Measurement of Reverse-Light-Induced Excited Spin State Trapping in Spin Crossover Systems: A Study Case with Zn1−xFex(6-mepy)3tren(PF6)2·CH3CN; x = 0.5%

Abstract

In an attempt to better understand the physics governing the apparition of reverse-light-induced excited spin state trapping (LIESST) phenomena in spin crossover (SCO) compounds, we have studied the LIESST effect and the possibility of a reverse-LIESST effect in the SCO complex Zn1−xFex(6-mepy)3tren(PF6)2·CH3CN, x = 0.5%. ((6-mepy)3tren = tris{4-[(6-methyl)-2-pyridyl]-3-aza-butenyl}amine)). This complex was chosen as a good candidate to show reverse-LIESST by comparison with its unsolvated analogue, since the introduction of acetonitrile in the structure leads to the stabilisation of the high-spin state and both exhibit a very abrupt thermal spin transition. Indeed, the steep thermal spin transitions of two differently polarised crystals of Zn1−xFex(6-mepy)3tren(PF6)2·CH3CN, x = 0.5% have been characterised in detail in a first step using absorption spectroscopy and no influence of the polarisation was found. These were then fitted within the mean field model to obtain the variation in the enthalpy and entropy and the critical temperatures associated with the process, which are significantly lower with respect to the unsolvated compound due to the incorporation of acetonitrile. In a second step, the light-induced low-spin-to-high-spin transition at low temperatures based on LIESST and its subsequent high-spin-to-low-spin relaxation at different temperatures were characterised by time-resolved absorption spectroscopy, with exponential behaviour in both cases. The stabilisation of the high-spin state due to the presence of acetonitrile was evidenced. Finally, light-induced high-spin-to-low-spin state transition at low temperature based on reverse-LIESST was attempted by time-resolved absorption spectroscopy but the Fe(II) concentration was too low to observe the effect.