In search of structure–function relationships in transition-metal based rectifiers

摘要: Heterometallic chains have been proposed as potential current rectifiers in molecular electronics, their left–right asymmetry providing, at least principle, a mechanism for differentiation of flow forward and reverse directions. Here we compare two known extended metal atom (EMACs), Ru2Ni(dpa)4(NCS)2 Ru2Cu(dpa)4(NCS)2, both which meet the first criterion rectification so much they are physically asymmetric. In cases dominant transport channel is doubly degenerate π* orbital localised, to approximation, on Ru2 unit. As result, limited by tunnelling across Au–SCN–Ni/Cu junction. The paramagnetic Ni centre tunes delocalisation channel, making minority-spin (β) more transparent than its spin-α counterpart this difference provides basis under bias.