Designing Optoelectronic Properties by On-Surface Synthesis

Formation and Electronic Structure of an Iron-Terpyridine Macromolecular Complex

Agustin Schiffrin, Martina Capsoni, Gelareh Farahi, Chen-Guang Wang, Cornelius Krull, Marina Castelli, Tanya Roussy, Katherine A. Cochrane, Yuefeng Yin, Nikhil V. Medhekar, Michael Fuhrer, Adam Q. Shaw, Wei Ji, Sarah A. Burke

Research output: Contribution to journalArticleResearchpeer-review

3 Citations (Scopus)

Abstract

Supramolecular chemistry protocols applied on surfaces offer compelling avenues for atomic-scale control over organic-inorganic interface structures. In this approach, adsorbate-surface interactions and two-dimensional confinement can lead to morphologies and properties that differ dramatically from those achieved via conventional synthetic approaches. Here, we describe the bottom-up, on-surface synthesis of one-dimensional coordination nanostructures based on an iron (Fe)-terpyridine (tpy) interaction borrowed from functional metal-organic complexes used in photovoltaic and catalytic applications. Thermally activated diffusion of sequentially deposited ligands and metal atoms and intraligand conformational changes lead to Fe-tpy coordination and formation of these nanochains. We used low-temperature scanning tunneling microscopy and density functional theory to elucidate the atomic-scale morphology of the system, suggesting a linear tri-Fe linkage between facing, coplanar tpy groups. Scanning tunneling spectroscopy reveals the highest occupied orbitals, with dominant contributions from states located at the Fe node, and ligand states that mostly contribute to the lowest unoccupied orbitals. This electronic structure yields potential for hosting photoinduced metal-to-ligand charge transfer in the visible/near-infrared. The formation of this unusual tpy/tri-Fe/tpy coordination motif has not been observed for wet chemistry synthetic methods and is mediated by the bottom-up on-surface approach used here, offering pathways to engineer the optoelectronic properties and reactivity of metal-organic nanostructures.

Original languageEnglish
Pages (from-to)6545-6553
Number of pages9
JournalACS Nano
Volume12
Issue number7
DOIs
Publication statusPublished - 24 Jul 2018

Keywords

  • coordination polymers
  • density functional theory
  • low-dimensional nanostructures
  • scanning tunneling microscopy
  • scanning tunneling spectroscopy
  • self-assembly
  • surface chemistry

Cite this

Schiffrin, Agustin ; Capsoni, Martina ; Farahi, Gelareh ; Wang, Chen-Guang ; Krull, Cornelius ; Castelli, Marina ; Roussy, Tanya ; Cochrane, Katherine A. ; Yin, Yuefeng ; Medhekar, Nikhil V. ; Fuhrer, Michael ; Shaw, Adam Q. ; Ji, Wei ; Burke, Sarah A. / Designing Optoelectronic Properties by On-Surface Synthesis : Formation and Electronic Structure of an Iron-Terpyridine Macromolecular Complex. In: ACS Nano. 2018 ; Vol. 12, No. 7. pp. 6545-6553.
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abstract = "Supramolecular chemistry protocols applied on surfaces offer compelling avenues for atomic-scale control over organic-inorganic interface structures. In this approach, adsorbate-surface interactions and two-dimensional confinement can lead to morphologies and properties that differ dramatically from those achieved via conventional synthetic approaches. Here, we describe the bottom-up, on-surface synthesis of one-dimensional coordination nanostructures based on an iron (Fe)-terpyridine (tpy) interaction borrowed from functional metal-organic complexes used in photovoltaic and catalytic applications. Thermally activated diffusion of sequentially deposited ligands and metal atoms and intraligand conformational changes lead to Fe-tpy coordination and formation of these nanochains. We used low-temperature scanning tunneling microscopy and density functional theory to elucidate the atomic-scale morphology of the system, suggesting a linear tri-Fe linkage between facing, coplanar tpy groups. Scanning tunneling spectroscopy reveals the highest occupied orbitals, with dominant contributions from states located at the Fe node, and ligand states that mostly contribute to the lowest unoccupied orbitals. This electronic structure yields potential for hosting photoinduced metal-to-ligand charge transfer in the visible/near-infrared. The formation of this unusual tpy/tri-Fe/tpy coordination motif has not been observed for wet chemistry synthetic methods and is mediated by the bottom-up on-surface approach used here, offering pathways to engineer the optoelectronic properties and reactivity of metal-organic nanostructures.",
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author = "Agustin Schiffrin and Martina Capsoni and Gelareh Farahi and Chen-Guang Wang and Cornelius Krull and Marina Castelli and Tanya Roussy and Cochrane, {Katherine A.} and Yuefeng Yin and Medhekar, {Nikhil V.} and Michael Fuhrer and Shaw, {Adam Q.} and Wei Ji and Burke, {Sarah A.}",
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Designing Optoelectronic Properties by On-Surface Synthesis : Formation and Electronic Structure of an Iron-Terpyridine Macromolecular Complex. / Schiffrin, Agustin; Capsoni, Martina; Farahi, Gelareh; Wang, Chen-Guang; Krull, Cornelius; Castelli, Marina; Roussy, Tanya; Cochrane, Katherine A.; Yin, Yuefeng; Medhekar, Nikhil V.; Fuhrer, Michael; Shaw, Adam Q.; Ji, Wei; Burke, Sarah A.

In: ACS Nano, Vol. 12, No. 7, 24.07.2018, p. 6545-6553.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Schiffrin, Agustin

AU - Capsoni, Martina

AU - Farahi, Gelareh

AU - Wang, Chen-Guang

AU - Krull, Cornelius

AU - Castelli, Marina

AU - Roussy, Tanya

AU - Cochrane, Katherine A.

AU - Yin, Yuefeng

AU - Medhekar, Nikhil V.

AU - Fuhrer, Michael

AU - Shaw, Adam Q.

AU - Ji, Wei

AU - Burke, Sarah A.

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KW - density functional theory

KW - low-dimensional nanostructures

KW - scanning tunneling microscopy

KW - scanning tunneling spectroscopy

KW - self-assembly

KW - surface chemistry

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