Probing Single-Molecule Dissociations from a Bimolecular Complex NO–Co-Porphyrin
Abstract
Axial coordinations of diatomic NO molecules to metalloporphyrins play key roles in dynamic processes of biological functions such as blood pressure control and immune response. Probing such reactions at the single molecule level is essential to understand their physical mechanisms but has been rarely performed. Here we report on our single molecule dissociation experiments of diatomic NO from NO-Co-porphyrin complexes describing its dissociation mechanisms. Under tunneling junctions of scanning tunneling microscope, both positive and negative energy pulses gave rise to dissociations of NO with threshold voltages, +0.68 and -0.74 V at 0.1 nA tunneling current on Au(111). From the observed power law relations between dissociation rate and tunneling current, we argue that the dissociations were inelastically induced with molecular orbital resonances by stochastically tunneling electrons, which is supported with our density functional theory calculations. Our study shows that single molecule dissociation experiments can be used to probe reaction mechanisms in a variety of axial coordinations between small molecules and metalloporphyrins.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
The RPBE exchange functional and van der Waals correction used in this study were previously shown to yield good agreement with experiments in terms of energetics and electronic structure for similar gas adsorption on an organometallic system.
“We used the RPBE exchange functional,22,23 and the van der Waals (vdW) correction24 which were previously shown to yield a good agreement with experiments in terms of energetics and electronic structure for similar gas adsorption on an organometallic system.25”
From Single-atom catalysts for CO <sub>2</sub> electroreduction with significant activity and selectivity improvements (2017) · cites this paper as [25]
Cites
Generalized Gradient Approximation Made Simple
Perdew, J. P., Burke, K., & Ernzerhof, M. (1996) · Physical Review Letters · doi:10.1103/physrevlett.77.3865 · Cited by 215,824 · see citing works
Projector augmented-wave method
Blöchl, P. E. (1994) · Physical Review B · doi:10.1103/physrevb.50.17953 · Cited by 92,732 · see citing works
Kresse, G., & Furthmüller, J. (1996) · Computational Materials Science · doi:10.1016/0927-0256(96)00008-0 · Cited by 75,541 · see citing works
Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction
Grimme, S. (2006) · Journal of Computational Chemistry · doi:10.1002/jcc.20495 · Cited by 30,925 · see citing works
(1999) · Choice Reviews Online · doi:10.5860/choice.37-0940 · Cited by 14,314 · see citing works
Composition, structure, and stability of RuO 2 ( 110 ) as a function of oxygen pressure
Reuter, K., & Scheffler, M. (2001) · Physical review. B, Condensed matter · doi:10.1103/physrevb.65.035406 · Cited by 2,113 · see citing works
Nitric oxide : biology and pathobiology
Ignarro, L. J. (2000) · Cited by 1,300 · see citing works
Atomic-Scale Desorption Through Electronic and Vibrational Excitation Mechanisms
Shen, T. C., Wang, C., Abeln, G. C., Tucker, J. R., Lyding, J. W., Avouris, P., & Walkup, R. E. (1995) · Science · doi:10.1126/science.268.5217.1590 · Cited by 788 · see citing works
Single-Molecule Dissociation by Tunneling Electrons
