scanning tunneling microscopy; density functional theory; ultra-high vacuum; surface science; nanotechnology; Ullmann coupling; polymerization; oligomers; monomers; on-surface synthesis; self-assembly; fast stm; high speed stm
Abstract :
[en] Ullmann coupling is a widely used reaction for the on-surface growth of low-dimensional carbon nanomaterials. The irreversible nature of this reaction prevents the "self-healing" of defects, and a detailed knowledge of its mechanism is therefore essential to enable the growth of extended ordered structures. However, the dynamics of the Ullmann polymerization remain largely unexplored, as coupling events occur on a timescale faster than conventional scanning probe microscopy imaging frequencies. Here, we reveal the dynamics of these surface events using high-speed variable-temperature scanning tunneling microscopy (STM) (10 frames per second). Performing the measurements at the onset reaction temperatures provides an unprecedented description of the evolution of organometallic (OM) and covalent surface species during the Ullmann polymerization of para-dibromobenzene on Cu(110). Our results demonstrate the existence of an intermediate OM phase with Cu adatoms that inhibits the polymerization. These observations now complete the picture of the pathways of on-surface Ullmann polymerization, which includes the complex interplay of the phenylene moieties and metal atoms. Our work demonstrates the unique capability of high-speed STM to capture the dynamics of molecular self-assembly and coupling.
Disciplines :
Physics
Author, co-author :
Dettmann, Dominik; Centre Énergie, Matériaux et Télécommunications, Institut National de la Recherche Scientifique Department, 1650 Boulevard Lionel-Boulet, Varennes, J3X 1P7 Québec, Canada ; Istituto di Struttura della Materia-CNR (ISM-CNR), Via Fosso del Cavaliere 100, 00133 Roma, Italy
Preetha Genesh, Navathej ; Centre Énergie, Matériaux et Télécommunications, Institut National de la Recherche Scientifique Department, 1650 Boulevard Lionel-Boulet, Varennes, J3X 1P7 Québec, Canada
Galeotti, Gianluca; Centre Énergie, Matériaux et Télécommunications, Institut National de la Recherche Scientifique Department, 1650 Boulevard Lionel-Boulet, Varennes, J3X 1P7 Québec, Canada
MacLean, Oliver ; Centre Énergie, Matériaux et Télécommunications, Institut National de la Recherche Scientifique Department, 1650 Boulevard Lionel-Boulet, Varennes, J3X 1P7 Québec, Canada ; Key Laboratory of Functional Materials Physics and Chemistry of the Ministry of Education, Jilin Normal University, 130103 Changchun, P. R. China
Farnesi Camellone, Matteo ; Consiglio Nazionale delle Ricerche-Istituto Officina dei Materiali (CNR-IOM), C/o SISSA, Via Bonomea 265, 34136 Trieste, Italy
Johal, Tarnjit Kaur; Centre Énergie, Matériaux et Télécommunications, Institut National de la Recherche Scientifique Department, 1650 Boulevard Lionel-Boulet, Varennes, J3X 1P7 Québec, Canada
Fabris, Stefano; Consiglio Nazionale delle Ricerche-Istituto Officina dei Materiali (CNR-IOM), C/o SISSA, Via Bonomea 265, 34136 Trieste, Italy
Africh, Cristina ; Consiglio Nazionale delle Ricerche-Istituto Officina dei Materiali (CNR-IOM), C/o SISSA, Via Bonomea 265, 34136 Trieste, Italy
Perepichka, Dmytro F ; Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, H3A 0B8 Québec, Canada
Rosei, Federico ; Department of Chemical and Pharmaceutical Sciences, University of Trieste, Via Giorgeri 1, 34127 Trieste, Italy
Contini, Giorgio ; Istituto di Struttura della Materia-CNR (ISM-CNR), Via Fosso del Cavaliere 100, 00133 Roma, Italy ; Department of Physics, University Tor Vergata, Via della Ricerca Scientifica 1, 00133 Roma, Italy
External co-authors :
yes
Language :
English
Title :
Real-Time Imaging of On-Surface Ullmann Polymerization Reveals an Inhibiting Effect of Adatoms.
