Electron-Transferred Donor/Acceptor Ferrimagnet with <i>T</i>_C = 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 D0.5+2A– formulation. This state formally derives a heterospin state composed of S = 1 for [RuII,II2], S = 3/2 for [RuII,III2]+, and S = 1/2 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 TC = 91 K because of the presence of interlayer ferromagnetic interactions.