High-Temperature Wide Thermal Hysteresis of an Iron(II) Dinuclear Double Helicate

Two new dinuclear iron(II) complexes (1·PF₆ and 1·AsF₆) of the general formula [Fe^II₂(L2^C3)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 L2^C3 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 [Fe^II₂(L2^C3)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 (T_c↑) and cooling (T_c↓) 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. View Full-Text