Grating of single Lu@C82 molecules using supramolecular network

Silly, Fabien; Shaw, Adam Q.; Porfyrakis, Kyriakos; Warner, Jamie H.; Watt, Andrew; Castell, Martin R.; Umemoto, Hisashi; Akachi, Takao; Shinohara, Hisanori; Briggs, G. Andrew D.

doi:10.1039/b809004a

Cited by 20 publications

(52 citation statements)

References 31 publications

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“…This Boltzmann estimate ignores 120°interfaces, presumes all tape alignments have identical entropy of formation and that graphene and solvent do not impact the relative assembly free energies (see Supporting Information). The SAE based estimates of A-[23 11,13 ] 2 slip and enantio-slip interface densities ( 14,16 ] 2 agree with the experimental results (none detected) but the predicted enantio-slip densities (<10 −5 /100 nm) underestimate the experimental results by 5 orders of magnitude (Table 1). For these two molecules, the thermodynamic (simulation) estimates of enantio-slip densities must incorporate incorrect assumptions.…”

Section: ■ Experimental Methodssupporting

confidence: 75%

“…Thus, A-[23 11,13 ] 2 monolayer samples formed by room temperature drop-casting may be nearly but not fully equilibrated. As kinetic barriers to desorption increase with chain length, 30 14,16 ] 2 appear "fuzzy", an indication of local free volume, nonoptimal packing, and dynamics at these domain interfaces. 33−36 Molecular mechanics simulations of monolayer sections on a graphene sheet were performed to model packing morphologies within domains and at interfaces and to evaluate their relative self-assembly energies (SAE).…”

Section: ■ Experimental Methodsmentioning

confidence: 98%

“…Within even-position alkadiynylanthracene monolayers, the enantio-slip interface structure is not robust. A-[25 12,14 14,16 ] 2 diastereotopic 120°interfaces (50 nm × 50 nm). The red lines are parallel.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

“…Areal frequencies of the three domain interface types were determined from multiple 100 nm ×100 nm sections of dropcast monolayers (not annealed) of A-[23 11 14,16 ] 2 monolayers produces longer range packing fidelity parallel to the anthracene columns.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

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Odd or Even? Monolayer Domain Size Depends on Diyne Position in Alkadiynylanthracenes

et al. 2013

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1,5-(Alkadiynyl)anthracenes self-assemble single component and multicomponent monolayers at the solution-HOPG interface. An alkadiynyl chain's kinked shape constrains the molecular structures with which it can close-pack. This affords rudimentary molecular recognition that has been used to direct self-assembly of 1-D patterned, multicomponent monolayers. The unit cell building blocks of single- and multicomponent alkadiynylanthracene monolayers repeat with high fidelity for 100s of nanometers along the side chain direction. Unit cell repeat fidelity along the orthogonal, anthracene column direction of the monolayer depends on diyne location within the side chain; even-position diyne side chains produce high fidelity of unit cell repeats and wider domain widths along the anthracene columns, whereas odd-position diyne side chains produce more frequent domain interfaces that disrupt the anthracene columns. Alkadiynylanthracene monolayers may be viewed as stacks of 1-D molecular tapes. 1-D tape molecular composition, sequence, and intratape side chain alignment are dictated by shape complementarity of the kinked alkadiynyl side chains. Stacking alignments of adjacent 1-D tapes are controlled by shape matching of tape peripheries and determine repeat fidelity along the anthracene columns. Tapes stacked with a constant intertape alignment comprise crystalline domains that repeat along the anthracene columns. The 1-D tapes formed by anthracenes with odd-position diynes have triangle wave peripheries that close-pack in multiple stacking alignments. This reduces unit cell repeat fidelity and decreases the widths of crystalline domains along the anthracene columns. Even-position diyne side chains form 1-D tapes with trapezoid wave peripheries that close-pack in only one stacking alignment. This generates higher stacking fidelity, larger domain widths, and fewer domain interfaces along the anthracene columns of even-position diyne monolayers. Even- and odd-position diyne monolayers exhibit comparable densities of interfaces between enantiotopic domains and between domains aligned along different graphite symmetry axes. These interfaces likely arise through collisions of independently nucleated/growing domains and persist for lack of kinetically competent pathways that interconvert or merge the domains.

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Section: ■ Experimental Methodssupporting

confidence: 75%

Section: ■ Experimental Methodsmentioning

confidence: 98%

Section: ■ Experimental Methodsmentioning

confidence: 99%

Section: ■ Experimental Methodsmentioning

confidence: 99%

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Odd or Even? Monolayer Domain Size Depends on Diyne Position in Alkadiynylanthracenes

et al. 2013

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“…[1][2][3] Conventionally, the assembled molecules are held together by non-covalent interactions, [4][5][6][7][8][9][10] among which the hydrogen bond (HB) is frequently adopted for structural controllability owing to its desirable bonding strength, selectivity, and directionality. [1] This strategy has been utilized in both uni- [6] and bimolecular [11][12][13][14][15] systems. Generally speaking, hydrogen bonds of similar bond strength are less versatile than hierarchical ones in tuning the assembled structures.…”

