Magnetic Switching by the In Situ Electrochemical Control of Quasi-Spin-Peierls Singlet States in a Three-Dimensional Spin Lattice Incorporating TTF-TCNQ Salts

Hiroki Fukunaga, Masanori Tonouchi, Kouji Taniguchi, Wataru Kosaka, Shojiro Kimura, Hitoshi Miyasaka

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

Abstract

Magnetic phase switching in a coordination polymer is reported, which is demonstrated by combining two processes: (A) the pre-organization of magnetic/redox-active molecules into a framework, and (B) a post-treatment through electrochemical tuning of the pre-organized molecules. A TTF.+–TCNQ.− salt (TTF=tetrathiafulvalene; TCNQ=7,7,8,8-tetracyano-p-quinodimethane) was incorporated into a three-dimensional framework with paddlewheel-type dimetal(II, II) units ([M2 II,II]; M=Ru with S=1, 1; and Rh with S=0, 2), where the [M2 II,II] and TCNQ.− units form the coordinating framework, and TTF.+is located in the pores of framework, forming an irregular π-stacking alternating column with the TCNQ.− in the framework. In 1, the spins of [Ru2 II,II] and TCNQ.− units make a magnetic correlation through the framework upon decreasing the temperature from 300 K, which is, however, suddenly suppressed below 137 K (=Td (1)) by the formation of a spin singlet in the TTF.+–TCNQ.− columns, as seen in the spin-Peierls transition (Td (2)=200 K). This material was incorporated as a cathode in a Li-ion battery (LIB); a long-range ferrimagnetic correlation was formed through the three-dimensional [{Ru2 II,II}2TCNQ] framework at Tc=78 K in the discharge process. The reversible magnetic phase switching between the non-volatile ferrimagnetic and paramagnetic states, resulting from the local spin tuning of quasi-spin-Peierls singlet, is demonstrated through the discharge/charge cycling of the LIB.

Original languageEnglish
Pages (from-to)4294-4303
Number of pages10
JournalChemistry - A European Journal
Volume24
Issue number17
DOIs
Publication statusPublished - 2018 Mar 20

Keywords

  • Li ion battery
  • MOF
  • magneto-electric coupling
  • molecular magnet
  • spin dimerization

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Fingerprint Dive into the research topics of 'Magnetic Switching by the In Situ Electrochemical Control of Quasi-Spin-Peierls Singlet States in a Three-Dimensional Spin Lattice Incorporating TTF-TCNQ Salts'. Together they form a unique fingerprint.

Cite this