An On‐Surface Reaction Confined within a Porous Molecular Template

Judd, Chris J.; Champness, Neil R.; Saywell, Alex

doi:10.1002/chem.201704693

Cited by 15 publications

(19 citation statements)

References 51 publications

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“…Combining this with measurements from additional images of the same surface, the centre-centre separation for TPB units within the MO structure is found to be 1.63 ± 0.1 nm. This is consistent with the expected dimensions for two TPB molecules bridged by a C-Ag-C link (compare with 1.61 ± 0.1 nm from our previous studies of TPB MO 20 and similar molecules, 1.61 ± 0.2 nm 26 ). The axis of this bond is misaligned to the < 110> set of crystal directions (substrate close-packed directions) by 25 ± 2°.…”

Section: Resultssupporting

confidence: 92%

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Structural characterisation of molecular conformation and the incorporation of adatoms in an on-surface Ullmann-type reaction

et al. 2020

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The on-surface synthesis of covalently bonded materials differs from solution-phase synthesis in several respects. The transition from a three-dimensional reaction volume to quasi-two-dimensional confinement, as is the case for on-surface synthesis, has the potential to facilitate alternative reaction pathways to those available in solution. Ullmann-type reactions, where the surface plays a role in the coupling of aryl-halide functionalised species, has been shown to facilitate extended one- and two-dimensional structures. Here we employ a combination of scanning tunnelling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and X-ray standing wave (XSW) analysis to perform a chemical and structural characterisation of the Ullmann-type coupling of two iodine functionalised species on a Ag(111) surface held under ultra-high vacuum (UHV) conditions. Our results allow characterisation of molecular conformations and adsorption geometries within an on-surface reaction and provide insight into the incorporation of metal adatoms within the intermediate structures of the reaction.

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Section: Resultssupporting

confidence: 92%

“…We denote the subunits within these structures as m-terphenyl (TP MO ) and 1,3,5-triphenylbenzene Annealing at 370 ± 50 K, based on XPS data, results in the formation of a covalently coupled product, TP CC (see refs. 18,20 ).…”

Section: Resultsmentioning

confidence: 99%

Structural characterisation of molecular conformation and the incorporation of adatoms in an on-surface Ullmann-type reaction

et al. 2020

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“…A representative example here are the nanoporous networks which are formed by linear and star‐shaped functional molecules . The nanocavities of these networks, having adjustable size and shape – controlled by the properties of the modifier, provide nanoconfinement for the guest molecules and enforce them to interact/react in a specific pre‐programmed way . Using this approach, very recently Judd and co‐workers have demonstrated the template‐directed self‐assembly and subsequent Ullmann coupling of 1,3,5‐tris(4‐iodophenyl)benzene inside porphyrin rings on Au(111) .…”

Section: Introductionmentioning

confidence: 99%

“…[9,10] The nanocavities of these networks, having adjustable size and shape -controlled by the properties of the modifier, provide nanoconfinement for the guest molecules and enforce them to interact/react in a specific pre-programmed way. [11][12][13] Using this approach, very recently Judd and co-workers have demonstrated the template-directed self-assembly and subsequent Ullmann coupling of 1,3,5-tris(4iodophenyl)benzene inside porphyrin rings on Au(111). [14] Moreover, steering lateral organization of linear and branched guest molecules by means of specially designed corrals nanoshaved on covalently modified graphite has been shown with the STM technique at the liquid/solid interface.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Modeling of the Surface‐Guided Self‐Assembly of Functional Molecules

Nieckarz

Szabelski

2020

ChemPhysChem

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Directing the self‐assembly of organic building blocks with 2D templates has been a promising method to create molecular superstructures having unique physicochemical properties. In this work the on‐surface self‐assembly of simple ditopic functional molecules confined inside periodic nanotemplates was modeled by means of the lattice Monte Carlo simulation method. Two types of confinement, that is honeycomb porous networks and parallel grooves of controlled diameter and width were used in the calculations. Additionally, the effect of (pro)chirality of the adsorbing molecules on the outcome of the templated self‐assembly was examined. To that end, enantiopure and racemic assemblies were studied and the resulting structures were identified and classified. The obtained findings demonstrated that suitable tuning of the structural parameters of the templates enables directing the self‐assembly towards linear and cyclic aggregates with controlled size. Moreover, chiral resolution of the molecular conformers using honeycomb networks with adjusted pore size was found possible. Our theoretical predictions can be helpful in designing structured surfaces to direct self‐assembly and polymerization of organic functional building blocks.

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“…In addition, the sub-molecular resolution offered by scanning probe techniques has allowed on-surface reactions to be characterised at various stages (e.g. initial, intermediate, and final states) 24,25 .…”

Section: Introductionmentioning

confidence: 99%

On-Surface Synthesis within a Porphyrin Nanoring Template

Judd

Kondratuk

Anderson

et al. 2019

Sci Rep

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On-surface synthesis provides a route for the production of 1D and 2D covalently bonded polymeric structures. Such reactions are confined to the surface of a substrate and the catalytic properties of the substrate are often utilised to initiate the reaction. Recent studies have focused on the properties of various crystallographic planes of metallic substrates, as well as native surface features such as step-edges, in an effort to provide control over the pathway of the reaction and the resultant products. An alternative approach is to template the catalytic surface with a porous molecular overlayer; giving rise to well-defined surface regions within which an on-surface reaction may be confined. Here we present a methodology where macromolecular templates are used to confine an on-surface reaction. Cyclic porphyrin polymers, nanorings - consisting of 40 porphyrin units with internal diameter 13 nm, are used to form a template on a Au(111) surface, and an on-surface Ullmann-type coupling reaction is initiated within the nanoring template. The surface confined template and covalently coupled reaction products are investigated and characterised with scanning tunnelling microscopy.

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An On‐Surface Reaction Confined within a Porous Molecular Template

Cited by 15 publications

References 51 publications

Structural characterisation of molecular conformation and the incorporation of adatoms in an on-surface Ullmann-type reaction

Structural characterisation of molecular conformation and the incorporation of adatoms in an on-surface Ullmann-type reaction

Theoretical Modeling of the Surface‐Guided Self‐Assembly of Functional Molecules

On-Surface Synthesis within a Porphyrin Nanoring Template

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