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

Wataru Kosaka; Yoshie Hiwatashi; Naoka Amamizu; Yasutaka Kitagawa; Jun Zhang; Hitoshi Miyasaka

doi:10.1002/anie.202312205

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

Angew Chem Int Ed Engl. 2023 Nov 27;62(48):e202312205. doi: 10.1002/anie.202312205. Epub 2023 Oct 26.

Authors

Wataru Kosaka^{1

2}, Yoshie Hiwatashi^{1

2}, Naoka Amamizu³, Yasutaka Kitagawa³, Jun Zhang⁴, Hitoshi Miyasaka^{1

2}

Affiliations

¹ Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan.
² Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, Sendai 980-8578, Japan.
³ Department of Materials Engineering Science, Osaka University, 1-3 Machikaneyama-chou, Toyonaka, Osaka 560-0043, Japan.
⁴ College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China.

PMID: 37840402
DOI: 10.1002/anie.202312205

Abstract

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 T_C =65 K. Upon loading CO₂ , 1 adsorbed one mole of CO₂ , forming 1⊃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.

Keywords: Donor-Acceptor Systems; Magnetic Properties; Metal-Organic Frameworks; Phase Transition; Ruthenium.