Optical microscopy imaging of the thermally-induced spin transition and isothermal multi-stepped relaxation in a low-spin stabilized spin-crossover material

Abstract

The thermal spin transition and the photo-induced high-spin → low-spin relaxation of the prototypical [Fe(ptz)₆](BF₄)₂ spin-crossover compound (ptz = 1-propyltetrazole) diluted in the isostructural ruthenium host lattice [Ru(ptz)₆](BF₄)₂, which stabilizes the Fe(II) low-spin state, have been investigated. We demonstrate the presence of a crystallographic phase transition around 145 K (i.e. from the high-temperature ordered high-spin phase to a low-temperature disordered low-spin phase) upon slow cooling from room temperature. This crystallographic phase transition is decoupled from the thermal spin transition. A supercooled ordered low-spin phase is observed as in the pure Fe(II) analogue upon fast cooling. A similar order–disorder phase transition is also observed for pure [Ru(ptz)₆](BF₄)₂ but at relatively higher temperature (i.e. at around 150 K) without involving any spin transition. For Ru-diluted [Fe(ptz)₆]²⁺, the crystallographic phase transition as well as strong cooperative effects involving various degrees of elastic frustration are at the origin of stepped sigmoidal high-spin → low-spin relaxation curves, which are modelled in the framework of a classical mean field model, considering both the tunnelling and thermally activated regimes. Optical microscopy studies performed on two different single crystals showed the existence of hysteretic thermal transitions with slight domain formation, hardly visible in the static crystal images. This behavior is attributed to the double effect upon Ru dilution, which decreases the cooperative character of the transition and simultaneously reduces the optical contrast between the LS and HS states. Moreover, the transition temperature revealed to be slightly crystal dependent, highlighting the crucial role of the spatial distribution of Ru from one crystal to another, in addition to the well-known effects of crystal shape and size.