Inter-layer magnetic tuning by gas adsorption in π-stacked pillared-layer framework magnets.

Magnetism of layered magnets depends on the inter-layer through-space magnetic interactions ( ). Using guest sorption to address inter-layer pores in bulk-layered magnets is an efficient approach to magnetism control because the guest-delicate inter-layer distance ( ) is a variable parameter for modulating . Herein, we demonstrated magnetic changes induced by the adsorption of CO, N, and O gases in various isostructural layered magnets with a π-stacked pillared-layer framework, , (M = Co, 1, Fe, 2, Cr, 3; Cp* = η-CMe; 2,3,5,6-FPhCO = 2,3,5,6-tetrafluorobenzoate; TCNQ = 7,7,8,8-tetracyano--quinodimethane).

Magnetic Correlation Engineering in Spin-Sandwiched Layered Magnetic Frameworks.

The insertion of "sandwiched spins" between magnetic layers could efficiently affect the interlayer magnetic correlations, but doing so increases the complexity in the interlayer spin alignment because of competition between the inserted spin-layer interaction J and the interlayer through-space interaction J if the magnitude of J is of the same order as J with reciprocal signs of the respective interactions. Herein, systematic tuning of the magnetic phase variations by J and J in two kinds of metal-variable isostructural series of supramolecular pillared layer magnets [MCp* ][{Ru (2,3,5,6-F CO ) } (TCNQ)]⋅2 DCE (M=Co, Fe, Cr; 2,3,5,6-F PhCO =2,3,5,6-tetrafluorobenzoate; TCNQ=7,7,8,8-tetracyano-p-quinodimethane; DCE=1,2-dichloroethane) and their DCE-free series, in which [MCp* ] (Cp*=η -C Me ) species with S=0, 1/2, and 3/2 for M=Co, Fe, Cr, respectively, are sandwiched between ferrimagnetic layers of [{Ru } (TCNQ)] , is demonstrated. The results showed that the flexible magnetic natures of these magnets are changeable in dependence on J and J , as well as on interlayer inserted spins M.