Evolution of adsorption heights in the on-surface synthesis and decoupling of covalent organic networks on Ag(111) by normal-incidence X-ray standing wave

Grossmann, Lukas; Duncan, David A.; Jarvis, Samuel; Jones, Robert G.; De, Soumen; Rosén, Johanna; Schmittel, Michael; Heckl, Wolfgang M.; Björk, Jonas; Lackinger, Markus

doi:10.1039/d1nh00486g

Cited by 21 publications

(28 citation statements)

References 56 publications

(91 reference statements)

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“…Previously, we used intercalation of an iodine monolayer between covalent networks and the metal surfaces on which they were grown for their post‐synthetic decoupling [15] . From X‐ray standing wave experiments, we inferred an increase of the average adsorption height of covalent triazine‐phenylene networks from 0.31 nm on pristine Ag(111) to 0.59 nm upon iodine intercalation [16] . This implies highly efficient decoupling by the iodine monolayer, which for fantrip becomes readily apparent in the DFT calculations in Figure 2.…”

Section: Resultsmentioning

confidence: 89%

“…[15] From X-ray standing wave experiments, we inferred an increase of the average adsorption height of covalent triazine-phenylene networks from 0.31 nm on pristine Ag(111) to 0.59 nm upon iodine intercalation. [16] This implies highly efficient decoupling by the iodine monolayer, which for fantrip becomes readily apparent in the DFT calculations in Figure 2. In comparison to pristine Au(111), fantrip adsorption not only becomes generally weaker on IÀ Au(111) as similarly inferred for hexadecylamine on chlorine and iodine passivated copper surfaces, [17] but even the energetic ordering of the two competing structures is reversed.…”

Section: Methodsmentioning

confidence: 92%

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Steering Self‐Assembly of Three‐Dimensional Iptycenes on Au(111) by Tuning Molecule‐Surface Interactions

et al. 2022

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Self-assembly of three-dimensional molecules is scarcely studied on surfaces. Their modes of adsorption can exhibit far greater variability compared to (nearly) planar molecules that adsorb mostly flat on surfaces. This additional degree of freedom can have decisive consequences for the expression of intermolecular binding motifs, hence the formation of supramolecular structures. The determining moleculesurface interactions can be widely tuned, thereby providing a new powerful lever for crystal engineering in two dimensions. Here, we study the self-assembly of triptycene derivatives with anthracene blades on Au-( 111) by Scanning Tunneling Microscopy, Near Edge Xray Absorption Fine Structure and Density Functional Theory. The impact of molecule-surface interactions was experimentally tested by comparing pristine with iodinepassivated Au(111) surfaces. Thereby, we observed a fundamental change of the adsorption mode that triggered self-assembly of an entirely different structure.

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Section: Resultsmentioning

confidence: 89%

Section: Methodsmentioning

confidence: 92%

Steering Self‐Assembly of Three‐Dimensional Iptycenes on Au(111) by Tuning Molecule‐Surface Interactions

et al. 2022

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“…Exchange‐correlation were described by the van der Waals density functional (vdW‐DF), [ 45 , 46 ] in the recent form by Hamada, [ 47 ] denoted by rev‐vdW‐DF2, which has shown to accurately describe molecular adsorption on gold and silver surfaces. [ 48 , 49 ] The Ag(111) and Au(111) surfaces were represented by four layered slabs. For the calculations of the monomer adsorption as well as the coupling between two monomers a p (8 × 8) surface unit cell together with a 4 × 4 k ‐point sampling for Ag(111) and a 8 × 8 k ‐point sampling for Au(111).…”

Section: Methodsmentioning

confidence: 99%

Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers

et al. 2022

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On-surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N-containing pentacene-based precursor (tetraazapentacene) is ex-professo synthesized endowed with terminal dibromomethylene (:CBr 2 ) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N-containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 °C, affording a pyrrolopyrrole-bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 °C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N-containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms.

