Exploring a prototype for cooperative structural phase transition in cobalt(ii) spin crossover compounds

Abstract

The creation of magnetically switchable materials that concurrently incorporate spin crossover (SCO) and a structural phase transition (SPT) presents a significant challenge in materials science. In this study, we prepared four structurally related cobalt(II)-based SCO compounds: two one-dimensional (1D) chains of {[(enbzp)Co(μ-L)](ClO₄)₂·sol}_n (L = bpee, sol = 2MeOH·H₂O, 1; L = bpea, sol = none, 2; enbzp = N,N′-(ethane-1,2-diyl)bis(1-phenyl-1-(pyridin-2-yl)methanimine); bpee = 1,2-bis(4-pyridyl)ethylene; and bpea = 1,2-bis(4-pyridyl)ethane) and their discrete segments, [{(enbzp)Co}₂(μ-L)](ClO₄)₄·2MeOH (L = bpee, 3; L = bpea, 4). In all of these complexes, each Co(II) center is equatorially chelated by the planar tetradentate ligand enbzp and connected to a chain or dinuclear structure through bpee or bpea ligands along its axial direction. All of the complexes, including their desolvated phases, displayed overall incomplete and gradual SCO properties. Interestingly, the desolvated phase of 1 exhibited an additional non-spin magnetic transition characterized by wide room-temperature hysteresis (>40 K), which was reversible and rate-dependent, showcasing the synergy between SCO and SPT manifested through slow kinetics. We discuss the possible reasons for the distinct features and our findings demonstrate that the combination of a rigid polymeric framework with flexible substituents holds promise for achieving synergy between SCO and SPT.