H2020 - 654360 - NFFA-Europe - NANOSCIENCE FOUNDRIES AND FINE ANALYSIS - EUROPE
Funders :
Regione Lazio Fonds de recherche du Québec – Nature et technologies Horizon 2020 Framework Programme Ministero degli Affari Esteri e della Cooperazione Internazionale Natural Sciences and Engineering Research Council of Canada Alliance de recherche numérique du Canada Government of Ontario Union Européenne
Rizzo, D. J.; Veber, G.; Cao, T.; Bronner, C.; Chen, T.; Zhao, F.; Rodriguez, H.; Louie, S. G.; Crommie, M. F.; Fischer, F. R. Topological band engineering of graphene nanoribbons. Nature 2018, 560 ( 7717), 204- 208, 10.1038/s41586-018-0376-8
Zhong, Y.; Cheng, B.; Park, C.; Ray, A.; Brown, S.; Mujid, F.; Lee, J.-U.; Zhou, H.; Suh, J.; Lee, K.-H.; Mannix, A. J.; Kang, K.; Sibener, S. J.; Muller, D. A.; Park, J. Wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices. Science 2019, 366 ( 6471), 1379- 1384, 10.1126/science.aax9385
Di Giovannantonio, M.; Kosmala, T.; Bonanni, B.; Serrano, G.; Zema, N.; Turchini, S.; Catone, D.; Wandelt, K.; Pasini, D.; Contini, G.; Goletti, C. Surface-Enhanced Polymerization via Schiff-Base Coupling at the Solid-Water Interface under pH Control. J. Phys. Chem. C 2015, 119 ( 33), 19228- 19235, 10.1021/acs.jpcc.5b05547
Cai, Z.-F.; Zhan, G.; Daukiya, L.; Eyley, S.; Thielemans, W.; Severin, K.; De Feyter, S. Electric-Field-Mediated Reversible Transformation between Supramolecular Networks and Covalent Organic Frameworks. J. Am. Chem. Soc. 2019, 141 ( 29), 11404- 11408, 10.1021/jacs.9b05265
Blunt, M. O.; Russell, J. C.; Champness, N. R.; Beton, P. H. Templating molecular adsorption using a covalent organic framework. Chem. Commun. 2010, 46 ( 38), 7157- 7159, 10.1039/c0cc01810d
Weiss, P. S.; Kamna, M. M.; Graham, T. M.; Stranick, S. J. Imaging Benzene Molecules and Phenyl Radicals on Cu{111}. Langmuir 1998, 14 ( 6), 1284- 1289, 10.1021/la970736i
Pham, T. A.; Tran, B. V.; Nguyen, M.-T.; Stöhr, M. Chiral-Selective Formation of 1D Polymers Based on Ullmann-Type Coupling: The Role of the Metallic Substrate. Small 2017, 13 ( 13), 1603675, 10.1002/smll.201603675
Wang, T.; Huang, J.; Lv, H.; Fan, Q.; Feng, L.; Tao, Z.; Ju, H.; Wu, X.; Tait, S. L.; Zhu, J. Kinetic Strategies for the Formation of Graphyne Nanowires via Sonogashira Coupling on Ag(111). J. Am. Chem. Soc. 2018, 140 ( 41), 13421- 13428, 10.1021/jacs.8b08477
Wang, C.; Chi, L.; Ciesielski, A.; Samorì, P. Chemical Synthesis at Surfaces with Atomic Precision: Taming Complexity and Perfection. Angew. Chem., Int. Ed. 2019, 58 ( 52), 18758- 18775, 10.1002/anie.201906645
Dettmann, D.; Sheverdyaeva, P. M.; Hamzehpoor, E.; Franchi, S.; Galeotti, G.; Moras, P.; Ceccarelli, C.; Perepichka, D. F.; Rosei, F.; Contini, G. Electronic Band Engineering of Two-Dimensional Kagome Polymers. ACS Nano 2024, 18 ( 1), 849- 857, 10.1021/acsnano.3c09476
