Magnet Creation by Guest Insertion into a Paramagnetic Charge-Flexible Layered Metal–Organic Framework

April 29, 2021

Title

Magnet Creation by Guest Insertion into a Paramagnetic Charge-Flexible Layered Metal–Organic Framework

Author

Jun Zhang, Wataru Kosaka, Hiroyasu Sato, Hitoshi Miyasaka

Year

2021

Journal

J. Am. Chem. Soc.

Abstract

Changing nonmagnetic materials to spontaneous magnets is an alchemy-inspiring concept in materials science; however, it is not impossible. Here, we demonstrate chemical modification from a nonmagnet to a bulk magnet of either a ferrimagnet or antiferromagnet, depending on the adsorbed guest molecule, in an electronic-state-flexible layered metal–organic framework, [{Ru2(2,4-F2PhCO2)4}2TCNQ(EtO)2] (1; 2,4-F2PhCO2– = 2,4-difluorobenzoate; TCNQ(EtO)2 = 2,5-diethoxy-7,7,8,8-tetracyanoquinodimethane). The guest-free paramagnet 1 undergoes a thermally driven intralattice electron transfer involving a structural transition at 380 K. This charge modification can also be implemented by guest accommodations at room temperature; 1 adsorbs several organic molecules, such as benzene (PhH), p-xylene (PX), 1,2-dichloroethane (DCE), dichloromethane (DCM), and carbon disulfide (CS2), forming 1-solv with intact crystallinity. This induces an intralattice electron transfer to produce a ferrimagnetically ordered magnetic layer. According to the interlayer environment tuned by the corresponding guest molecule, the magnetic phase is consequently altered to a ferrimagnet for the guests PhH, PX, DCE, and DCM or an antiferromagnet for CS2. This is the first demonstration of the postsynthesis of bulk magnets using guest-molecule accommodations.

Instrument

NRS-4500

Keywords

Raman spectroscopy, Paramagnetic, organic framework, magnet