Programmable spin-state switching in a mixed-valence spin-crossover iron grid

Photo-switchable systems, such as discrete spin-crossover complexes and bulk iron–cobalt Prussian blue analogues, exhibit, at a given temperature, a bistability between low- and high-spin states, allowing the storage of binary data. Grouping different bistable chromophores in a molecular framework was postulated to generate a complex that could be site-selectively excited to access multiple electronic states under identical conditions. Here we report the synthesis and the thermal and light-induced phase transitions of a tetranuclear iron(II) grid-like complex and its two-electron oxidized equivalent. The heterovalent grid is thermally inactive but the spin states of its constituent metal ions are selectively switched using different laser stimuli, allowing the molecule to exist in three discrete phases. Site-selective photo-excitation, herein enabling one molecule to process ternary data, may have major ramifications in the development of future molecular memory storage technologies. It has been suggested that photo-switchable magnetic systems could be grouped together to form complexes with multiple accessible electronic states. Here, the authors report a tetranuclear iron cluster, addressable by laser stimuli, which exhibits three discrete electronic phases.