Hapticity-dependent charge transport through carbodithioate-terminated [5,15-bis(phenylethynyl)porphinato]zinc(II) complexes in metal-molecule-metal junctions

Zhihai Li, Manuel Smeu, Tae Hong Park, Jeff Rawson, Yangjun Xing, Michael J. Therien, Mark A Ratner, Eric Borguet

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Single molecule break junction experiments and nonequilibrium Green's function calculations using density functional theory (NEGF-DFT) of carbodithioate- and thiol-terminated [5,15-bis(phenylethynyl)-10,20-diarylporphinato]zinc(II) complexes reveal the impact of the electrode-linker coordination mode on charge transport at the single-molecule level. Replacement of thiolate (-S-) by the carbodithioate (-CS2 -) anchoring motif leads to an order of magnitude increase of single molecule conductance. In contrast to thiolate-terminated structures, metal-molecule-metal junctions that exploit the carbodithioate linker manifest three distinct conductance values. We hypothesize that the magnitudes of these conductances depend upon carbodithoate linker hapticity with measured conductances across Au-[5,15-bis(4′-(dithiocarboxylate)phenylethynyl)-10,20-diarylporphinato]zinc(II)-Au junctions the greatest when both anchoring groups attach to the metal surface in a bidentate fashion. We support this hypothesis with NEGF-DFT calculations, which consider the electron transport properties for specific binding geometries. These results provide new insights into the origin of molecule-to-molecule conductance heterogeneity in molecular charge transport measurements and the factors that optimize electrode-molecule-electrode electronic coupling and maximize the conductance for charge transport.

Original languageEnglish
Pages (from-to)5493-5499
Number of pages7
JournalNano Letters
Volume14
Issue number10
DOIs
Publication statusPublished - Oct 8 2014

Fingerprint

Coordination Complexes
Charge transfer
Zinc
Electrodes
zinc
Metals
Molecules
metals
molecules
Electron Transport
Sulfhydryl Compounds
Green's function
Density functional theory
electrodes
Green's functions
density functional theory
Electron transport properties
thiols
metal surfaces
transport properties

Keywords

  • carbodithioate linker
  • Linker hapticity
  • molecular electronics
  • NEGF-DFT
  • STM break junction

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Bioengineering
  • Chemistry(all)
  • Materials Science(all)
  • Mechanical Engineering
  • Medicine(all)

Cite this

Hapticity-dependent charge transport through carbodithioate-terminated [5,15-bis(phenylethynyl)porphinato]zinc(II) complexes in metal-molecule-metal junctions. / Li, Zhihai; Smeu, Manuel; Park, Tae Hong; Rawson, Jeff; Xing, Yangjun; Therien, Michael J.; Ratner, Mark A; Borguet, Eric.

In: Nano Letters, Vol. 14, No. 10, 08.10.2014, p. 5493-5499.

Research output: Contribution to journalArticle

Li, Zhihai ; Smeu, Manuel ; Park, Tae Hong ; Rawson, Jeff ; Xing, Yangjun ; Therien, Michael J. ; Ratner, Mark A ; Borguet, Eric. / Hapticity-dependent charge transport through carbodithioate-terminated [5,15-bis(phenylethynyl)porphinato]zinc(II) complexes in metal-molecule-metal junctions. In: Nano Letters. 2014 ; Vol. 14, No. 10. pp. 5493-5499.
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