The synthesis, structures and magnetic properties of polynuclear RuIII–3d (3d = MnII/III, NiII, CuII) compounds based on [RuIII(Q)2(CN)2]−
Journal
Dalton Transactions
Journal Volume
42
Journal Issue
11
Pages
3876-3887
Date Issued
2013
Author(s)
Abstract
The synthesis, crystal structures and magnetic properties of six cyano-bridged heterobimetallic compounds prepared from a paramagnetic Ru(III) building block, trans-(PPh(4))[Ru(III)(Q)(2)(CN)(2)] (1) (Q = the anion of 8-hydroxyquinoline), are described. 1 reacts with hydrated MnCl(2) in MeOH or DMF to produce a trinuclear compound {[Ru(III)(Q)(2)(CN)(2)](2)[Mn(II)(MeOH)(4)]}·8MeOH (2), or a 1-D zigzag chain {[Mn(II)(DMF)(2)(Cl)](μ-CN)(2)[Ru(III)(Q)(2)]}(n)(3). The Mn(II) has a distorted octahedral environment in 2 and a trigonal-bipyramidal environment in 3. 1 reacts with [Mn(III)(L(1))(Cl)(H(2)O)] in MeOH to produce the 1-D {[Ru(III)(Q)(2)](μ-CN)(2)[Mn(III)(L(1))]}(n) (4) that consists of alternating Mn(III) and Ru(III) units. 1 also reacts with [Cu(II)(cyclam)Br(2)] and [Ni(II)(cyclam)Cl(2)] in MeOH to produce the trinuclear complexes [Ru(III)(Q)(2)(CN(2))](2)[M(II)(cyclam)] (M = Cu(II) (5) and Ni(II) (6)). On the other hand, the reaction of 1 with [Ni(II)(cyclen)Cl(2)] produces a 1-D zigzag chain {([Ru(III)(Q)(2)(CN(2))][Ni(II)(cyclen)])[Ru(III)(Q)(2)(CN(2))]}(n) (7). Compounds 2-4 exhibit antiferromagnetic coupling between Ru(III) and Mn(III/II) centres. Antiferromagnetic coupling also occurs between Ru(III) and Cu(II) centres in 5. On the other hand, compounds 6 and 7 exhibit ferromagnetic coupling between Ru(III) and Ni(II) through cyanide bridges.
Type
journal article