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“…Zuvor hatten wir die Interkalation einer Jod‐Monolage zwischen kovalenten Netzwerken und den Metalloberflächen, auf denen diese gewachsen wurden, für ihre postsynthetische Entkopplung genutzt [15] . Experimente mit stehenden Röntgenwellen ergaben eine Erhöhung der mittleren Adsorptionshöhe von kovalenten Triazin‐Phenylen‐Netzwerken von 0.31 nm auf reinem Ag(111) auf 0.59 nm nach der Jod‐Interkalation [16] . Dies impliziert eine hocheffiziente Entkopplung durch die Jod‐Monolage, im Einklang mit den DFT‐Berechnungen für Fantrip in Abbildung 2.…”

Section: Ergebnisse Und Diskussionunclassified

“…[15] Experimente mit stehenden Röntgenwellen ergaben eine Erhöhung der mittleren Adsorptionshöhe von kovalenten Triazin-Phenylen-Netzwerken von 0.31 nm auf reinem Ag(111) auf 0.59 nm nach der Jod-Interkalation. [16] Dies impliziert eine hocheffiziente Entkopplung durch die Jod-Monolage, im Einklang mit den DFT-Berechnungen für Fantrip in Abbildung 2. Im Vergleich zu reinem Au(111) ist die Adsorption von Fantrip auf IÀ Au(111) nicht nur insgesamt schwächer, wie dies auch für Hexadecylamin auf Chlorund Jod-passivierten Kupferoberflächen festgestellt wurde, [17]…”

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Steuerung der Selbstassemblierung von dreidimensionalen Iptycenen auf Au(111) durch Abstimmung der Molekül‐Oberflächen‐Wechselwirkungen

et al. 2022

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Die Selbstassemblierung dreidimensionaler Moleküle auf Oberflächen ist bislang kaum untersucht. Ihre Adsorptionsmodi können im Vergleich zu (nahezu) planaren Molekülen, die meist flach auf Oberflächen adsorbieren, eine viel größere Variabilität aufweisen. Dieser zusätzliche Freiheitsgrad kann entscheidende Konsequenzen für die Ausprägung intermolekularer Bindungsmotive und damit für die supramolekulare Strukturbildung haben. Dabei ist es möglich die bestimmenden Molekül‐Oberflächen‐Wechselwirkungen über weite Bereiche einzustellen, was einen neuen, wirkmächtigen Hebel zur Steuerung der Kristallisation in zwei Dimensionen darstellt. Hier untersuchen wir die Selbstassemblierung von Triptycen‐Derivaten mit Anthracen‐Einheiten auf Au(111) mit Hilfe der Raster‐Tunnel‐Mikroskopie, der Röntgen‐Nahkanten‐Absorptions‐Spektroskopie und der Dichte‐Funktional‐Theorie. Der Einfluss von Molekül‐Oberflächen‐Wechselwirkungen wurde experimentell durch den Vergleich von reinen mit Jod‐passivierten Au(111) Oberflächen untersucht. Dabei beobachteten wir eine grundlegende Änderung des Adsorptionsmodus, die zur Selbstassemblierung einer grundlegend verschiedenen Struktur führte.

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Evolution of adsorption heights in the on-surface synthesis and decoupling of covalent organic networks on Ag(111) by normal-incidence X-ray standing wave

Abstract: Structural characterization in on-surface synthesis is primarily carried out by Scanning Probe Microscopy (SPM) which provides high lateral resolution. Yet, important fresh perspectives on surface interactions and molecular conformations are...

Cited by 21 publications

References 56 publications

Steering Self‐Assembly of Three‐Dimensional Iptycenes on Au(111) by Tuning Molecule‐Surface Interactions

Steering Self‐Assembly of Three‐Dimensional Iptycenes on Au(111) by Tuning Molecule‐Surface Interactions

Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers

Steuerung der Selbstassemblierung von dreidimensionalen Iptycenen auf Au(111) durch Abstimmung der Molekül‐Oberflächen‐Wechselwirkungen

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