Lipton-Duffin, J. A.; Ivasenko, O.; Perepichka, D. F.; Rosei, F. Synthesis of Polyphenylene Molecular Wires by Surface-Confined Polymerization. Small 2009, 5 ( 5), 592- 597, 10.1002/smll.200801943
Eichhorn, J.; Nieckarz, D.; Ochs, O.; Samanta, D.; Schmittel, M.; Szabelski, P. J.; Lackinger, M. On-Surface Ullmann Coupling: The Influence of Kinetic Reaction Parameters on the Morphology and Quality of Covalent Networks. ACS Nano 2014, 8 ( 8), 7880- 7889, 10.1021/nn501567p
Wang, C.-X.; Chen, J.-L.; Shu, C.-H.; Shi, K.-J.; Liu, P.-N. On-surface synthesis of 2D COFs on Cu(111) via the formation of thermodynamically stable organometallic networks as the template. Phys. Chem. Chem. Phys. 2019, 21 ( 24), 13222- 13229, 10.1039/C9CP01843C
Xi, M.; Bent, B. E. Mechanisms of the Ullmann coupling reaction in adsorbed monolayers. J. Am. Chem. Soc. 1993, 115 ( 16), 7426- 7433, 10.1021/ja00069a048
Albrecht, F.; Fatayer, S.; Pozo, I.; Tavernelli, I.; Repp, J.; Peña, D.; Gross, L. Selectivity in single-molecule reactions by tip-induced redox chemistry. Science 2022, 377 ( 6603), 298- 301, 10.1126/science.abo6471
Mishra, S.; Fatayer, S.; Fernández, S.; Kaiser, K.; Peña, D.; Gross, L. Nonbenzenoid High-Spin Polycyclic Hydrocarbons Generated by Atom Manipulation. ACS Nano 2022, 16 ( 2), 3264- 3271, 10.1021/acsnano.1c11157
Ruan, Z.; Li, B.; Lu, J.; Gao, L.; Sun, S.; Zhang, Y.; Cai, J. Real-space imaging of a phenyl group migration reaction on metal surfaces. Nat. Commun. 2023, 14 ( 1), 970, 10.1038/s41467-023-36696-6
Dettmann, D.; Galeotti, G.; MacLean, O.; Tomellini, M.; Di Giovannantonio, M.; Lipton-Duffin, J.; Verdini, A.; Floreano, L.; Fagot-Revurat, Y.; Perepichka, D. F.; Rosei, F.; Contini, G. Identification of Topotactic Surface-Confined Ullmann-Polymerization. Small 2021, 17 ( 41), 2103044, 10.1002/smll.202103044
Galeotti, G.; Di Giovannantonio, M.; Lipton-Duffin, J.; Ebrahimi, M.; Tebi, S.; Verdini, A.; Floreano, L.; Fagot-Revurat, Y.; Perepichka, D. F.; Rosei, F.; Contini, G. The role of halogens in on-surface Ullmann polymerization. Faraday Discuss. 2017, 204 ( 0), 453- 469, 10.1039/C7FD00099E
Di Giovannantonio, M.; Tomellini, M.; Lipton-Duffin, J.; Galeotti, G.; Ebrahimi, M.; Cossaro, A.; Verdini, A.; Kharche, N.; Meunier, V.; Vasseur, G.; Fagot-Revurat, Y.; Perepichka, D. F.; Rosei, F.; Contini, G. Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization. J. Am. Chem. Soc. 2016, 138 ( 51), 16696- 16702, 10.1021/jacs.6b09728
Abadia, M.; Ilyn, M.; Piquero-Zulaica, I.; Gargiani, P.; Rogero, C.; Ortega, J. E.; Brede, J. Polymerization of Well-Aligned Organic Nanowires on a Ferromagnetic Rare-Earth Surface Alloy. ACS Nano 2017, 11 ( 12), 12392- 12401, 10.1021/acsnano.7b06374
Di Giovannantonio, M.; Contini, G. Reversibility and intermediate steps as key tools for the growth of extended ordered polymers via on-surface synthesis. J. Phys.: Condens. Matter 2018, 30 ( 9), 093001, 10.1088/1361-648X/aaa8cb
