Electrical Behaviour of Heterobimetallic [MM′(EtCS2)4] (MM′=NiPd, NiPt, PdPt) and MM′X-Chain Polymers [PtM(EtCS2)4I] (M=Ni, Pd)
Herein, we report the isolation of new heterobimetallic complexes [Ni0.6Pd1.4ACHTUNGTRENUNG(EtCS2)4] (1), [NiPtACHTUNGTRENUNG(EtCS2)4] (2) and [Pd0.4Pt1.6ACHTUNGTRENUNG(EtCS2)4] (3), which were constructed by using transmetallation procedures. Subsequent oxidation with iodine furnished the MM'X monodimensional chains [Ni0.6Pt1.4ACHTUNGTRENUNG(EtCS2)4I] (4) and [Ni0.1Pd0.3Pt1.6ACHTUNGTRENUNG(EtCS2)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 [Pt2ACHTUNGTRENUNG(EtCS2)4I] species. However, they were more sensitively dependent on the localised nature of the charge on the Ni ion, which caused spont…
Conductive nanostructures of MMX chains
Crystals of [Pt-2(n-pentylCS(2))(4)I] show a transition from semiconductor to metallic with the increase of the temperature (conductivity is 0.3-1.4 S.cm(-1) at room temperature) and a second metallic metallic transition at 330 K, inferred by electrical conductivity measurements. X-ray diffraction studies carried out at different temperatures (100, 298, and 350 K) confirm the presence of three different phases. The valence-ordering of these phases is analyzed using structural, magnetic, and electrical data. Density functional theory calculations allow a further analysis of the band structure derived for each phase. Nanostructures adsorbed on an insulating surface show electrical conductivit…