Organometallic polymers synthesized from prochiral molecules by a surface-assisted synthesis on Ag(111)

Lü, Hui; Wenlong, E; Ma, Zhibo; Yang, Xueming

doi:10.1039/c9cp06893g

Cited by 5 publications

(5 citation statements)

References 39 publications

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“…In practice, when simple prochiral molecules are deposited on a flat surface, the racemate (an equimolar mixture of enantiomers) is usually formed. Understanding the role of individual surface enantiomers in the bottom-up formation of 2D racemic mixtures is desirable, but possible only in experimental systems where surface enantiomers can form either a racemic phase (with a unit cell containing two different surface enantiomers) and/or homochiral domains with opposite chirality. − The prochiral molecules adsorbed on a flat surface have only the acquired chirality, which is immediately lost after desorption. To solve this problem, we can use computer simulations, which allow for the studying of diverse molecular systems with properly selected size and composition.…”

Section: Resultsmentioning

confidence: 99%

On-Surface Self-Assembly of Metal-Organic Architectures: Insights from Computer Simulations

Gdula

Nieckarz

2020

J. Phys. Chem. C

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Molecular self-assembly based on the spontaneous arrangement of simple, functional molecules on atomically flat surfaces has been recognized, in the past decades, as an extremely useful tool for the rational fabrication of one-atom-thick nanomaterials, with potential application in heterogeneous catalysis, selective adsorption, and sensing. The physicochemical properties of such supramolecular constructs are determined mainly by the proper choice of chemical interactions cementing their components. Particularly suitable for this purpose are directional, reversible ligand → metal coordinate bonds. In this contribution, we present the results of coarse-grained Monte Carlo (MC) computer simulations performed on the family of isomeric, starshaped molecular building blocks, coadsorbed with low-coordinated metal atoms on the triangular lattice. We have found that depending on the position of active centers (functional groups) attached to the terminal segments of investigated molecules, the bottom-up fabrication of complex metal-organic overlayers, like nanoporous networks, nonregular tessellations, and ladder-like chains, is possible. The obtained patterns are described and classified according to their geometrical properties. The herein presented theoretical predictions can be especially helpful for scanning tunneling microscopy (STM) experimentalists interested in the rational designing of novel surface-supported metal-organic architectures with an unusual morphology and tunable physicochemical properties.

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Section: Resultsmentioning

confidence: 99%

On-Surface Self-Assembly of Metal-Organic Architectures: Insights from Computer Simulations

Gdula

Nieckarz

2020

J. Phys. Chem. C

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“…Chiral-selective reactions have been used to synthesize various polymers on surfaces in the past and various strategies have been employed to achieve chiral-selectivity. These strategies mostly focus on the molecular structure, for instance by introducing bulky groups causing steric hindrance, to enable certain couplings over others 13 , 25 , 26 . On the other hand, also the type of inorganic surface may lead to chiral-selectivity 18 , 20 , 27 .…”

Section: Introductionmentioning

confidence: 99%

Kinetic control over the chiral-selectivity in the formation of organometallic polymers on a Ag(110) surface

Houtsma,

van Nyendaal,

Stöhr

2024

Commun Chem

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Methods to control chiral-selectivity in molecular reactions through external inputs are of importance, both from a fundamental and technological point of view. Here, the self-assembly of prochiral 6,12-dibromochrysene monomers on Ag(110) is studied using scanning tunneling microscopy. Deposition of the monomers on a substrate held at room temperature leads to the formation of 1D achiral organometallic polymers. When the monomers are instead deposited on a substrate held at 373 K, homochiral organometallic polymers consisting of either the left- or right-handed enantiomer are formed. Post-deposition annealing of room temperature deposited samples at >373 K does not transform the achiral 1D organometallic polymers into homochiral ones and thus, does not yield the same final structure as if depositing onto a substrate held at the same elevated temperature. Furthermore, annealing promotes neither the formation of 1D covalently-coupled polymers nor the formation of graphene nanoribbons. Our results identify substrate temperature as an important factor in on-surface chiral synthesis, thereby demonstrating the importance of considering kinetic effects and the decisive role they can play in structure formation.

