TY - JOUR
T1 - Magnetic Switching by the In Situ Electrochemical Control of Quasi-Spin-Peierls Singlet States in a Three-Dimensional Spin Lattice Incorporating TTF-TCNQ Salts
AU - Fukunaga, Hiroki
AU - Tonouchi, Masanori
AU - Taniguchi, Kouji
AU - Kosaka, Wataru
AU - Kimura, Shojiro
AU - Miyasaka, Hitoshi
PY - 2018/3/20
Y1 - 2018/3/20
N2 - 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.
AB - 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.
KW - Li ion battery
KW - MOF
KW - magneto-electric coupling
KW - molecular magnet
KW - spin dimerization
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U2 - 10.1002/chem.201704815
DO - 10.1002/chem.201704815
M3 - Article
C2 - 29446499
AN - SCOPUS:85042010932
VL - 24
SP - 4294
EP - 4303
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 17
ER -