Issue 34, 2018

Layered ferrimagnets constructed from charge-transferred paddlewheel [Ru2] units and TCNQ derivatives: the importance of interlayer translational distance in determining magnetic ground state

Abstract

A donor (D)/acceptor (A) assembly reaction using the paddlewheel-type diruthenium(II,II) complex [Ru2(3,5-F2PhCO2)4(THF)2] (3,5-F2PhCO2 = 3,5-difluorobenzoate; abbreviated hereafter as [Ru2]) as D and 7,7,8,8-tetracyano-p-quinodimethane derivatives (TCNQRx; 2,5-R-substituted TCNQ) as A in a DCM/TCE or DCE solvent system (DCM = dichloromethane, TCE = 1,1,2,2-tetrachloroethane, DCE = 1,2-dichloroethane) led to the formation of D2A-type two-dimensional layered compounds [{Ru2(3,5-F2PhCO2)4}2{TCNQRx}]·nsolv (Rx = H2 (1), Rx = Me2, (2), and Rx = (OEt)2 (3)). All the compounds had similar two-dimensional fishnet-type structures, where the two [Ru2] units were fully coordinated with the four cyano groups of TCNQRx. The compounds 1–3 were categorized as a one-electron transferred ionic state (1e-I) with D+–A–D formulation (D+[triple bond, length as m-dash][RuII,III2]+; A[triple bond, length as m-dash]TCNQRx˙). This subunit state formally derived a ferrimagnetically ordered state composed of up-spins with S = 1 for [RuII,II2] and S = 3/2 for [RuII,III2]+ and a down-spin of S = 1/2 for TCNQRx˙, with antiferromagnetic superexchange interactions in each layer. Eventually, 1–3 became three-dimensional ferrimagnets with Curie temperatures TC = 93, 93, and 92 K, respectively, owing to the presence of interlayer ferromagnetic interactions. The interlayer translational distances (l2) for the three compounds were 10.56, 10.54, and 10.84 Å, respectively, which agreed with the empirical prediction based on the threshold value of l2 > 10.3 Å for a valid ferromagnetic interaction.

Graphical abstract: Layered ferrimagnets constructed from charge-transferred paddlewheel [Ru2] units and TCNQ derivatives: the importance of interlayer translational distance in determining magnetic ground state

Supplementary files

Article information

Article type
Paper
Submitted
20 ⵉⴱⵔ 2018
Accepted
19 ⵢⵓⵏ 2018
First published
20 ⵢⵓⵏ 2018

Dalton Trans., 2018,47, 11760-11768

Layered ferrimagnets constructed from charge-transferred paddlewheel [Ru2] units and TCNQ derivatives: the importance of interlayer translational distance in determining magnetic ground state

W. Kosaka, Z. Liu and H. Miyasaka, Dalton Trans., 2018, 47, 11760 DOI: 10.1039/C8DT01566J

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