Light-induced spin-state switching in the mixed crystal series of the 2D coordination network {[Zn1−xFex(bbtr)3](BF4)2}∞: optical spectroscopy and cooperative effects

Abstract

Depending on the iron(II) concentration, the mixed crystals of {[Zn_1−xFe_x(bbtr)₃](BF₄)₂}_∞, bbtr = 1,4-di(1,2,3-triazol-1-yl)butane, 0.01 ≤ x ≤ 1, show macroscopic light-induced bistability between the high-spin and the low-spin state. In the highly diluted system with x = 0.01 and up to x = 0.31, the photoinduced low-spin state always relaxes back to the high-spin state independent of the initial light-induced low-spin fraction. In the highly concentrated mixed crystals with x = 0.67, 0.87 and 1, the strong cooperative effects coupled to a crystallographic phase transition result in light-induced bistability with decreasing critical light-induced low-spin fraction and increasing hysteresis width for increasing iron(II) concentrations. The lower limit for the light-induced bistability was estimated to be x ≈ 0.5.