1D and 3D surface-assisted self-organization

Koepf, Matthieu; Cherioux, Frédéric; Wytko, Jennifer A.; Weiss, Jean

doi:10.1016/j.ccr.2012.05.039

Cited by 53 publications

(52 citation statements)

References 139 publications

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“…The two most stable and essentially degenerate diagonal arrangements are shown in Fig. 6(b,c), which differ by a small change in relative positions of the TMTPP components as indicated by the core-to-core surface vectors of (5,4) and (6,3). In both bonded structures, the TMTPP molecules have a configuration and orientation similar to that of the most stable geometry of a single TMTPP molecule on the surface (Fig.…”

Section: (A)mentioning

confidence: 99%

“…Both products are more stable than two unreacted de-H molecules by 0.58 eV, which means that upon dehydrogenation two (or more) approaching molecules are energetically driven to bond. The covalently linked (5,4) and (6,3) accommodated products exhibit a trans conformation of the interconnecting 1,2-ethylene group with an inter-core distance of ~19.4 Å and 19.0 Å, respectively. These connections also lead to slight offsets between the diagonals of the two molecules [32].…”

Section: (A)mentioning

confidence: 99%

“…Figure 7(c,d) show examples of the 4Me-4Me (5,4) and (6,3) reaction products at the surface. A histogram of the distribution of products with the coreto-core vectors measured from our high-resolution data is shown in Fig.…”

Section: (A)mentioning

confidence: 99%

“…In all our simulations the molecules are initially fully hydrogenated and placed reasonably far apart in their stable configurations. As the final product geometry, we considered one of the two most favorable de-H (6,4) bonded pair shown in Fig. 6(b), with the two removed H atoms placed well away from the molecules on the free surface.…”

Section: Simulating the Mechanism Of Inter-molecular Couplingmentioning

confidence: 99%

“…Construction of molecular assemblies and networks at surfaces [1,2] provides a highly promising protocol for synthesizing new 2-D materials, delivering new functionalities for biological applications such as sensors and drug delivery [3] and advanced nanotechnology applications in energy harvesting, catalysis and nano-electronic devices [4,5,6]. For many applications, robust networks stabilized by covalent bonds between constituent molecules [1,2,[7][8][9][10][11][12] are technologically more promising, compared to supramolecular networks stabilized by other types of inter-molecular interactions such as H-bonding or van der Waals [13][14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Driving Forces for Covalent Assembly of Porphyrins by Selective C–H Bond Activation and Intermolecular Coupling on a Copper Surface

et al. 2016

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Recent synthesis of covalent organic assemblies at surfaces has opened up the promise of producing robust nanostructures for functional interfaces. To uncover how this new chemistry works at surfaces and understand the underlying mechanism(s) that control bond-breaking and bond-making processes at specific positions of the participating molecules, we study here the coupling reaction of tetra(mesityl)porphyrin molecules, which creates covalently connected networks on the Cu(110) surface by utilising the 4-methyl groups as unique connection points. Using scanning tunneling microscopy (STM), state-of-the-art density functional theory (DFT) andNudged Elastic Band (NEB) calculations, we show that the unique directionality of the covalent bonding is found to stem from a chain of highly selective C-H activation and dehydrogenation processes, followed by specific intermolecular C-C coupling reactions that are facilitated by the surface, by steric constraints and by anisotropic molecular diffusion. These insights provide the first steps towards developing synthetic rules for complex two-dimensional covalent organic chemistry that can be enacted directly at a surface to deliver specific macromolecular structures designed for specific functions.

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Section: (A)mentioning

confidence: 99%

Section: (A)mentioning

confidence: 99%

Section: (A)mentioning

confidence: 99%

Section: Simulating the Mechanism Of Inter-molecular Couplingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Driving Forces for Covalent Assembly of Porphyrins by Selective C–H Bond Activation and Intermolecular Coupling on a Copper Surface

et al. 2016

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Out‐Of‐Plane Metal Coordination for a True Solvent‐Free Building with Molecular Bricks: Dodging the Surface Ligand Effect for On‐Surface Vacuum Self‐Assembly

Biroli

Calloni

Bossi³

et al. 2021

Adv Funct Materials

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The desirable self‐assembly (SA) of repeated 2D stacked layers requires a “holistic analysis” of three interconnected components: the electrode, the interface, and the molecular component; among them, the contact interface bears the largest burden responsibilities. Epitaxial growth (EG) of coherent 2D+n stacked heterojunction by solvent‐free deposition holds great promise, although the feasibility has never been demonstrated given multiple drawbacks (e.g., surface‐ligand effect, SLE). Here, it is demonstrated how a coherent 2D+n (n = 3) layered heterorganic film is grown on an archetypal Fe metal electrode. The groundbreaking achievement is the result of the in‐vacuum integration of: i) chemical decoupling of the basal organic layer (a ZnII‐tetraphenylporphyrine, ZnTPP) from the metal electrode, ii) 2D‐ordering of the ZnTPP commensurate to the substrate, iii) rigid, stoichiometric, and orthogonally arranged, the molecule‐to‐molecule coupling between ZnTPP and a ditopic linear bridging ligand (i.e., DPNDI) guided by SA coordination chemistry, and iv) sharp (chemical) termination of the layered film.

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Cyano‐Functionalized Triarylamines on Au(111): Competing Intermolecular versus Molecule/Substrate Interactions

Gottardi

Müller

Moreno-López

et al. 2013

Adv Materials Inter

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The self-assembly of cyano-substituted triarylamine derivatives on Au(111) is studied with scanning tunneling microscopy and density functional theory calculations. Two different phases, each stabilized by at least two different cyano bonding motifs are observed. In the first phase, each molecule is involved in dipolar coupling and hydrogen bonding, while in the second phase, dipolar coupling, hydrogen bonding and metal-ligand interactions are present.Interestingly, the metal-ligand bond is already observed for deposition of the molecules with the sample kept at room temperature leaving the herringbone reconstruction unaffected. We propose that for establishing this bond, the Au atoms are slightly displaced out of the surface to bind to the cyano ligands. Despite the intact herringbone reconstruction, the Au substrate is found to considerably interact with the cyano ligands affecting the conformation and adsorption geometry, as well as leading to correlation effects on the molecular orientation.

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1D and 3D surface-assisted self-organization

Cited by 53 publications

References 139 publications

Driving Forces for Covalent Assembly of Porphyrins by Selective C–H Bond Activation and Intermolecular Coupling on a Copper Surface

Driving Forces for Covalent Assembly of Porphyrins by Selective C–H Bond Activation and Intermolecular Coupling on a Copper Surface

Out‐Of‐Plane Metal Coordination for a True Solvent‐Free Building with Molecular Bricks: Dodging the Surface Ligand Effect for On‐Surface Vacuum Self‐Assembly

Cyano‐Functionalized Triarylamines on Au(111): Competing Intermolecular versus Molecule/Substrate Interactions

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