Grossmann, L.; Hocke, M.; Galeotti, G.; Contini, G.; Floreano, L.; Cossaro, A.; Ghosh, A.; Schmittel, M.; Rosen, J.; Heckl, W. M.; Björk, J.; Lackinger, M. Mechanistic insights into on-surface reactions from isothermal temperature-programmed X-ray photoelectron spectroscopy. Nanoscale 2024, 16 ( 15), 7612- 7625, 10.1039/D4NR00468J
Lackinger, M. Possibilities and Limitations of Kinetic Studies in On-Surface Synthesis by Real Time X-ray Photoelectron Spectroscopy. ChemPhysChem 2024, 25 ( 11), e202400156 10.1002/cphc.202400156
Bieri, M.; Nguyen, M.-T.; Gröning, O.; Cai, J.; Treier, M.; Aït-Mansour, K.; Ruffieux, P.; Pignedoli, C. A.; Passerone, D.; Kastler, M.; Müllen, K.; Fasel, R. Two-Dimensional Polymer Formation on Surfaces: Insight into the Roles of Precursor Mobility and Reactivity. J. Am. Chem. Soc. 2010, 132 ( 46), 16669- 16676, 10.1021/ja107947z
Fritton, M.; Duncan, D. A.; Deimel, P. S.; Rastgoo-Lahrood, A.; Allegretti, F.; Barth, J. V.; Heckl, W. M.; Björk, J.; Lackinger, M. The Role of Kinetics versus Thermodynamics in Surface-Assisted Ullmann Coupling on Gold and Silver Surfaces. J. Am. Chem. Soc. 2019, 141 ( 12), 4824- 4832, 10.1021/jacs.8b11473
Zhang, Z.; Perepichka, D. F.; Khaliullin, R. Z. Adatoms in the Surface-Confined Ullmann Coupling of Phenyl Groups. J. Phys. Chem. Lett. 2021, 12, 11061- 11069, 10.1021/acs.jpclett.1c02914
Patera, L. L.; Bianchini, F.; Africh, C.; Dri, C.; Soldano, G.; Mariscal, M. M.; Peressi, M.; Comelli, G. Real-time imaging of adatom-promoted graphene growth on nickel. Science 2018, 359 ( 6381), 1243- 1246, 10.1126/science.aan8782
Dri, C.; Panighel, M.; Tiemann, D.; Patera, L. L.; Troiano, G.; Fukamori, Y.; Knoller, F.; Lechner, B. A. J.; Cautero, G.; Giuressi, D.; Comelli, G.; Fraxedas, J.; Africh, C.; Esch, F. The new FAST module: A portable and transparent add-on module for time-resolved investigations with commercial scanning probe microscopes. Ultramicroscopy 2019, 205, 49- 56, 10.1016/j.ultramic.2019.05.010
Rahn, B.; Magnussen, O. M. Formation and Diffusion of Subsurface Adsorbates at Electrodes. J. Am. Chem. Soc. 2018, 140 ( 29), 9066- 9069, 10.1021/jacs.8b04903
Matsushima, H.; Taranovskyy, A.; Haak, C.; Gründer, Y.; Magnussen, O. M. Reconstruction of Cu(100) Electrode Surfaces during Hydrogen Evolution. J. Am. Chem. Soc. 2009, 131 ( 30), 10362- 10363, 10.1021/ja904033t
Guezo, S.; Taranovskyy, A.; Matsushima, H.; Magnussen, O. M. Surface Dynamics of Lead Adsorbates at the Cu(100)-Electrolyte Interface. J. Phys. Chem. C 2011, 115 ( 39), 19336- 19342, 10.1021/jp2079988
Tansel, T.; Magnussen, O. M. Video STM Studies of Adsorbate Diffusion at Electrochemical Interfaces. Phys. Rev. Lett. 2006, 96 ( 2), 026101, 10.1103/PhysRevLett.96.026101
Galeotti, G.; Di Giovannantonio, M.; Cupo, A.; Xing, S.; Lipton-Duffin, J.; Ebrahimi, M.; Vasseur, G.; Kierren, B.; Fagot-Revurat, Y.; Tristant, D.; Meunier, V.; Perepichka, D. F.; Rosei, F.; Contini, G. An unexpected organometallic intermediate in surface-confined Ullmann coupling. Nanoscale 2019, 11 ( 16), 7682- 7689, 10.1039/C9NR00672A
