Abstract
Mixed-metal chain complexes constructed from lantern-type dinuclear ruthenium(II,III) carboxylate unit and tetracyanidonickelate(II), (PPh 4 ) n (Ru 2 (O 2 CCH 3 ) 4 Ni(CN) 4 ) n ·nH 2 O (1) and (PPh 4 ) n (Ru 2 {O 2 CC(CH 3 ) 3 } 4 ) 3n (Ni(CN) 4 ) 2n ·2nH 2 O (2), were synthesized and characterized by elemental analysis, IR, and UV-vis spectroscopies. These data are in accordance with the formation of the chain complex with an alternative arrangement of the dinuclear Ru 2 unit and tetracyanidonickelate(II). A broad band at near-IR and a band at visible region (1058 and 452 nm for 1 and 1082 and 454 nm for 2) were observed in the diffused refl ectance spectra and ascribed to a δ(Ru 2 )→δ*(Ru 2 ) and a π(RuO, Ru 2 )→π*(Ru 2 ) transitions, respectively. Temperature-dependence of magnetic susceptibility (4.5—300 K) showed that the antiferromagnetic interaction between the dinuclear units is weak (zJ = −0.2 cm −1 ) with D value of 75 cm −1 for both complexes.
Highlights
The chemistry of dinuclear metal carboxylates has attracted much attention over the past five decades because of the unique lantern-type dinuclear core [1,2,3,4,5]
Among the dinuclear metal carboxyletes, mixedvalent ruthenium(II,III) carboxylates [Ru (O CR) ]+ are interesting, because these dinuclear systems are paramagnetic with three unpaired electrons on the π*2δ*1 orbitals in the metal–metal bonds and with large zero-field splitting (ZFS)
We prepared many metal-assembled complexes from dinuclear species to one-dimensional chain compounds by application of linking ligands to dinuclear ruthenium carboxylates and found that most of them are antiferromagnetic between the dinuclear ruthenium units and the strength of the antiferromagnetic interaction depends on the linking ligands [16,17,18,19,20,21,22,23,24,25,26,27,28,29]
Summary
The chemistry of dinuclear metal carboxylates has attracted much attention over the past five decades because of the unique lantern-type (or paddlewheel-type) dinuclear core [1,2,3,4,5]. In these mixed-metal systems, a ferrimagnetic interaction between the dinuclear Ru2 spins and octacyanidometalate spins was observed for [{Ru2(O2CC(CH3)3)4}3(H2O)W(CN)8]n [37]. [Ni(CN)4]2– in order to obtain new metal-assembled complexes of ruthenium(II,III) carboxylate.
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