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, [{Ru2 (o-ClPhCO2 )4 }2 {TCNQ(OMe)2 }] ⋅ CO2 (1⊃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 TC =65 K. Upon loading CO2 , 1 adsorbed one mole of CO2 , forming 1⊃CO2 , and raising TC 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.