title: Structural, thermal and photomagnetic properties of spin crossover [Fe(bpp)2]2+ salts bearing [Cr(L)(ox)2]- anions.
abstract: This paper is divided into two parts: in the first part, the influence of solvate molecules on the magnetic properties of spin crossover salts of [Fe(bpp)(2)][Cr(L)(ox)(2)]ClO(4) x nS (bpp = 2,6-bis(pyrazol-3yl)pyridine; L = 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen); ox = oxalate dianion; S = solvent) is analyzed. The second part is devoted to the photomagnetic properties of the previously reported [Fe(bpp)(2)][Cr(L)(ox)(2)](2) family of compounds. The study describes the crystal structure, differential scanning calorimetry (DSC) and magnetic properties of [Fe(bpp)(2)][Cr(bpy)(ox)(2)]ClO(4) x EtOH x 4 H(2)O (1) and [Fe(bpp)(2)][Cr(phen)(ox)(2)]ClO(4) x 1.5 EtOH x 4 H(2)O (2). Both salts are high-spin (HS) compounds. Desolvation of 1 yields a material exhibiting a gradual spin crossover that involves 50% of the Fe(2+) cations. Rehydration of this desolvated salt induces a significant increase in the low-spin (LS) population. Desolvation of 2 affords a material showing a more abrupt spin crossover with thermal hysteresis (T(1/2)(increasing) = 286 K and T(1/2)(decreasing) = 273 K). This material is not very sensitive to rehydration. The anhydrous compounds [Fe(bpp)(2)][Cr(bpy)(ox)(2)](2) (3) and [Fe(bpp)(2)][Cr(phen)(ox)(2)](2) (4) display some quantitative photomagnetic conversion with T(LIESST) values of 41 and 51 K, respectively. Kinetic parameters governing the photo-induced HS-LS relaxation process have been determined and used to reproduce the T(LIESST) curves.
authors.affiliation: Instituto de Ciencia Molecular, Universitat de València, P. O. Box 22085, 46071-Valencia, Spain.
authors.forename: Miguel
authors.initials: M
authors.lastname: Clemente-León
authors.forename: Eugenio
authors.initials: E
authors.lastname: Coronado
authors.forename: M Carmen
authors.initials: MC
authors.lastname: Giménez-López
authors.forename: Francisco M
authors.initials: FM
authors.lastname: Romero
authors.forename: Saket
authors.initials: S
authors.lastname: Asthana
authors.forename: Cédric
authors.initials: C
authors.lastname: Desplanches
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Létard