confirmed by low temperature neutron diffraction data down to 10 K. Temperature dependent AC magnetic susceptibility data in various frequencies for both samples indicate that Li
NiOsO
exhibits spin-glass-like behavior, while the transition temperature for Li
Ni
OsO
is nearly frequency independent.
Single crystals of Ln
Fe
Co
Sb
Bi
(Ln = La, Ce; 0 ≤ x < 0.5; 0 ≤ y ≤ 0.2) were grown using Bi flux and self-flux methods. The compounds adopt the La
Fe
Sb
structure type with tetragonal space group ...I4/ mmm. The La
Fe
Sb
structure type is comprised of rare earth atoms capping square Sb nets in a square antiprismatic fashion and two transition-metal networks forming a PbO-type layer with Sb and transition-metal isosceles triangles. Substituting Co into the transition-metal sublattice results in a decrease in the transition temperature and reduced frustration, indicative of a transition from localized to itinerant behavior. In this manuscript, we demonstrated that Bi can be used as an alternate flux to grow single crystals of antimonides. Even with the incorporation of Bi into the Sb square net, the magnetic properties are not significantly affected. In addition, we have shown that the incorporation of Co into the Fe triangular sublattice leads to an itinerant magnetic system.
In this contribution, we review the crystal chemistry and magnetic exchange pathways in atomically well-ordered oxide garnets and spinels. While superficially the topologies of these two structures ...appear quite different, both are capable of accommodating a large number of magnetic elements from across the periodic table within multiple coordination environments, making them ideal for identifying new design principles. We present a comparison of the crystal chemistry for the two structures and an overview of the various magnetic properties that have been observed when one or more magnetic ions occupy the individual sublattices. We identify that the large number of degenerate superexchange pathways between each sublattice in either structure plays a critical role in producing novel magnetic behavior.
We present a comparison of the crystal chemistry for two structures and an overview of how the structures play a critical role in producing novel magnetic behavior. Display omitted
In this contribution, we report that CaY2Co2Ge3O12 exhibits an unusual anisotropic and chainlike antiferromagnetic arrangement of spins despite crystallizing in the highly symmetric garnet structure. ...Using low-temperature powder neutron diffraction and symmetry analysis, we identify a magnetic structure consisting of chainlike motifs oriented along the body diagonals of the cubic unit cell with moments pointing parallel to the chain direction due to the strong Ising character of the Co ions. Antiferromagnetic order sets in below 6 K and exhibits both temperature- and field-induced magnetic transitions at high fields. Combining the results, we present a magnetic phase diagram that suggests CaY2Co2Ge3O12 undergoes a quantum phase transition at low temperatures and moderate fields.
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