A nanoporous molecular magnet with reversible solvent-induced mechanical and magnetic properties

Interest in metal–organic open-framework structures has increased enormously in the past few years because of the potential benefits of using crystal engineering techniques to yield nanoporous materials with predictable structures and interesting properties. Here we report a new efficient methodology for the preparation of metal–organic open-framework magnetic structures based on the use of a persistent organic free radical (PTMTC), functionalized with three carboxylic groups. Using this approach, we create an open-framework structure Cu3(PTMTC)2(py)6(CH3CH2OH)2(H2O), which we call MOROF-1, combining very large pores (2.8–3.1 nm) with bulk magnetic ordering. MOROF-1 shows a reversible and highly selective solvent-induced 'shrinking–breathing' process involving large volume changes (25–35%) that strongly influence the magnetic properties of the material. This magnetic sponge-like behaviour could be the first stage of a new route towards magnetic solvent sensors.