High-temperaturewide thermal hysteresis of an iron(II) dinuclear double helicate

Abstract

Two new dinuclear iron(II) complexes (1•PF6 and 1•AsF6) of the general formula [Fe2II(L2C3)2](X)4·nH2O·mMeCN (X = PF6, n = m = 1.5 for 1•PF6 and X = AsF6, n = 3, m = 1 for 1•AsF6) have been prepared and structurally characterized, where L2C3 is a bis-1,2,3-triazolimine type Schiff-base ligand, 1,1'-[propane-1,3-diylbis(1H-1,2,3-triazole-1,4-diyl)]bis{N-[2-(pyridin-2-yl)ethyl]methanimine}. Single crystal X-ray structure analyses revealed that 1•PF6 and 1•AsF6 are isostructural. The complex-cation [Fe2II(L2C3)2]4+ of both has the same dinuclear double helicate architecture, in which each iron(II) center has an N6 octahedral coordination environment. Neighboring helicates are connected by intermolecular π-π interactions to give a chiral one-dimensional (1D) structure, and cationic 1D chains with the opposite chirality exist in the crystal lattice to give a heterochiral crystal. Magnetic and differential scanning calorimetry (DSC) studies were performed only for 1•AsF6, since the thermal stability in a high-temperature spin crossover (SCO) region of 1•PF6 is poorer than that of 1•AsF6. 1•AsF6 shows an unsymmetrical hysteretic SCO between the low-spin-low-spin (LS-LS) and high-spin-high-spin (HS-HS) states at above room temperature. The critical temperatures of warming (Tc↑) and cooling (Tc↓) modes in the abrupt spin transition area are 485 and 401 K, respectively, indicating the occurrence of 84 K-wide thermal hysteresis in the first thermal cycle.