Pressure-induced enhancement of magnetic-ordering temperature in an organic radical to 70 K: a magnetostructural correlation.

The structure of the canted antiferromagnet ß-p-NCC(6)F(4)CNSSN (1) was determined from synchrotron powder-diffraction studies in the pressure range 0-21.6 kbar. Radical 1 crystallizes in the orthorhombic space group Fdd2, but undergoes an asymmetric contraction of the unit-cell size with increasing pressure. At the molecular level, this contraction of the unit cell is simultaneously accommodated by: 1) an increase in twist angle between aryl and heterocyclic rings; and 2) a shortening of the intermolecular S···N contacts, which propagate the magnetic-exchange pathway. DFT calculations based on the structures in this pressure range revealed an increase in the magnetic-exchange interaction (J) with increasing pressure, and an excellent correlation was observed between J and the magnetic-ordering temperature, which increased from 36 K at ambient pressure up to 70 K at 16 kbar.

Single-source materials for metal-doped titanium oxide: syntheses, structures, and properties of a series of heterometallic transition-metal titanium oxo cages.

Titanium dioxide (TiO(2)) doped with transition-metal ions (M) has potentially broad applications in photocatalysis, photovoltaics, and photosensors. One approach to these materials is through controlled hydrolysis of well-defined transition-metal titanium oxo cage compounds. However, to date very few such cages have been unequivocally characterized, a situation which we have sought to address here with the development of a simple synthetic approach which allows the incorporation of a range of metal ions into titanium oxo cage arrangements. The solvothermal reactions of Ti(OEt)(4) with transition-metal dichlorides (M(II)Cl(2), M = Co, Zn, Fe, Cu) give the heterometallic transition-metal titanium oxo cages [Ti(4)O(OEt)(15)(MCl)] [M = Co (2), Zn (3), Fe (4), Cu (5)], having similar MTi(4)(µ(4)-O) structural arrangements involving ion pairing of [Ti(4)O(OEt)(15)](-) anion units with MCl(+) fragments. In the case of the reaction of MnCl(2), however, two Mn(II) ions are incorporated into this framework, giving the hexanuclear Mn(2)Ti(4)(µ(4)-O) cage [Ti(4)O(OEt)(15)(Mn(2)Cl(3))] (6) in which the MCl(+) fragments in 2-5 are replaced by a [ClMn(µ-Cl)MnCl](+) unit. Emphasizing that the nature of the heterometallic cage is dependent on the metal ion (M) present, the reaction of Ti(OEt)(4) with NiCl(2) gives [Ti(2)(OEt)(9)(NiCl)](2) (7), which has a dimeric Ni(µ-Cl)(2)Ni bridged arrangement arising from the association of [Ti(2)(OEt)(9)](-) ions with NiCl(+) units. The syntheses, solid-state structures, spectroscopic and magnetic properties of 2-7 are presented, a first step toward their applications as precursor materials.

Crystal and magnetic structures of hexagonal YMnO3.

The available data on the structural and magnetic transitions in multiferroic hexagonal YMnO3 have been reviewed, first making use of the computer programs from the group theoretical ISOTROPY software suite to list possible crystal and magnetic structures, then taking into account the capability of neutron diffraction and other physical methods to distinguish them. This leads to a clear view of the transformation sequence, as follows. Hexagonal YMnO3 is paraelectric in P63/mmc at elevated temperatures, and undergoes a single structural transition on cooling through 1250 K to a ferrielectric phase in P63cm that is retained through room temperature. At a much lower temperature, 70 K, there is a magnetic transition from paramagnetic to a triangular antiferromagnetic arrangement, most likely with symmetry P63'cm'. Comment is made on the unusual coupling of ferroelectric and magnetic domains reported to occur in this material, as well as on the so-called `giant magneto-elastic' effect.