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Title: Multi-electron Reduction Capacity and Multiple Binding Pockets in Metal–Organic Redox Assembly at Surfaces

Abstract

Metal–ligand complexation at surfaces utilizing redox-active ligands has been demonstrated to produce uniform single-site metals centers in regular coordination networks. Two key design considerations are the electron storage capacity of the ligand and the metal-coordinating pockets on the ligand. In an effort to move toward greater complexity in the systems, particularly dinuclear metal centers, we designed and synthesized tetraethyltetra-aza-anthraquinone, TAAQ, which has superior electron storage capabilities and four ligating pockets in a diverging geometry. Cyclic voltammetry studies of the free ligand demonstrate its ability to undergo up to a four-electron reduction. Solution-based studies with an analogous ligand, diethyldi-aza-anthraquinone, demonstrate these redox capabilities in a molecular environment. Surface studies conducted on the Au(111) surface demonstrate TAAQ's ability to complex with Fe. This complexation can be observed at different stoichiometric ratios of Fe:TAAQ as Fe 2p core level shifts in X-ray photoelectron spectroscopy. Scanning tunneling microscopy experiments confirmed the formation of metal–organic coordination structures. The striking feature of these structures is their irregularity, which indicates the presence of multiple local binding motifs. Density functional theory calculations confirm several energetically accessible Fe:TAAQ isomers, which accounts for the non-uniformity of the chains.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [1]; ORCiD logo [4];  [1]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [5]
  1. Departments of ChemistryIndiana University Bloomington IN 47401 USA
  2. Department of PhysicsIndiana University Bloomington IN 47401 USA
  3. Departments of ChemistryIndiana University Bloomington IN 47401 USA; NAVSEA Crane Crane IN 47522 USA
  4. Department of PhysicsUniversity of Central Florida Orlando FL USA
  5. Departments of ChemistryIndiana University Bloomington IN 47401 USA; Department of PhysicsIndiana University Bloomington IN 47401 USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1529239
Alternate Identifier(s):
OSTI ID: 1501742
Grant/Contract Number:  
SC0016367
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: 21; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English

Citation Formats

Morris, Tobias W., Huerfano, I. J., Wang, Miao, Wisman, David L., Cabelof, Alyssa C., Din, Naseem U., Tempas, Christopher D., Le, Duy, Polezhaev, Alexander V., Rahman, Talat S., Caulton, Kenneth G., and Tait, Steven L. Multi-electron Reduction Capacity and Multiple Binding Pockets in Metal–Organic Redox Assembly at Surfaces. United States: N. p., 2019. Web. doi:10.1002/chem.201900002.
Morris, Tobias W., Huerfano, I. J., Wang, Miao, Wisman, David L., Cabelof, Alyssa C., Din, Naseem U., Tempas, Christopher D., Le, Duy, Polezhaev, Alexander V., Rahman, Talat S., Caulton, Kenneth G., & Tait, Steven L. Multi-electron Reduction Capacity and Multiple Binding Pockets in Metal–Organic Redox Assembly at Surfaces. United States. doi:10.1002/chem.201900002.
Morris, Tobias W., Huerfano, I. J., Wang, Miao, Wisman, David L., Cabelof, Alyssa C., Din, Naseem U., Tempas, Christopher D., Le, Duy, Polezhaev, Alexander V., Rahman, Talat S., Caulton, Kenneth G., and Tait, Steven L. Mon . "Multi-electron Reduction Capacity and Multiple Binding Pockets in Metal–Organic Redox Assembly at Surfaces". United States. doi:10.1002/chem.201900002.
@article{osti_1529239,
title = {Multi-electron Reduction Capacity and Multiple Binding Pockets in Metal–Organic Redox Assembly at Surfaces},
author = {Morris, Tobias W. and Huerfano, I. J. and Wang, Miao and Wisman, David L. and Cabelof, Alyssa C. and Din, Naseem U. and Tempas, Christopher D. and Le, Duy and Polezhaev, Alexander V. and Rahman, Talat S. and Caulton, Kenneth G. and Tait, Steven L.},
abstractNote = {Metal–ligand complexation at surfaces utilizing redox-active ligands has been demonstrated to produce uniform single-site metals centers in regular coordination networks. Two key design considerations are the electron storage capacity of the ligand and the metal-coordinating pockets on the ligand. In an effort to move toward greater complexity in the systems, particularly dinuclear metal centers, we designed and synthesized tetraethyltetra-aza-anthraquinone, TAAQ, which has superior electron storage capabilities and four ligating pockets in a diverging geometry. Cyclic voltammetry studies of the free ligand demonstrate its ability to undergo up to a four-electron reduction. Solution-based studies with an analogous ligand, diethyldi-aza-anthraquinone, demonstrate these redox capabilities in a molecular environment. Surface studies conducted on the Au(111) surface demonstrate TAAQ's ability to complex with Fe. This complexation can be observed at different stoichiometric ratios of Fe:TAAQ as Fe 2p core level shifts in X-ray photoelectron spectroscopy. Scanning tunneling microscopy experiments confirmed the formation of metal–organic coordination structures. The striking feature of these structures is their irregularity, which indicates the presence of multiple local binding motifs. Density functional theory calculations confirm several energetically accessible Fe:TAAQ isomers, which accounts for the non-uniformity of the chains.},
doi = {10.1002/chem.201900002},
journal = {Chemistry - A European Journal},
number = 21,
volume = 25,
place = {United States},
year = {2019},
month = {3}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996