Polymerization of Polyanthrylene on a Titanium Dioxide (011)‐(2×1) Surface

Kolmer, Marek; Zebari, Amir A. Ahmad; Prauzner‐Bechcicki, Jakub S.; Piskorz, Witold; Zasada, Filip; Godlewski, Szymon; Such, Bartosz; Sojka, Zbigniew; Szymoński, Marek

doi:10.1002/ange.201303657

Cited by 25 publications

(28 citation statements)

References 33 publications

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“…15,18,19 For example, efforts to grow GNRs from DBBA directly on an insulating TiO 2 (011)-(2 × 1) substrate only lead to polymerization but without cyclodehydrogenation. 20 This is strong evidence that the metal surface is crucial for cyclodehydrogenation 21 and thus for the transformation of self-assembled polyanthrylene to GNRs.…”

Section: Introductionmentioning

confidence: 97%

Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons

Xiao

et al. 2019

npj Comput Mater

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Graphene nanoribbons (GNRs) can be synthesized from molecular precursors with atomic precision. A prominent case is the 7atom-wide armchair GNR made from 10,10′-dibromo-9,9′-bianthryl (DBBA) precursors on metal substrates through dehalogenation/ polymerization followed by cyclodehydrogenation. We investigate the key aspects of the cyclodehydrogenation process by evaluating the energy profiles of various reaction pathways using density functional theory and the nudged elastic band method. The metal substrate plays a critical catalytic role by providing stronger adsorption for products and facilitating H desorption. For polyanthrylene on an extra layer of GNR on Au, the underlying GNR insulates it from the Au substrate and increases the reaction barriers, rendering the polyanthrylene "quasi-freestanding". However, positive charge injection can induce localized cyclodehydrogenation. We find that this is due to the stabilization of an intermediate state through an arenium ion mechanism and favorable orbital symmetries. These results provide mechanistic insight into the effects of the metal substrate and charge injection on cyclodehydrogenation during GNR synthesis and offer guidance for the design and growth of new graphitic structures.

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Section: Introductionmentioning

confidence: 97%

Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons

Xiao

et al. 2019

npj Comput Mater

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“…Over recent years, surface‐confined covalent coupling has been emerging as an alternative approach to traditional solvent‐based chemical routes for the “bottom‐up” synthesis of conjugated nanostructures which are currently considered as fundamental building blocks for the development of future electronic devices . Various types of well‐known chemical reactions have so far been employed to obtain one‐ and two‐dimensional (1D/2D) covalently bonded nanostructures on metal surfaces under ultrahigh vacuum (UHV) conditions, such as Ullmann coupling, imine coupling, Glaser–Hay coupling, dehydration, dehydrogenation, Click reactions, and others . Among them, Ullmann coupling of aryl halides on metal surfaces has attracted much attention from the scientific community and is the most studied on‐surface reaction to date.…”

Section: Introductionmentioning

confidence: 99%

Comparing Ullmann Coupling on Noble Metal Surfaces: On‐Surface Polymerization of 1,3,6,8‐Tetrabromopyrene on Cu(111) and Au(111)

Pham

Song

Nguyen

et al. 2016

Chemistry A European J

106

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The on-surface polymerization of 1,3,6,8-tetrabromopyrene (Br4 Py) on Cu(111) and Au(111) surfaces under ultrahigh vacuum conditions was investigated by a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Deposition of Br4 Py on Cu(111) held at 300 K resulted in a spontaneous debromination reaction, generating the formation of a branched coordination polymer network stabilized by C-Cu-C bonds. After annealing at 473 K, the C-Cu-C bonds were converted to covalent C-C bonds, leading to the formation of a covalently linked molecular network of short oligomers. In contrast, highly ordered self-assembled two-dimensional (2D) patterns stabilized by both Br-Br halogen and Br-H hydrogen bonds were observed upon deposition of Br4 Py on Au(111) held at 300 K. Subsequent annealing of the sample at 473 K led to a dissociation of the C-Br bonds and the formation of disordered metal-coordinated molecular networks. Further annealing at 573 K resulted in the formation of covalently linked disordered networks. Importantly, we found that the chosen substrate not only plays an important role as catalyst for the Ullmann reaction, but also influences the formation of different types of intermolecular bonds and thus, determines the final polymer network morphology. DFT calculations further support our experimental findings obtained by STM and XPS and add complementary information on the reaction pathway of Br4 Py on the different substrates.

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“…The progression of DBBA to GNRs has been described at length [5][6][7][8][9][10]. The use of DBBA has apparently been motivated by a wish to use the advantageous Ullmann dissociation reaction to polymerize DBBA in an ordered, Br-end to Br-end, fashion [5].…”

Section: Introductionmentioning

confidence: 99%

Dibromobianthryl ordering and polymerization on Ag(100)

Smalley

Lahti

Pussi

et al. 2017

The Journal of Chemical Physics

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We study the interaction between dibromobianthryl (DBBA) and the Ag(100) surface using scanning tunneling microscopy and density functional theory. DBBA is prochiral on adsorption and forms racemic domains with molecular rows aligned with the substrate nearest-neighbor [011] and [011] directions. Deposition at elevated temperature leads to the formation of disordered meandering graphene nanowires of constant width.⇤ jsmerdon@uclan.ac.uk

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Polymerization of Polyanthrylene on a Titanium Dioxide (011)‐(2×1) Surface

Cited by 25 publications

References 33 publications

Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons

Ab initio investigation of the cyclodehydrogenation process for polyanthrylene transformation to graphene nanoribbons

Comparing Ullmann Coupling on Noble Metal Surfaces: On‐Surface Polymerization of 1,3,6,8‐Tetrabromopyrene on Cu(111) and Au(111)

Dibromobianthryl ordering and polymerization on Ag(100)

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