Kosaka Wataru, Hiwatashi Yoshie, Amamizu Naoka, Kitagawa Yasutaka, Zhang Jun, Miyasaka Hitoshi
Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan.
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, Sendai 980-8578, Japan.
Angew Chem Int Ed Engl. 2023 Nov 27;62(48):e202312205. doi: 10.1002/anie.202312205. Epub 2023 Oct 26.
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 CO -aided charge ordering demonstrated in a CO -post-captured layered magnet, [{Ru (o-ClPhCO ) } {TCNQ(OMe) }] ⋅ CO (1⊃CO ; o-ClPhCO =ortho-chlorobenzoate; TNCQ(OMe) =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 =65 K. Upon loading CO , 1 adsorbed one mole of CO , forming 1⊃CO , and raising T 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.
材料电荷有序态中的部分电荷涨落通常由结构无序和/或缺陷引发，这会显著改变其物理特性，如磁长程有序。然而，通过后化学方法固定这种偶然的部分涨落以重建均匀的电荷有序态是困难的。在此，我们报道了在一种CO后捕获的层状磁体[{Ru(o-ClPhCO)₂}{TCNQ(OMe)₂}]·CO(1⊃CO；o-ClPhCO=邻氯苯甲酸酯；TNCQ(OMe)=2,5-二甲氧基-7,7,8,8-四氰基对苯二醌二甲烷)中展示的CO辅助电荷有序化。原始的多孔层状磁体1具有部分电荷涨落的有序态，在T = 65 K时呈现亚铁磁有序。加载CO后，1吸附一摩尔CO，形成1⊃CO，并将T提高到100 K。这是因为电荷涨落消失，而框架结构没有显著变化。这项研究说明了在海绵状磁体中后可及的主客体化学与电荷、自旋和晶格有序化的巧妙结合。此外，它突出了这种创新方法如何为技术和纳米级磁操控开辟新的可能性。
