[2 + 2] Photocyclization converts thermally induced spin crossover effect into “hidden hysteresis” one

Abstract

The light induced [2 + 2] cyclization of the flexible coumarin-based ligand (L) converts the spin crossover active HS1 ⇆ LS1 mononuclear system [Fe(L)₆](BF₄)₂·4CH₃CN (1) into the high spin 1D coordination polymer (2). The contribution of the resulting high spin form HS2 is directly related to the degree of photoconversion and, at the same time, practically does not affect the properties of the remaining thermally active spin crossover centers (HS1). The origin of such a fundamental change in properties is an appearance of strain caused by ligand dimerization, which acts directly on the metal chromophores and is transmitted to the crystal lattice. The spin state of 2 can be changed by applying pressure as well as by light irradiation revealing a “hidden hysteresis” phenomenon (Appl. Phys. Lett., 2008, 93, 21906), referring to the appearance of the low spin state not accessible through thermal activation but through reversed-LIESST. A unique feature of 2 is the feasibility to attain any steady state within the hidden hysteresis region by combination of perturbations triggered by changes in temperature and light (808 nm HS2 → LS2 and 532 nm LS2 → HS2). Such states are stable within a time scale of several hours.