Thermal and Optical Switching of Iron(II) Complexes

Abstract Transition metal chemistry contains a class of complex compounds for which the spin state of the central atom changes from high spin to low spin when the temperature is lowered. This is accompanied by changes of the magnetic and optical properties that make the thermally induced spin transition (also called spin crossover) easy to follow. The phenomenon is found in the solid state as well as in solution. Amongst this class, iron( II ) spin crossover compounds are distinguished for their great variety of spin transition behavior; it can be anything from gradual to abrupt, stepwise, or with hysteresis effects. Many examples have been thoroughly studied by Mössbauer and optical spectroscopy, measurements of the magnetic susceptibilities and the heat capacities, as well as crystal structure analysis. Cooperative interactions between the complex molecules can be satisfactorily explained from changes in the elastic properties during the spin transition, that is, from changes in molecular structure and volume. Our investigations of iron( II ) spin crossover compounds have shown that green light will switch the low spin state to the high spin state, which then can have a virtually unlimited lifetime at low temperatures (this phenomenom is termed light‐induced excited spin state trapping—acronym: LIESST). Red light will switch the metastable high spin state back to the low spin state. We have elucidated the mechanism of the LIESST effect and studied the deactivation kinetics in detail. It is now well understood within the theoretical context of radiationless transitions. Applications of the LIESST effect in optical information technology can be envisaged.