Di Giovannantonio, M.; El Garah, M.; Lipton-Duffin, J.; Meunier, V.; Cardenas, L.; Fagot Revurat, Y.; Cossaro, A.; Verdini, A.; Perepichka, D. F.; Rosei, F.; Contini, G. Insight into Organometallic Intermediate and Its Evolution to Covalent Bonding in Surface-Confined Ullmann Polymerization. ACS Nano 2013, 7 ( 9), 8190- 8198, 10.1021/nn4035684
Di Giovannantonio, M.; El Garah, M.; Lipton-Duffin, J.; Meunier, V.; Cardenas, L.; Fagot-Revurat, Y.; Cossaro, A.; Verdini, A.; Perepichka, D. F.; Rosei, F.; Contini, G. Reply to “Comment on ‘Insight into Organometallic Intermediate and Its Evolution to Covalent Bonding in Surface-Confined Ullmann Polymerization’. ACS Nano 2014, 8 ( 3), 1969- 1971, 10.1021/nn500322r
Karimi, M.; Tomkowski, T.; Vidali, G.; Biham, O. Diffusion of Cu on Cu surfaces. Phys. Rev. B: Condens. Matter Mater. Phys. 1995, 52 ( 7), 5364- 5374, 10.1103/PhysRevB.52.5364
Zhang, D.; Wang, G.; Chen, C.; Joshi, T.; Chen, X.-K.; Evans, A. M.; Matsumoto, M.; Dichtel, W. R.; Li, H.; Crommie, M. F.; Bredas, J. L. Mechanism of Formation of Benzotrithiophene-Based Covalent Organic Framework Monolayers on Coinage-Metal Surfaces: C-C Coupling Selectivity and Monomer-Metal Interactions. Chem. Mater. 2020, 32 ( 24), 10688- 10696, 10.1021/acs.chemmater.0c03901
Björk, J.; Sánchez-Sánchez, C.; Chen, Q.; Pignedoli, C. A.; Rosen, J.; Ruffieux, P.; Feng, X.; Narita, A.; Müllen, K.; Fasel, R. The Role of Metal Adatoms in a Surface-Assisted Cyclodehydrogenation Reaction on a Gold Surface. Angew. Chem., Int. Ed. 2022, 61 ( 49), e202212354 10.1002/anie.202212354
Briegel, K. D.; Riccius, F.; Filser, J.; Bourgund, A.; Spitzenpfeil, R.; Panighel, M.; Dri, C.; Lechner, B. A. J.; Esch, F. PyfastSPM: A Python package to convert 1D FastSPM data streams into publication quality movies. SoftwareX 2023, 21, 101269, 10.1016/j.softx.2022.101269
Perdew, J. P.; Ernzerhof, M.; Burke, K. Rationale for mixing exact exchange with density functional approximations. J. Chem. Phys. 1996, 105 ( 22), 9982- 9985, 10.1063/1.472933
Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B: Condens. Matter Mater. Phys. 1999, 59 ( 3), 1758- 1775, 10.1103/PhysRevB.59.1758
Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132 ( 15), 154104, 10.1063/1.3382344
Humphrey, W.; Dalke, A.; Schulten, K. VMD: visual molecular dynamics. J. Mol. Graph. 1996, 14 ( 1), 33- 38, 10.1016/0263-7855(96)00018-5
Tersoff, J.; Hamann, D. R. Theory of the scanning tunneling microscope. Phys. Rev. B: Condens. Matter Mater. Phys. 1985, 31 ( 2), 805- 813, 10.1103/PhysRevB.31.805
Vanpoucke, D. E. P.; Brocks, G. Formation of Pt-induced Ge atomic nanowires on Pt/Ge(001): A density functional theory study. Phys. Rev. B: Condens. Matter Mater. Phys. 2008, 77 ( 24), 241308, 10.1103/PhysRevB.77.241308
