scholarly journals Principles of molecular assemblies leading to molecular nanostructures

Author(s):  
Kunal S. Mali ◽  
Steven De Feyter

Self-assembled physisorbed monolayers consist of regular two-dimensional arrays of molecules. Two-dimensional self-assembly of organic and metal–organic building blocks is a widely used strategy for nanoscale functionalization of surfaces. These supramolecular nanostructures are typically sustained by weak non-covalent forces such as van der Waals, electrostatic, metal–ligand, dipole–dipole and hydrogen bonding interactions. A wide variety of structurally very diverse monolayers have been fabricated under ambient conditions at the liquid–solid and air–solid interface or under ultra-high-vacuum (UHV) conditions at the UHV–solid interface. The outcome of the molecular self-assembly process depends on a variety of factors such as the nature of functional groups present on assembling molecules, the type of solvent, the temperature at which the molecules assemble and the concentration of the building blocks. The objective of this review is to provide a brief account of the progress in understanding various parameters affecting two-dimensional molecular self-assembly through illustration of some key examples from contemporary literature.

Nanomaterials ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 2102
Author(s):  
Elie Geagea ◽  
Judicael Jeannoutot ◽  
Louise Morgenthaler ◽  
Simon Lamare ◽  
Frank Palmino ◽  
...  

On-surface metal-organic polymers have emerged as a class of promising 2D materials. Here, we propose a new strategy to obtain coordination polymers by transforming supramolecular networks into coordination polymers by surface-assisted cyclo-dehydrogenation of organic building blocks. All nanostructures are fully characterized by using scanning tunneling microscopy under ultra-high vacuum on a gold surface. We demonstrated that the balance between molecule-molecule interaction and molecule-substrate interaction can be drastically modified by a strong modification of the geometry of the molecules thanks to a thermal annealing. This new way is an efficient method to elaborate on-surface coordination polymers.


2021 ◽  
Vol 22 (13) ◽  
pp. 6880
Author(s):  
Zilong Wang ◽  
Minlong Tao ◽  
Daxiao Yang ◽  
Zuo Li ◽  
Mingxia Shi ◽  
...  

We report an ultra-high vacuum low-temperature scanning tunneling microscopy (STM) study of the C60 monolayer grown on Cd(0001). Individual C60 molecules adsorbed on Cd(0001) may exhibit a bright or dim contrast in STM images. When deposited at low temperatures close to 100 K, C60 thin films present a curved structure to release strain due to dominant molecule–substrate interactions. Moreover, edge dislocation appears when two different wavy structures encounter each other, which has seldomly been observed in molecular self-assembly. When growth temperature rose, we found two forms of symmetric kagome lattice superstructures, 2 × 2 and 4 × 4, at room temperature (RT) and 310 K, respectively. The results provide new insight into the growth behavior of C60 films.


Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2393
Author(s):  
Artur Trembułowicz ◽  
Agata Sabik ◽  
Miłosz Grodzicki

The surface of quasi-hexagonal reconstructed Au(100) is used as the template for monolayer pentacene (PEN) self-assembly. The system is characterized by means of scanning tunneling microscopy at room temperature and under an ultra-high vacuum. A new modulated pattern of molecules with long molecular axes (MA) arranged along hex stripes is found. The characteristic features of the hex reconstruction are preserved herein. The assembly with MA across the hex rows leads to an unmodulated structure, where the molecular layer does not recreate the buckled hex phase. The presence of the molecules partly lifts the reconstruction—i.e., the gold hex phase is transformed into a (1×1) phase. The arrangement of PEN on the gold (1×1) structure is the same as that of the surrounding molecular domain on the reconstructed surface. The apparent height difference between phases allows for the distinction of the state of the underlying gold surface.


Author(s):  
Zhenpeng Yao ◽  
Benjamin Sanchez-Lengeling ◽  
N. Scott Bobbitt ◽  
Benjamin J. Bucior ◽  
Sai Govind Hari Kumar ◽  
...  

