Nanopatterns of arylene–alkynylene squares on graphite: self-sorting and intercalation

Keller, Tristan J.; Bahr, Joshua; Gratzfeld, Kristin; Schönfelder, Nina; Majewski, Marcin A.; Stępień, Marcin; Höger, Sigurd; Jester, Stefan‐S.

doi:10.3762/bjoc.15.180

Cited by 10 publications

(13 citation statements)

References 41 publications

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“…STM visualization of TCB molecules coadsorbed in macrocyclic interiors 41,72−74 as well as in the space between adsorbed molecules was reported previously. 41,75 To support this hypothesis, we performed molecular mechanics (MM) simulations using the COMPASS force field for a single molecule of unsubstituted PyBM adsorbed on a graphene bilayer as a graphite model and compared it with a complex incorporating two molecules of TCB in the nanopore (Figure 3). The positions of TCB molecules were optimized as two TCB molecules facing to generate Cl•••H hydrogen bonds by performing calculations from various initial geometries.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…[14][15][16][17][18][19][20][21][22][23][24][25][26] The other one is the use of macrocycles having an intrinsic porous space. [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] Although the former approach is favorable in view of the facile modification of size and shape of the porous space, these networks are susceptible to dramatic changes depending on the external environment such as solvent, concentration, and temperature, because network structure is sustained by relatively weak non-covalent interactions.…”

Section: Introductionmentioning

confidence: 99%

“…There are two possible approaches to construct porous spaces for guest binding on surfaces. One is the self-assembly of acyclic building blocks to form extrinsic porous 2D space. − The other is the use of macrocycles having an intrinsic porous space. − Although the former approach is favorable in view of the facile modification of size and shape of the porous space, these networks are susceptible to dramatic changes depending on the external environment such as solvent, concentration, and temperature because network structure is sustained by relatively weak noncovalent interactions. In this respect, robust porous 2D networks (so-called 2D-COFs) − formed by covalent linking of acyclic building blocks on surfaces have been shown to cover this disadvantage, immobilizing guest molecules in size-complement manner. − The latter approach is advantageous in view of the strict control of the physical and chemical environment of the intrinsic porous space, though synthesis of macrocycles is more labor demanding compared to acyclic building blocks.…”

Section: Introductionmentioning

confidence: 99%

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Electrostatically Driven Guest Binding in Self-Assembled Molecular Network of Hexagonal Pyridine Macrocycle at the Liquid/Solid Interface: Symmetry Breaking Induced by Coadsorbed Solvent Molecules

et al. 2019

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We present here the construction of a self-assembled two-dimensional network at the liquid/solid interface using a hexagonal pyridine macrocycle which binds an organic cation in its intrinsic porous space by electrostatic interactions. For this purpose, a hexagonal pyridinylene-butadiynylene macrocycle (PyBM) having six octyloxymethyl groups, PyBM-C8, was synthesized. As guests, tropylium (Tr) tetrafluoroborate and trioxatriangulenium (TOTA) hexafluorophosphate were used. In this study, we focused on (i) the network patterns of PyBM-C8 which change in response to its concentration and (ii) the position of the guest immobilized in the porous space of the macrocycle. Scanning tunneling microscopy (STM) observations at the interface of 1,2,4-trichlorobenzene (TCB) and highly oriented pyrolytic graphite (HOPG) revealed that PyBM-C8 formed four different polymorphs, oblique, loose hexagonal, linear, and rectangular, depending on the solute concentration and annealing treatment. Solvent TCB molecules are likely co-adsorbed not only the intrinsically porous space of PyBM-C8 (internal TCB) but also the space outside of the macrocycle between its alkyl chains (external TCB) in most of the cases. Upon adding the guest cation, whereas small Tr was not visualized in the pore due to size mismatching, larger TOTA was clearly observed in each pore. In addition, based on high resolution STM images of the rhombus packing pattern of PyBM-C8, we 3 revealed experimentally that TOTA was placed at an off-center position of the deformed hexagonal macrocyclic core in the rhombus pattern. Based on the molecular mechanics calculations, we hypothesize that the off-center location of TOTA is due to deformation of the hexagonal macrocycle through interaction with two external TCB molecules located at opposite edges of the macrocyclic core. Symmetry-breaking of the macrocyclic host framework induced by co-adsorbed surrounding solvent molecules thus play a significant role in host-guest complexation at the liquid/solid interface.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electrostatically Driven Guest Binding in Self-Assembled Molecular Network of Hexagonal Pyridine Macrocycle at the Liquid/Solid Interface: Symmetry Breaking Induced by Coadsorbed Solvent Molecules

