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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
Author(s) -
Fukunaga Hiroki,
Tonouchi Masanori,
Taniguchi Kouji,
Kosaka Wataru,
Kimura Shojiro,
Miyasaka Hitoshi
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704815
Subject(s) - ferrimagnetism , singlet state , tetrathiafulvalene , paramagnetism , chemistry , molecule , condensed matter physics , spins , crystallography , spin (aerodynamics) , materials science , magnetization , atomic physics , magnetic field , physics , organic chemistry , quantum mechanics , thermodynamics , excited state
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 ([ M 2 II,II ]; M =Ru with S= 1, 1 ; and Rh with S= 0, 2 ), where the [ M 2 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 [Ru 2 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 (= T d ( 1 )) by the formation of a spin singlet in the TTF .+ –TCNQ .− columns, as seen in the spin‐Peierls transition ( T d ( 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 [{Ru 2 II,II } 2 TCNQ] − framework at T c =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.