Guest Induced Strong Cooperative One- and Two-Step Spin Transitions in Highly Porous Iron(II) Hofmann-Type Metal-Organic Frameworks.

The synthesis, crystal structure, magnetic, calorimetric, and Mössbauer studies of a series of new Hofmann-type spin crossover (SCO) metal-organic frameworks (MOFs) is reported. The new SCO-MOFs arise from self-assembly of FeII , bis(4-pyridyl)butadiyne (bpb), and [Ag(CN)2 ]- or [MII (CN)4 ]2- (MII = Ni, Pd). Interpenetration of four identical 3D networks with α-Po topology are obtained for {Fe(bpb)[AgI (CN)2 ]2 } due to the length of the rod-like bismonodentate bpb and [Ag(CN)2 ]- ligands. The four networks are tightly packed and organized in two subsets orthogonally interpenetrated, while the networks in each subset display parallel interpenetration. This nonporous material undergoes a very incomplete SCO, which is rationalized from its intricate structure. In contrast, the single network Hofmann-type MOFs {Fe(bpb)[MII (CN)4 ]}·nGuest (MII = Ni, Pd) feature enhanced porosity and display complete one-step or two-step cooperative SCO behaviors when the pores are filled with two molecules of nitrobenzene or naphthalene that interact strongly with the pyridyl and cyano moieties of the bpb ligands via π-π stacking. The lack of these guest molecules favors stabilization of the high-spin state in the whole range of temperatures. However, application of hydrostatic pressure induces one- and two-step SCO.