TY - JOUR
T1 - Metamagnetism with TN = 97 K in a layered assembly of paddlewheel [Ru2] units and TCNQ
T2 - An empirical rule for interlayer distances determining the magnetic ground state
AU - Kosaka, Wataru
AU - Itoh, Masahisa
AU - Miyasaka, Hitoshi
N1 - Funding Information:
This study was supported by a Grant-in-Aid for Scientific Research (Grant No. 16H02269) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan; a Grand-in-Aid for Scientific Research on Innovative Areas (‘‘p-System Figuration’’ Area 2601, No. JP17H05137) from the Japan Society for the Promotion of Science (JSPS); and the E-IMR project.
Funding Information:
This study was supported by a Grant-in-Aid for Scientific Research (Grant No. 16H02269) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan; a Grand-in-Aid for Scientific Research on Innovative Areas (''p-System Figuration'' Area 2601, No. JP17H05137) from the Japan Society for the Promotion of Science (JSPS); and the E-IMR project.
Publisher Copyright:
© 2018 Royal Society of Chemistry. All rights reserved.
PY - 2018
Y1 - 2018
N2 - A donor (D)/acceptor (A) assembly reaction of the paddlewheel-type diruthenium(II,II) complex [Ru2(m-ClPhCO2)4(THF)2] (m-ClPhCO2 = meta-chlorobenzoate; abbreviated hereafter as [Ru2]) with 2,5-dimethoxy-7,7,8,8-tetracyano-p-quinodimethane (TCNQ(MeO)2) in a dichloromethane (DCM)/1,1,2,2tetrachloroethane (TCE) solvent system led to the formation of a two-dimensional layered D2A compound with crystallization solvents located between layers: [{Ru2(m-ClPhCO2)4}2{TCNQ(MeO)2}]3.3DCM2TCE (1). Compound 1 undergoes an intra-lattice one-electron transfer to form a charge-distributed state with the formula [{RuII,III 2 }+-TCNQ-{RuII,II 2 }] with intra-layer ferrimagnetic spin ordering through dp*-pp* orbital overlap that results in ferrimagnetic arrangement with antiferromagnetic interactions over heterospins of S = 1 for [RuII,II 2 ] and S = 3/2 for [RuII,III 2 ] via S = 1/2 for TCNQ. Consequently, because of the presence of interlayer antiferromagnetic interactions, 1 has an antiferromagnetic ground state with TN = 97 K. On applying a field of less than 0.5 T, a spin flip is induced, yielding a field-induced ferrimagnet (a type of metamagnet) with a large coercive field of 1.2 T at 1.8 K. Compound 1 has interlayer translational (i.e., interlayer [Ru2] [Ru2] or TCNQ TCNQ distance) (l2) and interlayer vertical (l1) distances of 10.30 and 9.82 Å, respectively. By comparison of the magnetostructural correlations of this type of layered magnet, this class of antiferromagnets, including 1, reveal a trend of having l2 r 10.3 Å.
AB - A donor (D)/acceptor (A) assembly reaction of the paddlewheel-type diruthenium(II,II) complex [Ru2(m-ClPhCO2)4(THF)2] (m-ClPhCO2 = meta-chlorobenzoate; abbreviated hereafter as [Ru2]) with 2,5-dimethoxy-7,7,8,8-tetracyano-p-quinodimethane (TCNQ(MeO)2) in a dichloromethane (DCM)/1,1,2,2tetrachloroethane (TCE) solvent system led to the formation of a two-dimensional layered D2A compound with crystallization solvents located between layers: [{Ru2(m-ClPhCO2)4}2{TCNQ(MeO)2}]3.3DCM2TCE (1). Compound 1 undergoes an intra-lattice one-electron transfer to form a charge-distributed state with the formula [{RuII,III 2 }+-TCNQ-{RuII,II 2 }] with intra-layer ferrimagnetic spin ordering through dp*-pp* orbital overlap that results in ferrimagnetic arrangement with antiferromagnetic interactions over heterospins of S = 1 for [RuII,II 2 ] and S = 3/2 for [RuII,III 2 ] via S = 1/2 for TCNQ. Consequently, because of the presence of interlayer antiferromagnetic interactions, 1 has an antiferromagnetic ground state with TN = 97 K. On applying a field of less than 0.5 T, a spin flip is induced, yielding a field-induced ferrimagnet (a type of metamagnet) with a large coercive field of 1.2 T at 1.8 K. Compound 1 has interlayer translational (i.e., interlayer [Ru2] [Ru2] or TCNQ TCNQ distance) (l2) and interlayer vertical (l1) distances of 10.30 and 9.82 Å, respectively. By comparison of the magnetostructural correlations of this type of layered magnet, this class of antiferromagnets, including 1, reveal a trend of having l2 r 10.3 Å.
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U2 - 10.1039/c7qm00534b
DO - 10.1039/c7qm00534b
M3 - Article
AN - SCOPUS:85045994002
VL - 2
SP - 497
EP - 504
JO - Materials Chemistry Frontiers
JF - Materials Chemistry Frontiers
SN - 2052-1537
IS - 3
ER -