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Magnetic Switching by the In Situ Electrochemical Control of Quasi-Spin-Peierls Singlet States in a Three-Dimensional Spin Lattice Incorporating TTF-TCNQ Salts
- Source :
- Chemistry - A European Journal. 24:4294-4303
- Publication Year :
- 2018
- Publisher :
- Wiley, 2018.
-
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 ([M2II,II ]; M=Ru with S=1, 1; and Rh with S=0, 2), where the [M2II,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 [Ru2II,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 [{Ru2II,II }2 TCNQ]- 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.
- Subjects :
- Spins
Coordination polymer
Organic Chemistry
02 engineering and technology
General Chemistry
010402 general chemistry
021001 nanoscience & nanotechnology
01 natural sciences
Catalysis
0104 chemical sciences
Paramagnetism
chemistry.chemical_compound
Crystallography
chemistry
Ferrimagnetism
Molecule
Singlet state
0210 nano-technology
Spin (physics)
Tetrathiafulvalene
Subjects
Details
- ISSN :
- 09476539
- Volume :
- 24
- Database :
- OpenAIRE
- Journal :
- Chemistry - A European Journal
- Accession number :
- edsair.doi.dedup.....f01ad39c4af4b57ede239b418ac1618d