Tuning the electrical conductance of metalloporphyrin supramolecular wires

Sci Rep. 2016 Nov 21:6:37352. doi: 10.1038/srep37352.

Abstract

In contrast with conventional single-molecule junctions, in which the current flows parallel to the long axis or plane of a molecule, we investigate the transport properties of M(II)-5,15-diphenylporphyrin (M-DPP) single-molecule junctions (M=Co, Ni, Cu, or Zn divalent metal ions), in which the current flows perpendicular to the plane of the porphyrin. Novel STM-based conductance measurements combined with quantum transport calculations demonstrate that current-perpendicular-to-the-plane (CPP) junctions have three-orders-of-magnitude higher electrical conductances than their current-in-plane (CIP) counterparts, ranging from 2.10-2 G0 for Ni-DPP up to 8.10-2 G0 for Zn-DPP. The metal ion in the center of the DPP skeletons is strongly coordinated with the nitrogens of the pyridyl coated electrodes, with a binding energy that is sensitive to the choice of metal ion. We find that the binding energies of Zn-DPP and Co-DPP are significantly higher than those of Ni-DPP and Cu-DPP. Therefore when combined with its higher conductance, we identify Zn-DPP as the favoured candidate for high-conductance CPP single-molecule devices.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cobalt / chemistry
  • Coordination Complexes / chemistry*
  • Copper / chemistry
  • Electric Conductivity*
  • Electrochemistry
  • Metalloporphyrins / chemistry*
  • Nickel / chemistry
  • Zinc / chemistry

Substances

  • Coordination Complexes
  • Metalloporphyrins
  • Cobalt
  • Copper
  • Nickel
  • Zinc