6533b857fe1ef96bd12b4e1e

RESEARCH PRODUCT

A novel paramagnetic molecular superconductor formed by bis(ethylenedithio)tetrathiafulvalene, tris(oxalato)ferrate(iii) anions and bromobenzene as guest molecule: ET4[(H3O)Fe(C2O4)3]·C6H5Br

Eugenio CoronadoCarlos Giménez-saizSimona CurreliCarlos J. Gómez-garcía

subject

SuperconductivityCondensed matter physicsSpin statesMagnetoresistanceGeneral ChemistryMagnetic susceptibilityParamagnetismchemistry.chemical_compoundCrystallographyTransition metalchemistryMeissner effectMaterials ChemistryTetrathiafulvalene

description

The new paramagnetic molecular superconductor ET4[(H3O)Fe(C2O4)3]·C6H5Br (1) (Tc = 4.0 K) contains layers of superconducting ET donors alternating with paramagnetic hexagonal layers formed by (H3O)+, [Fe(C2O4)3]3− and guest C6H5Br molecules located in the hexagonal cavities. Conductivity measurements show metallic behavior from room temperature with a minimum in the resistivity at ca. 50 K followed by a smooth increase and a sharp drop in the resistivity with an onset at 4.0 K and a zero resistance at ca. 1.0 K. Magnetoresistance measurements indicate that Hc1 is about 7 mT and that Hc2 is very anisotropic (Hc2⊥ ≥ 5.5 T and Hc2|| ≈ 0.5 T). Magnetic susceptibility measurements show the expected paramagnetic behavior of the high spin S = 5/2 Fe(III) ions and an extra temperature independent paramagnetism (Pauli-type) typical of metallic systems. Low field DC and AC magnetic measurements show the expected Meissner effect below ca. 3.5 K and confirm the value of Hc1 obtained from magnetoresistance measurements. X and Q-band ESR spectra show a dysonian narrow line coming from the conducting sublattice plus 5 lines from the [Fe(C2O4)3]3− anion, as expected for an S = 5/2 ground spin state with low ZFS. Heat capacity measurements also confirm the superconducting transition at low temperatures and show a broad transition at higher temperatures that can be attributed to an order–disorder transition of some of the terminal ethylene groups of the ET molecules.

https://doi.org/10.1039/b500107m