Electrical behaviour of heterobimetallic [MM'(EtCS_2) _4] (MM'=NiPd, NiPt, PdPt) and MM'X-chain polymers [PtM(EtCS _2)_4I] (M=Ni, Pd)

摘要

Herein, we report the isolation of new heterobimetallic complexes [Ni _(0.6)Pd_(1.4)(EtCS_2)_4] (1), [NiPt(EtCS_2)_4] (2) and [Pd_(0.4)Pt _(1.6)(EtCS_2)_4] (3), which were constructed by using transmetallation procedures. Subsequent oxidation with iodine furnished the MM'X monodimensional chains [Ni_(0.6)Pt_(1.4)(EtCS _2)_4I] (4) and [Ni_(0.1)Pd_(0.3)Pt _(1.6)(EtCS_2)_4I] (5). The physical properties of these systems were investigated and the chain structures 4 and 5 were found to be reminiscent of the parent [Pt_2(EtCS_2)_4I] species. However, they were more sensitively dependent on the localised nature of the charge on the Ni ion, which caused spontaneous breaking of the conduction bands. In the year MM'X: The direct oxidation of heterobimetallic complexes allowed the expansion of so-called MMX 1D chains, which afforded the first mixed-metal mixed-valence MM'X system with dithiocarboxylate ligands (see picture).