Densely Packed CO2 Aids Charge, Spin, and Lattice Ordering Partially Fluctuated in a Porous Metal-Organic Framework Magnet

Partial charge fluctuations in the charge-ordered state of a material, often triggered by structural disorders and/or defects, can significantly alter its physical characteristics, such as magnetic long-range ordering. However, it is difficult to post-chemically fix such accidental partial fluctuations to reconstruct a uniform charge-ordered state. Herein, we report CO2-aided charge ordering demonstrated in a CO2-post-captured layered magnet, [{Ru-2(o-ClPhCO2)(4)}(2){TCNQ(OMe)(2)}] & sdot; CO2 (1 superset of CO2; o-ClPhCO2-=ortho-chlorobenzoate; TNCQ(OMe)(2)=2,5-dimethoxy-7,7,8,8-tetracyanoquinodimethane). Pristine porous layered magnet 1 had a partially charge-fluctuated ordered state, which provided ferrimagnetic ordering at T-C=65 K. Upon loading CO2, 1 adsorbed one mole of CO2, forming 1 superset of CO2, and raising T-C to 100 K. This was because of the vanishing charge fluctuations without significantly changing the framework structure. This research illustrates the post-accessible host-guest chemistry delicately combined with charge, spin, and lattice ordering in a spongy magnet. Furthermore, it highlights how this innovative approach opens up new possibilities for technology and nanoscale magnetism manipulation.