Issue 6, 2014

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

Abstract

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

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

Supplementary files

Article information

Article type
Paper
Submitted
19 mars 2014
Accepted
30 avr. 2014
First published
05 mai 2014

Inorg. Chem. Front., 2014,1, 468-477

Author version available

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

T. Weng, D. DeBrincat, V. Arcisauskaite and J. E. McGrady, Inorg. Chem. Front., 2014, 1, 468 DOI: 10.1039/C4QI00038B

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