Thermodynamic versus kinetic control in self-assembly of zero-, one-, quasi-two-, and two-dimensional metal-organic coordination structures

2015 ◽  
Vol 142 (10) ◽  
pp. 101909 ◽  
Author(s):  
Tao Lin ◽  
Qi Wu ◽  
Jun Liu ◽  
Ziliang Shi ◽  
Pei Nian Liu ◽  
...  
Keyword(s):  
Self Assembly ◽  
Kinetic Control ◽  
Two Dimensional ◽  
Metal Organic

scholarly journals Principles of molecular assemblies leading to molecular nanostructures

2013 ◽  
Vol 371 (2000) ◽  
pp. 20120304 ◽  
Author(s):  
Kunal S. Mali ◽  
Steven De Feyter
Keyword(s):  
Self Assembly ◽  
Contemporary Literature ◽  
High Vacuum ◽  
Building Blocks ◽  
Ultra High Vacuum ◽  
Two Dimensional ◽  
Ambient Conditions ◽  
Solid Interface ◽  
Metal Organic ◽  
Molecular Nanostructures

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.

Self-assembly of a binodal metal–organic framework exhibiting a demi-regular lattice

2017 ◽  
Vol 204 ◽  
pp. 111-121 ◽  
Author(s):  
Linghao Yan ◽  
Guowen Kuang ◽  
Qiushi Zhang ◽  
Xuesong Shang ◽  
Pei Nian Liu ◽  
...  
Keyword(s):  
Self Assembly ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Critical Value ◽  
Nanometer Scale ◽  
Two Dimensional ◽  
Regular Lattice ◽  
Molecular Density ◽  
Regular Lattices ◽  
Metal Organic

Designing metal–organic frameworks with new topologies is a long-standing quest because new topologies often accompany new properties and functions. Here we report that 1,3,5-tris[4-(pyridin-4-yl)phenyl]benzene molecules coordinate with Cu atoms to form a two-dimensional framework in which Cu adatoms form a nanometer-scale demi-regular lattice. The lattice is articulated by perfectly arranged twofold and threefold pyridyl–Cu coordination motifs in a ratio of 1 : 6 and features local dodecagonal symmetry. This structure is thermodynamically robust and emerges solely when the molecular density is at a critical value. In comparison, we present three framework structures that consist of semi-regular and regular lattices of Cu atoms self-assembled out of 1,3,5-tris[4-(pyridin-4-yl)phenyl]benzene and trispyridylbenzene molecules. Thus a family of regular, semi-regular and demi-regular lattices can be achieved by Cu–pyridyl coordination.

scholarly journals Assembly and Covalent Cross-Linking of an Amine-Functionalised Metal-Organic Cage

2021 ◽  
Vol 9 ◽  
Author(s):  
Matthew L. Schneider ◽  
Adrian W. Markwell-Heys ◽  
Oliver M. Linder-Patton ◽  
Witold M. Bloch
Keyword(s):  
Functional Groups ◽  
Self Assembly ◽  
Metal Organic Framework ◽  
The Self ◽  
Porous Solids ◽  
Cross Linking ◽  
Two Dimensional ◽  
Amine Functionalized ◽  
Metal Organic ◽  
Organic Framework

The incorporation of reactive functional groups onto the exterior of metal-organic cages (MOCs) opens up new opportunities to link their well-defined scaffolds into functional porous solids. Amine moieties offer access to a rich catalogue of covalent chemistry; however, they also tend to coordinate undesirably and interfere with MOC formation, particular in the case of Cu2 paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized Cu4L4 lantern cage (1). Importantly, we show control over the coordinative propensity of the exterior amine of the ligand, which enables us to isolate a crystalline, two-dimensional metal-organic framework composed entirely of MOC units (2). Furthermore, we show that the nucleophilicity of the exterior amine of 1 can be accessed in solution to generate a cross-linked cage polymer (3) via imine condensation.

Hydrogen-bonding self-assembly of two dimensional (2D) layer structures generating metal–organic nanotubes

CrystEngComm ◽  
2011 ◽  
Vol 13 (3) ◽  
pp. 734-737 ◽  
Author(s):  
Hailong Sun ◽  
Haibo Mei ◽  
Guanghui An ◽  
Jianlin Han ◽  
Yi Pan
Keyword(s):  
Hydrogen Bonding ◽  
Self Assembly ◽  
Two Dimensional ◽  
Layer Structures ◽  
Metal Organic ◽  
Organic Nanotubes

Kinetic Control of Interpenetration in Fe-Biphenyl-4,4′-dicarboxylate MOFs by Coordination and Oxidation Modulation

2018 ◽  
Author(s):  
Dominic Bara ◽  
Claire Wilson ◽  
Max Mörtel ◽  
Marat M. Khusniyarov ◽  
ben slater ◽  
...  
Keyword(s):  
Self Assembly ◽  
Surface Areas ◽  
Metal Precursors ◽  
Additional Coordination ◽  
Fine Control ◽  
Multiple Alternative ◽  
Metal Organic ◽  
Dft Simulations ◽  
High Valent ◽  
And Control

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>

Synthesis and Structure of a Clathrated Two-Dimensional Metal-Organic Framework: [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2·H2O (L = Bis(1-pyrazinylethylidene)hydrazine)

2008 ◽  
Vol 73 (1) ◽  
pp. 24-31
Author(s):  
Dayu Wu ◽  
Genhua Wu ◽  
Wei Huang ◽  
Zhuqing Wang
Keyword(s):  
Metal Organic Framework ◽  
Channel Structure ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Square Planar ◽  
Metal Organic ◽  
Aqueous Meoh ◽  
Organic Framework

The compound [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2 was obtained by the reaction of Cd(ClO4)2, bis(1-pyrazinylethylidene)hydrazine (L) and 4,4'-bipyridine in aqueous MeOH. Single-crystal X-ray diffraction has revealed its two-dimensional metal-organic framework. The 2-D layers superpose on each other, giving a channel structure. The square planar grids consist of two pairs of shared edges with Cd(II) ion and a 4,4'-bipyridine molecule each vertex and side, respectively. The square cavity has a dimension of 11.817 × 11.781 Å. Two guest molecules of bis(1-pyrazinylethylidene)hydrazine are clathrated in every hydrophobic host cavity, being further stabilized by π-π stacking and hydrogen bonding. The results suggest that the hydrazine molecules present in the network serve as structure-directing templates in the formation of crystal structures.

Two-Dimensional Metal–Organic Framework Nanosheets as an Enzyme Inhibitor: Modulation of the α-Chymotrypsin Activity

2017 ◽  
Vol 139 (24) ◽  
pp. 8312-8319 ◽  
Author(s):  
Ming Xu ◽  
Shuai Yuan ◽  
Xin-Yu Chen ◽  
Yu-Jie Chang ◽  
Gregory Day ◽  
...  
Keyword(s):  
Enzyme Inhibitor ◽  
Metal Organic Framework ◽  
Two Dimensional ◽  
Chymotrypsin Activity ◽  
Metal Organic ◽  
Organic Framework
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