No abstract

A kagomé antiferromagnet presents an ideal construct for studying the unusual physics that result from the placement of magnetically frustrated spins on a low-dimensional lattice. Jarosites are the prototype for a spin-frustrated magnetic structure, because these materials are composed exclusively of kagomé layers. Notwithstanding, jarosite-type materials have escaped precise magnetic characterization over the past three decades, because they are notoriously difficult to prepare in pure and single-crystal forms. These hurdles have been overcome with the development of redox-based hydrothermal methods. Armed with pure and crystalline materials, several perplexing issues surrounding the magnetic properties of the jarosites have been resolved, yielding a detailed and comprehensive picture of the ground-state physics of this kagomé lattice.

Variable-temperature magnetic susceptibility shows that electrons on the vanadium centers of the Na+, K+, and Rb+ intercalates of layered vanadyl phosphate are ferromagnetically coupled via V(OPO)2V rings within the layers. The superexchange pathway is preserved in the Sr2+-intercalated system, but antiferromagnetic coupling is observed in the intralayer. This disparate behaviour correlates with the orientation of the basal planes of the (VO)O4 subunits in the X-ray-characterized Rb+-intercalated layered phosphate as well as in the previously characterized Na+, K+, and Sr+ systems.

Redox-based, hydrothermal synthetic methodologies have enabled the preparation of a new series of stoichiometrically pure jarosites of the formula, AV(3)(OH)(6)(SO(4))(2) with A = Na(+), K(+), Rb(+), Tl(+), and NH(4)(+). These jarosites represent the first instance of strong ferromagnetism within a Kagomé layered framework. The exchange interaction, which is invariant to the nature of the A(+) ion (theta(CW) approximately equal to +53(1) K), propagates along the d(2) magnetic sites of the triangular Kagomé lattice through bridging hydroxyl groups. An analysis of the frontier orbitals suggests this superexchange pathway to possess significant pi-orbital character. Measurements on a diamagnetic host jarosite doped with magnetically dilute spin carriers, KGa(2.96)V(0.04)(OH)(6)(SO(4))(2), reveal significant single-ion anisotropy for V(3+) ion residing in the tetragonal crystal field. This anisotropy confines the exchange-coupled moments to lie within the Kagomé layer. Coupling strengths are sufficiently strong to prevent saturation of the magnetization when an external field is applied orthogonal to the Kagomé layer. Antiferromagnetic ordering of neighboring ferromagnetic Kagomé layers becomes dominant at low temperatures, characteristic of metamagnetic behavior for the AV(3)(OH)(6)(SO(4))(2) jarosites. This interlayer exchange coupling decreases monotonically with increasing layer spacing along the series, A = Na(+), K(+), Rb(+), NH(4)(+), and Tl(+), and it may be overcome by the application of external field strengths in excess of approximately 6 kOe.

A dominant ferromagnetic exchange interaction propagates about the magnetic sites of the Kagomé lattice of the title compound through the bridging hydroxy groups (see section of the structure). This is at variance with the antiferromagnetic exchange observed for jarosite and its derivatives. The ferromagnetism probably arises from the d2 electron count of the VIII centers.