Multiple Bistability and Tristability with Dual Spin-State Conversions in [Fe(dpp)2][Ni(mnt)2]2·MeNO2

Abstract

The multicomponent system of [Fe(dpp)(2)][Ni(mnt)(2)](2).MeNO(2) (1; dpp = 2,6-bis(pyrazol-1-yl)pyridine and mnt = maleonitriledithiolate) was prepared by the reaction of [Fe(dpp)(2)](BF(4))(2) with (Bu(4)N)[Ni(mnt)(2)] in MeNO(2). Variable-temperature X-ray structural analyses, magnetic susceptibility, and heat capacity measurements confirmed that 1 undergoes multiple spin-state conversions in both the cationic and anionic components. The asymmetric unit in the crystal contains one [Fe(dpp)(2)](2+) cation, two [Ni(mnt)(2)](-) anions ([Ni1](-) and [Ni2](-)), and one solvent molecule. Magnetic susceptibility measurements revealed that a paramagnetic state in the high-temperature region (HT phase) was abruptly converted to a diamagnetic low-temperature (LT) phase below 180 K as the temperature was lowered from 270 K. As the temperature was raised from 125 to 270 K, successive phase transitions occurred to the HT phase via intermediate phases (IM1, IM2, and IM3) at 175.5, 186.5, 194.0, and 244.0 K, respectively. In the HT phase [Fe(dpp)(2)](2+) is in the high-spin state, and each [Ni1](-) and [Ni2](-) moiety is arranged in monomeric form with an S = (1)/(2) spin ground state. In the LT phase [Fe(dpp)(2)](2+) is in the low-spin state and the nickel moieties are dimerized and diamagnetic. In the IM1 and IM2 phases the iron(II) sites are partially in the HS state and both [Ni](-) moieties are dimeric, as suggested by (57)Fe Mossbauer measurements. In the IM3 phase, [Fe(dpp)(2)](2+) is in the HS state and the anions exist in both their monomeric ([Ni1](-)) and dimeric ([Ni2](-)) forms. Rapid thermal quenching from 300 to 5 K yielded a metastable HS phase, which relaxed to the LT phase via the IM1 phase as the temperature was raised to 150 K. A partial light induced spin transition on the iron site was observed at 5 K.