Molecule-based solids represent a rare opportunity to combine, adjust, and interrelate structural and physical functionalities to develop multifunctional materials. Here we report on a series of porous supramolecular magnets whose magnetic properties are related to their sorption state. A family of magnets of the formula [{Mn(HL)(H2O)}(2)Mn{Mo(CN)(7)}(2)]center dot 2H(2)O have been obtained by assembling the heptacyanometalate building unit {Mo(CN)(7)}(4-) with Mn(II) in the presence of protonated N,N-dimethylalaninol (L) as ligand, the latter being either as a racemic mixture or as a chiral R-or S-enantiomer. The resulting magnets possess an open framework structure and exhibit a T-c with a switching behavior (T-c = 85 K <-> 106 K) as a function of the hydration state. Moreover, chiral magnets are formed with the optically active ligands. The H2O and gas (N-2, CO2, CO) sorption features, the magnetic behavior of both the hydrated and dehydrated magnets, and the crystal structures of the hydrated chiral (S) and racemic magnets are described.