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“…These alveolate sectors, known as pores or cavities, can be fine-tuned to serve as well-defined matrices for the positioning and spatial organization of guest atoms/molecules. They can also act as 2D sieves, allowing size/shape segregation of mixed chemical entities, or as nanometer-sized reactors. − Additionally, due to the confinement of the molecules in a plane and their vertical interaction with the substrate, the flat-lying admolecules lose conformational freedom and may exist in the form of one, two, , or few surface conformers. , This fact is of great importance as the final outcome of the surface-supported SA is usually much more predictable and controllable than the analogous processes occurring in the bulk. Furthermore, the supramolecular architectures comprising laterally interconnected admolecules can be visually inspected by means of high-resolution scanning tunneling microscopy (STM) and other advanced non-destructive techniques, which strongly facilitates their structural analysis .…”

Section: Introductionmentioning

confidence: 99%

“…They can also act as 2D sieves, allowing size/shape segregation of mixed chemical entities, or as nanometer-sized reactors. 23−26 Additionally, due to the confinement of the molecules in a plane and their vertical interaction with the substrate, the flat-lying admolecules lose conformational freedom and may exist in the form of one, 6 two, 27,28 or few surface conformers. 15,19 of great importance as the final outcome of the surfacesupported SA is usually much more predictable and controllable than the analogous processes occurring in the bulk.…”

Section: Introductionmentioning

confidence: 99%

Steering the Surface-Confined Self-Assembly of Multifunctional Star-Shaped Molecules

Nieckarz

2023

J. Phys. Chem. C

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Directing the self-assembly (SA) of small organic molecules into low-dimensional porous patterns is a versatile method for the bottom-up fabrication of flat nanomaterials with controllable architecture and functions. However, the rational synthesis of the self-assembled monolayers (SAMs) requires carefully choosing the building blocks with a proper size, shape, and functionalization scheme. Among the molecular bricks used for this purpose, especially promising are the (N-hetero)aromatic star-shaped molecules equipped from three to six electronegative functional groups, providing anisotropic in-plane intermolecular interactions. Therefore, in this work, the surface-confined SA of tripodal polytopic molecules was investigated using lattice Markov chain Monte Carlo (MCMC) computer simulations in the canonical ensemble. Specifically, the simulated building blocks were equipped with terminal interaction centers providing short-range directional interactions and represented on a flat triangular lattice in a simplified but credible way. By altering the number and intramolecular position of sticky sites attached to these rigid tectons, we observed the emergence of various supramolecular constructs, including isolated well-shaped aggregates, twodimensional (2D) open porous networks, and a series of hierarchically organized floral phases, which were classified according to their morphological properties. Our theoretical findings may be helpful in predicting the SA of π-aromatic multifunctional tripod molecules on close-packed crystalline surfaces and relevant to the scanning tunneling microscopy (STM) laboratory experimentalists seeking new linkers for the construction of novel surface-supported supramolecular constructs with a predefined topology.

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Organometallic polymers synthesized from prochiral molecules by a surface-assisted synthesis on Ag(111)

Abstract: Organometallic polymers have been successfully synthesized on a Ag(111) surface via a surface-assisted synthesis by choosing prochiral molecules as the precursor.

Cited by 5 publications

References 39 publications

On-Surface Self-Assembly of Metal-Organic Architectures: Insights from Computer Simulations

On-Surface Self-Assembly of Metal-Organic Architectures: Insights from Computer Simulations

Kinetic control over the chiral-selectivity in the formation of organometallic polymers on a Ag(110) surface

Steering the Surface-Confined Self-Assembly of Multifunctional Star-Shaped Molecules

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