Dissymmetric On-Surface Dehalogenation Reaction Steered by Preformed Self-Assembled Structure

Lü, Hui; Wenlong, E; Cai, Liangliang; Ma, Zhibo; Xu, Wei; Yang, Xueming

doi:10.1021/acs.jpclett.9b03688

Cited by 16 publications

(16 citation statements)

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“…[6][7][8] During this transformation halogenated organic tectons adsorbed on catalytically active metallic surfaces (e. g. Cu(111), Ag(111), Au(111)), usually under high vacuum conditions, lose halogen atoms and use the resulting reactive centers to form covalent CÀ C bonds. To date, numerous experimental studies of the Ullmann reaction have been performed in which such molecules as terphenyls, [9,10] polyaromatic hydrocarbons (PAHs), [11][12][13][14] porphyrins [15,16] and others [17,18] with differently introduced halogen atoms were used. Those studies demonstrated the possibility of creation of covalent polymers with diverse architectures, including macrocycles, [10,19] chains, [9,17,20] strands, [21] nanoribbons, [22,23] and networks.…”

Section: Introductionmentioning

confidence: 99%

“…To date, numerous experimental studies of the Ullmann reaction have been performed in which such molecules as terphenyls, [9,10] polyaromatic hydrocarbons (PAHs), [11][12][13][14] porphyrins [15,16] and others [17,18] with differently introduced halogen atoms were used. Those studies demonstrated the possibility of creation of covalent polymers with diverse architectures, including macrocycles, [10,19] chains, [9,17,20] strands, [21] nanoribbons, [22,23] and networks. [24,25] In certain instances, an important step of the Ullmann coupling involves the formation of labile metal-organic precursors preceding the final covalent bonding of dehalogenated monomeric units.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Modeling of the Metal‐Organic Precursors of Anthracene‐Based Covalent Networks on Surfaces

Lisiecki

Szabelski

2022

ChemPhysChem

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Surface‐assisted fabrication of molecular network architectures has been a promising route to low‐dimensional materials with unique physicochemical properties and functionalities. One versatile way in this field is the Ullmann coupling reaction of halogenated organic monomers on catalytically active metallic surfaces. In this work, using the coarse‐grained Monte Carlo simulations, we studied the on‐surface self‐assembly of metal‐organic precursors preceding the covalent Ullman‐type linkage of tetrahalogenated anthracene building blocks. To that end, a series of positional isomers was examined and classified with respect to their ability of creation of extended network structures. Our simulations focused on the identification of basic types of self‐assembly scenarios distinguishing enantiopure and racemic systems and producing periodic and aperiodic networks. The calculations carried out for selected tectons demonstrated wide possibilities of controlling porosity (e. g. pore size, shape, periodicity, chirality, heterogeneity) of the networks by suitable functionalization of the monomeric unit. The findings reported herein can be helpful in rational designing of 2D polymeric networks with predefined structures and properties.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical Modeling of the Metal‐Organic Precursors of Anthracene‐Based Covalent Networks on Surfaces

Lisiecki

Szabelski

2022

ChemPhysChem

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“…It is well known that debromination from sp 2 carbons usually occurs on Ag(111) even at RT. 27,57,58 In fact, we also observed dissociated Br atoms from 1 on the terraces as indicated by circles in Fig. 2a and Fig.…”

Section: Resultsmentioning

confidence: 59%

Multiple molecular interactions between alkyl groups and dissociated bromine atoms on Ag(111)

Kawai

Sugawara

et al. 2022

Phys. Chem. Chem. Phys.

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“…To start with, the bimetallic substrate of Bi–Ag(111) is prepared by depositing roughly 0.1 monolayer (ML) Bi onto Ag(111) (herein, the full coverage of bismuth on Ag(111) is referred to as 0.33 ML Bi with the root 3 by root 3 superstructure, and details can be found in the literature. , According to previous reports, Ag(111) can partially dissociate at RT the C–Br bond of halogenated precursors and thus induce the formation of organometallic (OM) species upon adsorption. − Interestingly, once on the Bi–Ag(111) surface, Br 2 Py molecules (about 0.1 ML) self-assemble into a porous structure witnessed by STM in Figure a, while Bi adatoms are randomly parked on the surface. Additional deposition of Br 2 Py precursors (0.4 ML in total) onto Bi–Ag(111) as presented in Figure b leads to the extension of the porous network together with the formation of a close-packed phase.…”

Section: Resultsmentioning

confidence: 99%

Tuning Dehalogenative Coupling of Br₂Py on Bimetallic Templates

Wang

Liang

et al. 2022

Langmuir

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Considerable attention has been paid to on-surface Ullmann coupling during the past decade owing to the feasible synthesis of artificial nanostructures. While previous reports mainly concentrated on coupling reactions on single-metal-atom surfaces, herein we present the Ullmann coupling of 2,7-dibromopyrene (Br2Py) on bimetallic surfaces, Bi–Ag(111) and Bi–Au(111), respectively, with scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). On the Bi-decorated Ag(111), self-assembly of intact Br2Py is realized due to the reduced activity at the interface. Subsequent annealing promotes the dehalogenation of Br2Py on Bi–Ag(111), while Bi adatoms do not bring any visible influence on coupling reactions. Furthermore, post-deposition of Bi onto preassembled nanostructures on Ag(111) immediately initiates the Ullmann coupling by inducing more Ag adatoms available on the surface, while stepwise annealing afterward leads to complete polymerization and formation of covalent chains with lateral displacement compared to that on the bare Ag(111), probably due to the space hindrance and confinement. For Bi–Au(111) with the modified reconstruction, higher-temperature annealing is required to trigger Ullmann coupling compared to that on Au(111). The exception is that the C–C coupling reaction remains impervious to Bi adatoms, and recovery of the Bi–Au reconstruction is realized after intensive annealing. In principle, bimetallic surfaces herein present intriguing behavior toward the controllable Ullmann coupling, and this report might provide different insights into the comprehensive atomistic elucidation of reaction mechanisms as well as the design of a new platform to effectively regulate Ullmann coupling.

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Dissymmetric On-Surface Dehalogenation Reaction Steered by Preformed Self-Assembled Structure

Cited by 16 publications

References 43 publications

Theoretical Modeling of the Metal‐Organic Precursors of Anthracene‐Based Covalent Networks on Surfaces

Theoretical Modeling of the Metal‐Organic Precursors of Anthracene‐Based Covalent Networks on Surfaces

Multiple molecular interactions between alkyl groups and dissociated bromine atoms on Ag(111)

Tuning Dehalogenative Coupling of Br₂Py on Bimetallic Templates

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Dissymmetric On-Surface Dehalogenation Reaction Steered by Preformed Self-Assembled Structure

Cited by 16 publications

References 43 publications

Theoretical Modeling of the Metal‐Organic Precursors of Anthracene‐Based Covalent Networks on Surfaces

Theoretical Modeling of the Metal‐Organic Precursors of Anthracene‐Based Covalent Networks on Surfaces

Multiple molecular interactions between alkyl groups and dissociated bromine atoms on Ag(111)

Tuning Dehalogenative Coupling of Br2Py on Bimetallic Templates

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Tuning Dehalogenative Coupling of Br₂Py on Bimetallic Templates