The Fate of Bromine After Temperature-induced Dehydrogenation of On-surface Synthesized Bisheptahelicene

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2019 Apr 19

PMID 30996879

Citations 9

Authors

Anais Mairena

Milos Baljozovic

Maciej Kawecki

Konstantin Grenader

Martin Wienke

Kevin Martin

Laetitia Bernard

Narcis Avarvari

Andreas Terfort

Karl-Heinz Ernst

Christian Wackerlin

Affiliations

Soon will be listed here.

Abstract

The on-surface synthesis of bisheptahelicene by Ullmann coupling of 9-bromoheptahelicene on Au(111) and its temperature-induced dehydrogenation is studied using temperature-programmed reaction spectroscopy and time-of-flight secondary ion mass spectrometry. Specific dehydrogenation products of bisheptahelicene after loss of 6, 8 and 10 hydrogen atoms are identified, corresponding to molecules having undergone Diels-Alder transformations and intramolecular C-C coupling reactions. By combining with atomic hydrogen produced by dehydrogenation, the Ullmann coupling side-product bromine desorbs as HBr. H desorption emerges only after all Br has desorbed. Such characteristic behavior is explained by a kinetic model which explicitly considers the coverage of transient atomic H on the surface. Heating experiments performed with saturated layers of different Br-containing molecules reveal that the onset of HBr desorption depends strictly on the dehydrogenation step and therefore on the structure of the molecules.

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References

Grill L, Dyer M, Lafferentz L, Persson M, Peters M, Hecht S . Nano-architectures by covalent assembly of molecular building blocks. Nat Nanotechnol. 2008; 2(11):687-91. DOI: 10.1038/nnano.2007.346. View

Otero G, Biddau G, Sanchez-Sanchez C, Caillard R, Lopez M, Rogero C . Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation. Nature. 2008; 454(7206):865-8. DOI: 10.1038/nature07193. View

Cai J, Ruffieux P, Jaafar R, Bieri M, Braun T, Blankenburg S . Atomically precise bottom-up fabrication of graphene nanoribbons. Nature. 2010; 466(7305):470-3. DOI: 10.1038/nature09211. View

Bieri M, Nguyen M, Groning O, Cai J, Treier M, Ait-Mansour K . Two-dimensional polymer formation on surfaces: insight into the roles of precursor mobility and reactivity. J Am Chem Soc. 2010; 132(46):16669-76. DOI: 10.1021/ja107947z. View

Treier M, Pignedoli C, Laino T, Rieger R, Mullen K, Passerone D . Surface-assisted cyclodehydrogenation provides a synthetic route towards easily processable and chemically tailored nanographenes. Nat Chem. 2010; 3(1):61-7. DOI: 10.1038/nchem.891. View

Nowakowski J, Wackerlin C, Girovsky J, Siewert D, Jung T, Ballav N . Porphyrin metalation providing an example of a redox reaction facilitated by a surface reconstruction. Chem Commun (Camb). 2013; 49(23):2347-9. DOI: 10.1039/c3cc39134e. View

Bjork J, Hanke F, Stafstrom S . Mechanisms of halogen-based covalent self-assembly on metal surfaces. J Am Chem Soc. 2013; 135(15):5768-75. DOI: 10.1021/ja400304b. View

Biet T, Fihey A, Cauchy T, Vanthuyne N, Roussel C, Crassous J . Ethylenedithio-tetrathiafulvalene-helicenes: electroactive helical precursors with switchable chiroptical properties. Chemistry. 2013; 19(39):13160-7. DOI: 10.1002/chem.201301095. View

Eichhorn J, Strunskus T, Rastgoo-Lahrood A, Samanta D, Schmittel M, Lackinger M . On-surface Ullmann polymerization via intermediate organometallic networks on Ag(111). Chem Commun (Camb). 2014; 50(57):7680-2. DOI: 10.1039/c4cc02757d. View

10.

Wiengarten A, Seufert K, Auwarter W, Ecija D, Diller K, Allegretti F . Surface-assisted dehydrogenative homocoupling of porphine molecules. J Am Chem Soc. 2014; 136(26):9346-54. DOI: 10.1021/ja501680n. View

11.

Rockert M, Franke M, Tariq Q, Ditze S, Stark M, Uffinger P . Coverage- and temperature-dependent metalation and dehydrogenation of tetraphenylporphyrin on Cu(111). Chemistry. 2014; 20(29):8948-53. DOI: 10.1002/chem.201402420. View

12.

Smykalla L, Shukrynau P, Korb M, Lang H, Hietschold M . Surface-confined 2D polymerization of a brominated copper-tetraphenylporphyrin on Au(111). Nanoscale. 2015; 7(9):4234-41. DOI: 10.1039/c4nr06371f. View

13.

Fan Q, Gottfried J, Zhu J . Surface-catalyzed C-C covalent coupling strategies toward the synthesis of low-dimensional carbon-based nanostructures. Acc Chem Res. 2015; 48(8):2484-94. DOI: 10.1021/acs.accounts.5b00168. View

14.

Wiengarten A, Lloyd J, Seufert K, Reichert J, Auwarter W, Han R . Surface-Assisted Cyclodehydrogenation; Break the Symmetry, Enhance the Selectivity. Chemistry. 2015; 21(35):12285-90. DOI: 10.1002/chem.201502001. View

15.

Dong L, Liu P, Lin N . Surface-Activated Coupling Reactions Confined on a Surface. Acc Chem Res. 2015; 48(10):2765-74. DOI: 10.1021/acs.accounts.5b00160. View

16.

Pham T, Song F, Nguyen M, Li Z, Studener F, Stohr M . Comparing Ullmann Coupling on Noble Metal Surfaces: On-Surface Polymerization of 1,3,6,8-Tetrabromopyrene on Cu(111) and Au(111). Chemistry. 2016; 22(17):5937-44. DOI: 10.1002/chem.201504946. View

17.

de Oteyza D, Garcia-Lekue A, Vilas-Varela M, Merino-Diez N, Carbonell-Sanroma E, Corso M . Substrate-Independent Growth of Atomically Precise Chiral Graphene Nanoribbons. ACS Nano. 2016; 10(9):9000-8. PMC: 5043421. DOI: 10.1021/acsnano.6b05269. View

18.

Smerieri M, Pis I, Ferrighi L, Nappini S, Lusuan A, Di Valentin C . Synthesis of graphene nanoribbons with a defined mixed edge-site sequence by surface assisted polymerization of (1,6)-dibromopyrene on Ag(110). Nanoscale. 2016; 8(41):17843-17853. DOI: 10.1039/c6nr05952j. View

19.

Wackerlin C, Li J, Mairena A, Martin K, Avarvari N, Ernst K . Surface-assisted diastereoselective Ullmann coupling of bishelicenes. Chem Commun (Camb). 2016; 52(86):12694-12697. DOI: 10.1039/c6cc05849c. View

20.

Stetsovych O, Svec M, Vacek J, Chocholousova J, Jancarik A, Rybacek J . From helical to planar chirality by on-surface chemistry. Nat Chem. 2017; 9(3):213-218. DOI: 10.1038/nchem.2662. View