mentioning

confidence: 99%

Two‐Dimensional Molecular Porous Networks Formed by Trimesic Acid and 4,4′‐Bis(4‐pyridyl)biphenyl on Au(111) through Hierarchical Hydrogen Bonds: Structural Systematics and Control of Nanopore Size and Shape

et al. 2011

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Two-dimensional (2D) molecular porous networks (MPNs) self-assembled on surfaces are of great interest due to their potential applications in nanoscience. [1][2][3] Conventionally, the assembled molecules are held together by non-covalent interactions, [4][5][6][7][8][9][10] among which the hydrogen bond (HB) is frequently adopted for structural controllability owing to its desirable bonding strength, selectivity, and directionality. [1] This strategy has been utilized in both uni- [6] and bimolecular [11][12][13][14][15] systems. Generally speaking, hydrogen bonds of similar bond strength are less versatile than hierarchical ones in tuning the assembled structures. In nature, hierarchical hydrogen-bond systems with disparate bonding capabilities and strengths are widely adopted by biosystems such as DNA and bioactive structures which consist of only limited building blocks. Researchers have utilized metal coordination [16,17] or hydrogen bonds [4,18] to form various porous networks on surfaces. Controls of the network pattern and the resulting pore size and shape can be achieved by tuning parameters [17,[19][20][21] such as ligand chain lengths or molecular backbones, [19] surface coverage [20] and substrate temperature.[22] These strategies have been demonstrated for a number of uni- [16,20] or bimolecular systems. [18,23] For example, by adjusting the metal-to-ligand ratio and the annealing temperature, mononuclear, 1D-polymeric and 2D-reticulated metal-organic coordination networks can be obtained by vapor deposition of 1,4-benzenedicarboxylic acid molecules and iron atoms on a Cu(100) surface, giving rise to an interesting series of square, rectangular and rhombic pores. [16] Another excellent example demonstrating controls of the network pattern and pore morphology is the 2D mono-and bicomponent self-assembly of three closely related diaminotriazine-based molecular building blocks and a complementary perylenetetracarboxylic diimide on Au(111) surface. The interplay, and the hierarchy, of hydrogen bonding, metalligand coordination, and dipolar interactions, resulted in various MPNs. In one case, mixtures of square, rhombic, and hexagonal nanopores were obtained.[24] A third example illustrating the construction of tunable 2D binary molecular nanostructures on an inert surface is the co-deposition of copper hexadecafluorophthalocyanine with p-sexiphenyl, pentacene, or diindenoperylene on graphite. By varying the binary molecular ratio and the molecular geometry, various molecular networks with tunable intermolecular distances were fabricated. [18,25] Yet other studies of porous networks via coadsorption of multi-component or multi-functional adsorbates or solvent incorporation on surfaces, producing a wide variety of interesting nanostructures, can also be found in the literature. [26][27][28][29][30][31] These results offer various routes for fabricating tunable molecular networks with tailorable nanopores potentially useful in engineering molecular sensors, molecular spintronic devices, and molecular nano h...

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Two‐Dimensional Supramolecular Chemistry

Phillips

Beton

Champness

2012

Supramolecular Chemistry

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Two‐dimensional assembly of molecular assemblies on surfaces represents a significant challenge to chemists, materials scientists, and physicists. Supramolecular chemistry offers many advantageous strategies for the development of such arrays through the use of intermolecular interactions to control the process of molecular organization and self‐assembly. This article reveals how hydrogen bonds, dipole–dipole, van der Waals interactions, and metal–ligand coordination can be used to assemble two‐dimensional arrays on surfaces. Such supramolecular assemblies can be used to trap guest species mimicking host–guest chemistry in the solution phase. By the use of the molecular resolution of scanning‐probe microscopies, particularly scanning tunneling microscopy, the precise arrangement of the supramolecular assemblies can be probed and evaluated including the relative orientation with respect to the surface. The influence of the surface on the self‐assembly process is discussed and it is shown that far from playing a passive role in the self‐assembly process the substrate can strongly influence the supramolecular chemistry observed. Such images provide great insight into the advantages and restrictions of working in two dimensions in comparison to the solution phase or the solid state.

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Grating of single Lu@C82 molecules using supramolecular network

Abstract: A supramolecular grating of single Lu@C(82) molecules was obtained by depositing Lu@C(82) molecules onto a room temperature PTCDI-melamine network.

Cited by 20 publications

References 31 publications

Odd or Even? Monolayer Domain Size Depends on Diyne Position in Alkadiynylanthracenes

Odd or Even? Monolayer Domain Size Depends on Diyne Position in Alkadiynylanthracenes

Two‐Dimensional Molecular Porous Networks Formed by Trimesic Acid and 4,4′‐Bis(4‐pyridyl)biphenyl on Au(111) through Hierarchical Hydrogen Bonds: Structural Systematics and Control of Nanopore Size and Shape

Two‐Dimensional Supramolecular Chemistry

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