Reticular frameworks are crystalline porous materials that form <i>via</i> the self-assembly of molecular building blocks (<i>i.e.</i>, nodes and linkers) in different topologies. Many of them have high internal surface areas and other desirable properties for gas storage, separation, and other applications. The notable variety of the possible building blocks and the diverse ways they can be assembled endow reticular frameworks with a near-infinite combinatorial design space, making reticular chemistry both promising and challenging for prospective materials design. Here, we propose an automated nanoporous materials discovery platform powered by a supramolecular variational autoencoder (SmVAE) for the generative design of reticular materials with desired functions. We demonstrate the automated design process with a class of metal-organic framework (MOF) structures and the goal of separating CO<sub>2</sub> from natural gas or flue gas. Our model exhibits high fidelity in capturing structural features and reconstructing MOF structures. We show that the autoencoder has a promising optimization capability when jointly trained with multiple top adsorbent candidates identified for superior gas separation. MOFs discovered here are strongly competitive against some of the best-performing MOFs/zeolites ever reported. This platform lays the groundwork for the design of reticular frameworks for desired applications.


2020 ◽  
Author(s):  
Zhenpeng Yao ◽  
Benjamin Sanchez-Lengeling ◽  
N. Scott Bobbitt ◽  
Benjamin J. Bucior ◽  
Sai Govind Hari Kumar ◽  
...  

Reticular frameworks are crystalline porous materials that form <i>via</i> the self-assembly of molecular building blocks (<i>i.e.</i>, nodes and linkers) in different topologies. Many of them have high internal surface areas and other desirable properties for gas storage, separation, and other applications. The notable variety of the possible building blocks and the diverse ways they can be assembled endow reticular frameworks with a near-infinite combinatorial design space, making reticular chemistry both promising and challenging for prospective materials design. Here, we propose an automated nanoporous materials discovery platform powered by a supramolecular variational autoencoder (SmVAE) for the generative design of reticular materials with desired functions. We demonstrate the automated design process with a class of metal-organic framework (MOF) structures and the goal of separating CO<sub>2</sub> from natural gas or flue gas. Our model exhibits high fidelity in capturing structural features and reconstructing MOF structures. We show that the autoencoder has a promising optimization capability when jointly trained with multiple top adsorbent candidates identified for superior gas separation. MOFs discovered here are strongly competitive against some of the best-performing MOFs/zeolites ever reported. This platform lays the groundwork for the design of reticular frameworks for desired applications.


2012 ◽  
Vol 1455 ◽  
Author(s):  
Oliver Ochedowski ◽  
Benedict Kleine Bußmann ◽  
Marika Schleberger

ABSTRACTWe have employed atomic force and Kelvin-Probe force microscopy to study graphene sheets exfoliated on TiO2 under the influence of local heating achieved by laser irradiation. Exfoliation and irradiation took place under ambient conditions, the measurements were performed in ultra high vacuum. We show that after irradiation times of 6 min, an increase of the surface potential is observed which indicates a decrease of p-type carrier concentration. We attribute this effect to the removal of adsorbates like water and oxygen. After irradiation times of 12 min our topography images reveal severe structural modifications of graphene. These resemble the nanocrystallite network which form on graphene/SiO2 but after much longer irradiation times. From our results we propose that short laser heating at moderate powers might offer a way to clean graphene without inducing unwanted structural modifications.


2011 ◽  
Vol 257 (10) ◽  
pp. 4559-4565 ◽  
Author(s):  
Xinrui Miao ◽  
Li Xu ◽  
Chenyi Liao ◽  
Zhuomin Li ◽  
Jian Zhou ◽  
...  

2014 ◽  
Vol 50 (97) ◽  
pp. 15327-15329 ◽  
Author(s):  
Tao Lin ◽  
Guowen Kuang ◽  
Xue Song Shang ◽  
Pei Nian Liu ◽  
Nian Lin

A two-step strategy consisting of on-surface synthesis and supramolecular assembly is developed for constructing low-dimensional molecular nanostructures on surfaces.


2015 ◽  
Vol 6 ◽  
pp. 632-639 ◽  
Author(s):  
Ping Du ◽  
David Bléger ◽  
Fabrice Charra ◽  
Vincent Bouchiat ◽  
David Kreher ◽  
...  

Two-dimensional (2D), supramolecular self-assembly at surfaces is now well-mastered with several existing examples. However, one remaining challenge to enable future applications in nanoscience is to provide potential functionalities to the physisorbed adlayer. This work reviews a recently developed strategy that addresses this key issue by taking advantage of a new concept, Janus tecton materials. This is a versatile, molecular platform based on the design of three-dimensional (3D) building blocks consisting of two faces linked by a cyclophane-type pillar. One face is designed to steer 2D self-assembly onto C(sp2)-carbon-based flat surfaces, the other allowing for the desired functionality above the substrate with a well-controlled lateral order. In this way, it is possible to simultaneously obtain a regular, non-covalent paving as well as supramolecular functionalization of graphene, thus opening interesting perspectives for nanoscience applications.


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