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 (J NNNI). 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 (l trans) is a variable parameter for modulating J NNNI. Herein, we demonstrated magnetic changes induced by the adsorption of CO2, N2, and O2 gases in various isostructural layered magnets with a π-stacked pillared-layer framework, , (M = Co, 1, Fe, 2, Cr, 3; Cp* = η5-C5Me5; 2,3,5,6-F4PhCO2 - = 2,3,5,6-tetrafluorobenzoate; TCNQ = 7,7,8,8-tetracyano-p-quinodimethane). Each compound had almost identical adsorption capability for the three types of gases; only CO2 adsorption was found to have a gated profile. A breathing-like structural modulation involving the extension of l trans occurred after the insertion of gases into the isolated pores between the [Ru2]2-TCNQ ferrimagnetic layers, which is more significant for CO2 than for O2 and N2, due to the CO2-gated transition. While adsorbent 1 with M = Co (S = 0) was an antiferromagnet with T N = 75 K, 1⊃CO2 was a ferrimagnet with T C = 76 K, whereas 1⊃N2 and 1⊃O2 were antiferromagnets with T N = 68 K. The guest-insertion effect was similarly confirmed in 2 and 3, and was characteristically dependent on the type of sandwiched spin in as M = Fe (S = 1/2) and Cr (S = 3/2), respectively. This study reveals that common gases such as CO2, O2, and N2 can serve as crucial triggers for the change in magnetism as a function of variable parameter l trans.

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 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 ][{Ru2 II,II (2,3,5,6-F4 CO2 )4 }2 (TCNQ)]⋅2 DCE (M=Co, Fe, Cr; 2,3,5,6-F4 PhCO2 - =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 -C5 Me5 ) 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.