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 JNNI and the interlayer through‐space interaction JNNNI if the magnitude of JNNI is of the same order as JNNNI with reciprocal signs of the respective interactions. Herein, systematic tuning of the magnetic phase variations by JNNI and JNNNI in two kinds of metal‐variable isostructural series of supramolecular pillared layer magnets [MCp*2][{Ru2II,II(2,3,5,6‐F4CO2)4}2(TCNQ)]⋅2 DCE (M=Co, Fe, Cr; 2,3,5,6‐F4PhCO2−=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*2]+ (Cp*=η5‐C5Me5) species with S=0, 1/2, and 3/2 for M=Co, Fe, Cr, respectively, are sandwiched between ferrimagnetic layers of [{Ru2}2(TCNQ)]−, is demonstrated. The results showed that the flexible magnetic natures of these magnets are changeable in dependence on JNNI and JNNNI, as well as on interlayer inserted spins M.

Magnetism of layered magnets depends on the inter-layer through-space magnetic interactions (JNNNI). Using guest sorption to address inter-layer pores in bulk-layered magnets is an efficient approach to magnetism control because...