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 language | English |
|---|---|
| Pages (from-to) | 6545-6553 |
| Number of pages | 9 |
| Journal | ACS Nano |
| Volume | 12 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - 24 Jul 2018 |
Keywords
- coordination polymers
- density functional theory
- low-dimensional nanostructures
- scanning tunneling microscopy
- scanning tunneling spectroscopy
- self-assembly
- surface chemistry
Cite this
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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 journal › Article › Research › peer-review
TY - JOUR
T1 - Designing Optoelectronic Properties by On-Surface Synthesis
T2 - Formation and Electronic Structure of an Iron-Terpyridine Macromolecular Complex
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.
PY - 2018/7/24
Y1 - 2018/7/24
N2 - 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.
AB - 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.
KW - coordination polymers
KW - density functional theory
KW - low-dimensional nanostructures
KW - scanning tunneling microscopy
KW - scanning tunneling spectroscopy
KW - self-assembly
KW - surface chemistry
UR - http://www.scopus.com/inward/record.url?scp=85050769230&partnerID=8YFLogxK
U2 - 10.1021/acsnano.8b01026
DO - 10.1021/acsnano.8b01026
M3 - Article
VL - 12
SP - 6545
EP - 6553
JO - ACS Nano
JF - ACS Nano
SN - 1936-0851
IS - 7
ER -