Stipe, B. C., Rezaei, M. A., Ho, W., Gao, S., Persson, M., & Lundqvist, B. I. (1997) · Physical Review Letters · doi:10.1103/physrevlett.78.4410 · Cited by 622 · see citing works
Mechanistic aspects of the reactions of nitric oxide with transition-metal complexes
Ford, P. C., & Lorkovic, I. M. (2002) · Chemical Reviews · doi:10.1021/cr0000271 · Cited by 525 · see citing works
Scudiero, L., Barlow, D. E., Mazur, U., & Hipps, K. W. (2001) · Journal of the American Chemical Society · doi:10.1021/ja0100726 · Cited by 257 · see citing works
Controlling spins in adsorbed molecules by a chemical switch
Wäckerlin, C., Chylarecka, D., Kleibert, A., Müller, K., Iacoviță, C., Nolting, F., Jung, T. A., & Ballav, N. (2010) · Nature Communications · doi:10.1038/ncomms1057 · Cited by 257 · see citing works
Cryogenic UHV-STM Study of Hydrogen and Deuterium Desorption from Si(100)
Foley, E. T., Kam, A. F., Lyding, J. W., & Avouris, P. (1998) · Physical Review Letters · doi:10.1103/physrevlett.80.1336 · Cited by 208 · see citing works
State-selective dissociation of a single water molecule on an ultrathin MgO film
Shin, H., Jung, J., Motobayashi, K., Yanagisawa, S., Morikawa, Y., Kim, Y., & Kawai, M. (2010) · Nature Materials · doi:10.1038/nmat2740 · Cited by 187 · see citing works
Self-citationTwo-electron dissociation of single molecules by atomic manipulation at room temperature
Sloan, P., & Palmer, R. E. (2005) · Nature · doi:10.1038/nature03385 · Cited by 187 · see citing works
Nitric oxide complexes of metalloporphyrins: an overview of some mechanistic studies
Hoshino, M., Laverman, L. E., & Ford, P. C. (1999) · Coordination Chemistry Reviews · doi:10.1016/s0010-8545(98)00228-8 · Cited by 168 · see citing works
Molecularly Adsorbed Oxygen Species on Si(111)-(7×7): STM-Induced Dissociative Attachment Studies
Martel, R., Avouris, P., & Lyo, I.-W. (1996) · Science · doi:10.1126/science.272.5260.385 · Cited by 153 · see citing works
Flechtner, K., Kretschmann, A., Steinrück, H., & Gottfried, J. M. (2007) · Journal of the American Chemical Society · doi:10.1021/ja0756725 · Cited by 151 · see citing works
Auwärter, W., Seufert, K., Klappenberger, F., Reichert, J., Weber‐Bargioni, A. F., Verdini, A., Cvetko, D., Dell’Angela, M., Floreano, L., Cossaro, A., et al. (2010) · Physical Review B · doi:10.1103/physrevb.81.245403 · Cited by 140 · see citing works
Reversible Single Spin Control of Individual Magnetic Molecule by Hydrogen Atom Adsorption
Liu, L., Yang, K., Jiang, Y., Song, B., Xiao, W., Li, L., Zhou, H., Wang, Y., Du, S., Ouyang, M., et al. (2013) · Scientific Reports · doi:10.1038/srep01210 · Cited by 137 · see citing works
STM-Induced Hydrogen Desorption via a Hole Resonance
Stokbro, K., Thirstrup, C., Sakurai, M., Quaade, U. J., Hu, B. Y.-K., Pérez‐Murano, F., & Grey, F. (1998) · Physical Review Letters · doi:10.1103/physrevlett.80.2618 · Cited by 132 · see citing works
Reversible Change of the Spin State in a Manganese Phthalocyanine by Coordination of CO Molecule
Stróżecka, A., Soriano, M., Pascual, J. I., & Palacios, J. J. (2012) · Physical Review Letters · doi:10.1103/physrevlett.109.147202 · Cited by 121 · see citing works
Cis-dicarbonyl binding at cobalt and iron porphyrins with saddle-shape conformation
Seufert, K., Bocquet, M., Auwärter, W., Weber‐Bargioni, A. F., Reichert, J., Lorente, N., & Barth, J. V. (2011) · Nature Chemistry · doi:10.1038/nchem.956 · Cited by 104 · see citing works
