Abstract
In this study, crystals of the hybrid layered structure, combined with Fe(III) Spin-Crossover (SCO) complexes with metal-dithiolate anionic radicals, and the precursors with nitrate and iodine counterions, are obtained and characterized. [Fe(III)(3-OMe-Sal(2)trien)][Ni(dmit)(2)] (1), [Fe(III)(3-OMe-Sal(2)trien)]NO(3)·H(2)O (2), [Fe(III)(3-OMe-Sal(2)trien)]I (3) (3-OMe-Sal(2)trien = hexadentate N(4)O(2) Schiff base is the product of the condensation of triethylenetetramine with 3-methoxysalicylaldehyde; H(2)dmit = 2-thioxo-1,3-dithiole-4,5-dithiol). Bulk SCO transition was not achieved in the range 2.0-350 K for all three compounds. Alternatively, the hybrid system (1) exhibited irreversible segregation into the spatial fractions of Low-Spin (LS) and High-Spin (HS) phases of the ferric moiety, induced by thermal cycling. Fractioning was studied using both SQUID and EPR methods. Magnetic properties of the LS and HS phases were analyzed in the framework of cooperative interactions with anionic sublattice: Anion radical layers Ni(dmit)(2) (1), and H-bonded chains with NO(3) and I (2,3). LS phase of (1) exhibited unusual quasi-two-dimensional conductivity related to the Arrhenius mechanism in the anion radical layers, ρ(||c) = 2 × 10(5) Ohm·cm and ρ(⟂c) = 7 × 10(2) Ohm·cm at 293 K. Ground spin state of the insulating HS phase was distinctive by ferromagnetically coupled spin pairs of HS Fe(3+), S = 5/2, and metal-dithiolate radicals, S = 1/2.