Hysteretic Spin Crossover above Room Temperature and Magnetic Coupling in Trinuclear Transition‐Metal Complexes with Anionic 1,2,4‐Triazole Ligands

Abstract

The reaction of 4-(1,2,4-triazol-4-yl)ethanesulfonate (L) with Zn(2+), Cu(2+), Ni(2+), Co(2+), and Fe(2+) gave a series of analogous neutral trinuclear complexes with the formula [M3(μ-L)6(H2O)6] (1-5). These compounds were characterized by single-crystal X-ray diffraction, thermogravimetry, and elemental analysis. The magnetic properties of compounds 2-5 were studied. Complexes 2-4 show weak antiferromagnetic superexchange, with J values of -0.33 (2), -9.56 (3), and -4.50 cm(-1) (4) (exchange Hamiltonian H = -2 J (S1S2+S2S3)). Compound 5 shows two additional crystallographic phases (5 b and 5 c) that can be obtained by dehydration and/or thermal treatment. These three phases exhibit distinct magnetic behavior. The Fe(2+) centers in 5 are in high-spin (HS) configuration at room temperature, with the central one exhibiting a non-cooperative gradual spin transition below 250 K with T1/2 = 150 K. In 5 b, the central Fe(2+) stays in its low-spin (LS) state at room temperature, and cooperative spin transition occurs at higher temperatures and with the appearance of memory effect (T1/2↑ = 357 K and T1/2↓ = 343 K). In the case of 5 c, all iron centers remain in their HS configuration down to very low temperatures, with weak antiferromagnetic coupling (J = -1.16 cm(-1)). Compound 5 b exhibits spin transition with memory effect at the highest temperature reported, which matches the remarkable features of coordination polymers.