Sloan, P., Hedouin, M. F. G., Palmer, R. E., & Persson, M. (2003) · Physical Review Letters · doi:10.1103/physrevlett.91.118301 · Cited by 83 · see citing works
Kim, H., Chang, Y. H., Lee, S.-H., Kim, Y., & Kahng, S. (2013) · ACS Nano · doi:10.1021/nn4039595 · Cited by 70 · see citing works
Self-citationSeufert, K., Auwärter, W., & Barth, J. V. (2010) · Journal of the American Chemical Society · doi:10.1021/ja1054884 · Cited by 67 · see citing works
Wanat, A., Wolak, M., Orzeł, Ł., Brindell, M., van Eldik, R., & Stochel, G. (2002) · Coordination Chemistry Reviews · doi:10.1016/s0010-8545(02)00091-7 · Cited by 45 · see citing works
Yoder, N. L., Guisinger, N. P., Hersam, M. C., Jorn, R., Kaun, C., & Seideman, T. (2006) · Physical Review Letters · doi:10.1103/physrevlett.97.187601 · Cited by 44 · see citing works
Kim, Y., Heben, M. J., & Zhang, S. (2004) · Physical Review Letters · doi:10.1103/physrevlett.92.176102 · Cited by 40 · see citing works
Self-citationFinite-Temperature Hydrogen Adsorption and Desorption Thermodynamics Driven by Soft Vibration Modes
Woo, S.-J., Lee, E.-S., Yoon, M., & Kim, Y. (2013) · Physical Review Letters · doi:10.1103/physrevlett.111.066102 · Cited by 39 · see citing works
Self-citationBurema, S. R., Seufert, K., Auwärter, W., Barth, J. V., & Bocquet, M. (2013) · ACS Nano · doi:10.1021/nn4010582 · Cited by 28 · see citing works
Single-Molecule Imaging of Activated Nitrogen Adsorption on Individual Manganese Phthalocyanine
Zhang, J. L., Wang, Z., Zhong, J., Yuan, K., Shen, Q., Xu, L. L., Niu, T. C., Gu, C. D., Wright, C. A., Tadich, A., et al. (2015) · Nano Letters · doi:10.1021/acs.nanolett.5b00290 · Cited by 27 · see citing works
Kim, H., Son, W., Jang, W. J., Yoon, J. K., Han, S., & Kahng, S. (2009) · Physical Review B · doi:10.1103/physrevb.80.245402 · Cited by 25 · see citing works
Self-citationKim, H., Chang, Y. H., Lee, S.-H., Lim, S., Noh, S.-K., Kim, Y., & Kahng, S. (2014) · Chemical Science · doi:10.1039/c3sc52004h · Cited by 14 · see citing works
Self-citation
Flagged first, then by citations
1 of the 35 references couldn’t be matched to a known paper.
Cited by
Sorted by citations
Back, S., Lim, J., Kim, N.-Y., Kim, Y.-H., & Jung, Y. (2017) · Chemical Science · doi:10.1039/c6sc03911a · Cited by 542 · see citing works
Self-citationDerivation of a governing rule in triboelectric charging and series from thermoelectricity
Shin, E.-C., Ko, J., Lyeo, H.-K., & Kim, Y. (2022) · Physical Review Research · doi:10.1103/physrevresearch.4.023131 · Cited by 44 · see citing works
Self-citationConformational Control of Chemical Reactivity for Surface‐Confined Ru‐Porphyrins
Knecht, P., Reichert, J., Deimel, P. S., Feulner, P., Haag, F., Allegretti, F., Garnica, M., Schwarz, M., Auwärter, W., Ryan, P. T. P., et al. (2021) · Angewandte Chemie International Edition · doi:10.1002/anie.202104075 · Cited by 23 · see citing works
Tuning and sensing spin interactions in Co-porphyrin/Au with NH3 and NO2 binding
Chang, M. H., Chang, Y. H., Kim, N.-Y., Kim, H., Lee, S.-H., Choi, M., Kim, Y., & Kahng, S. (2019) · Physical review. B./Physical review. B · doi:10.1103/physrevb.100.245406 · Cited by 21 · see citing works
Self-citationChang, M. H., Kim, N.-Y., Chang, Y. H., Lee, Y., Jeon, U. S., Kim, H., Kim, Y., & Kahng, S. (2019) · Nanoscale · doi:10.1039/c9nr00843h · Cited by 20 · see citing works
Self-citationSmall molecule binding to surface-supported single-site transition-metal reaction centres