et al. 2019

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“…Moreover, the smaller intermolecular (and hexagonal as well as pentagonal intramolecular) nanopores in the cocrystal (cf. Figure 5 a/d/g) lead to a confinement of motion of 21 (and 19 as well as 3×2) intercalated TCB solvent molecules and appear as medium‐bright punctate features [23] . In contrast, the nonspecific intercalation of 1 (possible in the honeycomb pattern of pure 1 , cf.…”

Section: Figurementioning

confidence: 96%

Supramolecular Nanopatterns of Molecular Spoked Wheels with Orthogonal Pillars: The Observation of a Fullerene Haze

et al. 2021

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Molecular spoked wheels with intraannular functionalizable pillars are synthesized in a modular approach. The functionalities at their ends are variable, and a propargyl alcohol, a [6,6]‐phenyl‐C61‐butyrate, and a perylene monoimide are investigated. All compounds form two‐dimensional crystals on highly oriented pyrolytic graphite at the solid–liquid interface. As determined by submolecularly resolved scanning tunneling microscopy, the pillars adopt equilibrium distances of 6.0 nm. The fullerene has a residual mobility, limited by the length of the flexible connector unit. The experimental results are supported and rationalized by molecular dynamics simulations. These also show that, in contrast, the more rigidly attached perylene monoimide units remain oriented along the surface normal and maintain a smallest distance of 2 nm above the graphite substrate. The robust packing concept also holds for cocrystals with molecular hexagons that expand the pillar–pillar distances by 15 % and block unspecific intercalation.

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“…Alkyl chain interdigitation, hydrogen bonding and metal‐ligand coordination are typical non‐covalent bonds used for in‐plane interactions that allow the generation of complex structures on the surface, sometimes forming porous networks capable to incorporate additional molecules [10a,c,d,11] . Beside these “intermolecular cavities”, shape‐persistent macrocycles contain additional “intramolecular cavities” without [11] or with [12] specific functionalities.…”

Section: Introductionmentioning

confidence: 99%

Highly Strained Nanoscale Bicyclophane Monolayers Entering the Third Dimension: A Combined Synthetic and Scanning Tunneling Microscopy Investigation

et al. 2021

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Tetrabromo aromatics can be synthesized by the Fischer-Zimmermann condensation of appropriate pyrylium salts with arylene dicarboxylic acid salts. Their cyclization by intramolecular Yamamoto coupling yields strained bicyclophanes with adjustable sizes and different intraannular bridges. All compounds adsorb at the solid/liquid interface on highly oriented pyrolytic graphite (HOPG) and are investigated by scanning tunneling microscopy (STM) with submolecular resolution. The observed two-dimensional (2D) supramolecular nanopatterns depend only on the sizes and alkoxy periphery of the cyclophanes and are independent of the specific structures of the intraannular bridges. Since the central arylene moieties of the smaller species are oriented perpendicular to the planes of the bicyclophanes, their substituents protrude from the surface by up to 1.6 nm after adsorption. Therefore, these molecules are attractive platforms for addressing the volume phase above the graphite surface.

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Nanopatterns of arylene–alkynylene squares on graphite: self-sorting and intercalation

Cited by 10 publications

References 41 publications

Electrostatically Driven Guest Binding in Self-Assembled Molecular Network of Hexagonal Pyridine Macrocycle at the Liquid/Solid Interface: Symmetry Breaking Induced by Coadsorbed Solvent Molecules

Electrostatically Driven Guest Binding in Self-Assembled Molecular Network of Hexagonal Pyridine Macrocycle at the Liquid/Solid Interface: Symmetry Breaking Induced by Coadsorbed Solvent Molecules

Supramolecular Nanopatterns of Molecular Spoked Wheels with Orthogonal Pillars: The Observation of a Fullerene Haze

Highly Strained Nanoscale Bicyclophane Monolayers Entering the Third Dimension: A Combined Synthetic and Scanning Tunneling Microscopy Investigation

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