Self-assembly of metal–organic coordination networks using on-surface synthesized ligands

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.

Polyhedron ◽  
2015 ◽  
Vol 102 ◽  
pp. 1-7 ◽  
Author(s):  
Fatih Semerci ◽  
Okan Zafer Yeşilel ◽  
Fatma Yüksel

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.


2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  

Phase control in the self-assembly of metal-organic frameworks (MOFs) – materials wherein organic ligands connect metal ions or clusters into network solids with potential porosity – is often a case of trial and error. Judicious control over a number of synthetic variables is required to select for the desired topology and control features such as interpenetration and defectivity, which have significant impact on physical properties and application. Herein, we present a comprehensive investigation of self-assembly in the Fe-biphenyl-4,4'-dicarboxylate system, demonstrating that coordination modulation, the addition of competing ligands into solvothermal syntheses, can reliably tune between the kinetic product, non-interpenetrated MIL-88D(Fe), and the thermodynamic product, two-fold interpenetrated MIL-126(Fe). DFT simulations reveal that correlated disorder of the terminal anions on the metal clusters in the interpentrated phase results in H-bonding between adjacent nets and is the thermodynamic driving force for its formation. Coordination modulation slows self-assembly and therefore selects the thermodynamic product MIL-126(Fe), while offering fine control over defectivity, inducing mesoporosity, but electron microscopy shows the MIL-88D(Fe) phase persists in many samples despite not being evident in diffraction experiments, suggesting its presence accounts for the lower than predicted surface areas reported for samples to date. Interpenetration control is also demonstrated by utilizing the 2,2'-bipyridine-5,5'-dicarboxylate linker; DFT simulations show that it is energetically prohibitive for it to adopt the twisted conformation required to form the interpenetrated phase, and are confirmed by experimental data, although multiple alternative phases are identified due to additional coordination of the Fe cations to the N-donors of the ligand. Finally, we introduce oxidation modulation – the concept of using metal precursors in a different oxidation state to that found in the final MOF – as a further protocol to kinetically control self-assembly. Combining coordination and oxidation modulation allows the synthesis of pristine MIL-126(Fe) with BET surface areas close to the predicted maximum capacity for the first time, suggesting that combining the two may be a powerful methodology for the controlled self-assembly of high-valent MOFs.<br><br>


2021 ◽  
Vol 6 (4) ◽  
pp. 712-716
Author(s):  
Xiao Liu ◽  
Yaoyu Liang ◽  
Jiayu Liu ◽  
Se Shi ◽  
Yuefei Wang ◽  
...  

Author(s):  
Zaoming Wang ◽  
Gavin A. Craig ◽  
Alexandre Legrand ◽  
Frederik Haase ◽  
Saori Minami ◽  
...  
Keyword(s):  

ACS Omega ◽  
2021 ◽  
Author(s):  
Juan M. Garcia-Garfido ◽  
Javier Enríquez ◽  
Ignacio Chi-Durán ◽  
Iván Jara ◽  
Leonardo Vivas ◽  
...  

CrystEngComm ◽  
2020 ◽  
Vol 22 (47) ◽  
pp. 8274-8274
Author(s):  
Carmen Ramírez de Arellano ◽  
Rosa Adam ◽  
Rafael Ballesteros-Garrido ◽  
Belen Abarca ◽  
Rafael Ballesteros ◽  
...  

Correction for ‘A C(π-hole)⋯Cl–Zn tetrel interaction driving a metal–organic supramolecular assembly’ by Carmen Ramírez de Arellano et al., CrystEngComm, 2020, 22, 6979–6982, DOI: 10.1039/D0CE01272F.


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