DeJong, M., Price, A. J. A., Mårsell, E., Tom, G., Nguyen, G. D., Johnson, E. R., & Burke, S. A. (2022) · Nature Communications · doi:10.1038/s41467-022-35193-6 · Cited by 16 · see citing works
Origin of Vibrational Instabilities in Molecular Wires with Separated Electronic States
Foti, G., & Vázquez, H. (2018) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.8b00940 · Cited by 16 · see citing works
Omiya, T., Poli, P., Arnolds, H., Raval, R., Persson, M., & Kim, Y. (2017) · Chemical Communications · doi:10.1039/c7cc01310h · Cited by 10 · see citing works
Self-citationProbing Franck–Condon-like Excitations in Anchoring of Phthalocyanine Molecules on Au(111)
Jeong, Y.-C., Song, S. Y., Kim, H. W., Shin, H., Kang, J., & Seo, J. (2017) · The Journal of Physical Chemistry C · doi:10.1021/acs.jpcc.7b06158 · Cited by 6 · see citing works
Self-citationSingle-molecule imaging of dinitrogen molecule adsorption on individual iron phthalocyanine
Gu, C., Zhang, J. L., Zhong, J., Shen, Q., Zhou, X., Yuan, K., Sun, S., Lian, X., Ma, Z., & Chen, W. (2020) · Nano Research · doi:10.1007/s12274-020-2863-0 · Cited by 5 · see citing works
Liu, H., Hu, Y., Wang, H., Jiang, B., Xu, X., & Cai, Y. (2016) · Surface Science · doi:10.1016/j.susc.2016.09.003 · Cited by 4 · see citing works
Conformational Control of Chemical Reactivity for Surface‐Confined Ru‐Porphyrins
Knecht, P., Reichert, J., Deimel, P. S., Feulner, P., Haag, F., Allegretti, F., Garnica, M., Schwarz, M., Auwärter, W., Ryan, P. T. P., et al. (2021) · Angewandte Chemie · doi:10.1002/ange.202104075 · Cited by 4 · see citing works
Triboelectric charge transfer theory driven by thermoelectric effect
Mun, J.-H., Shin, E.-C., Seo, J., & Kim, Y.-H. (2025) · Physical Review Research · doi:10.1103/x3x7-s32f · Cited by 1 · see citing works
Self-citationMolecule-Supported Magnetic-Atom Dimers on Au(111): Multiple Structures and Kondo Resonances
Chang, M. H., Jung, J., Seo, J., Kang, M. J., Kim, Y., & Kahng, S. (2024) · Applied Surface Science · doi:10.1016/j.apsusc.2024.161168
Self-citation
- Authors
- Kim, H., Chang, Y. H., Jang, W.-J., Lee, E.-S., Kim, Y.-H., & Kahng, S.-J.
- Affiliations
- Korea University (KR)
- Korea Advanced Institute of Science and Technology (KR)
- Corresponding author
- Kim, Yong-Hyun
- Kahng, Se-Jong
- Venue
- ACS Nano
- Publisher
- American Chemical Society (ACS)
- Published
- 2015-07-17
- Volume
- 9
- Issue
- 7
- Pages
- 7722-7728
- ISSN
- 1936-0851 (ISSN-L)
- 1936-086X
- OpenAlex
- W915013320
- Cited by
- 14
- References
- 35
- Citations by year
- 2025: 1 · 2024: 1 · 2022: 2 · 2021: 2 · 2020: 1 · 2019: 2 · 2018: 1 · 2017: 2 · 2016: 2
- FWCI
- 0.80
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ACS Nano (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Research Foundation of Korea (2012-01013222, 2012R1A2A2A01046191, 2014-11051782)
- Global Frontier R&D program (2011-0031566: Center for Multiscale Energy Systems)
- Topics
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Molecular Junctions and Nanostructures
- Physical Sciences › Engineering › Biomedical Engineering › Surface Chemistry and Catalysis
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Force Microscopy Techniques and Applications
- Keywords
- nitric oxide, metalloporphyrins, cobalt porphyrin, axial coordination, inelastic electron tunneling, dissociation rate, threshold voltage, Au(111), reaction mechanism
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review