Electron-Transferred Donor/Acceptor Ferrimagnet with TC = 91 K in a Layered Assembly of Paddlewheel [Ru2] Units and TCNQ

The donor (D)/acceptor (A) assembly reaction of the paddlewheel-type diruthenium(II,II) complex [Ru2(2,4,6-F3PhCO2)4(THF)2] (2,4,6-F3PhCO2(-) = 2,4,6-trifluorobenzoate; abbreviated hereafter as [Ru2]) with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) in a p-xylene/CH2Cl2 solvent system led to the formation of a two-dimensional layered compound, [{Ru2(2,4,6-F3PhCO2)4}2(TCNQ)]·2(p-xylene)·2CH2Cl2 (1). As expected from this D/A combination, 1 has a one-electron-transfer ionic state with the D(0.5+)2A(-) formulation. This state formally derives a heterospin state composed of S = 1 for [Ru(II,II)2], S = 3/2 for [Ru(II,III)2](+), and S = ½ for TCNQ(•-), possibly causing intralayer ferrimagnetic spin ordering. Most of these types of compounds have an antiferromagnetic ground state because of the coupling of ferrimagnetically ordered layers in dipole antiferromagnetic interactions. However, 1 became a three-dimensional ferrimagnet with T(C) = 91 K because of the presence of interlayer ferromagnetic interactions.