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

Chiral anionic layers in tartramide spiroborate salts and variable solvation for [NR 4][B(TarNH2)2] (R = Et, Pr or Bu)

2020 ◽  
Vol 76 (7) ◽  
pp. 695-705
Author(s):  
Aristyo Soecipto ◽  
Lawrence W.-Y. Wong ◽  
Herman H.-Y. Sung ◽  
Ian D. Williams
Keyword(s):  
Hydrogen Bonding ◽  
Self Assembly ◽  
Interfacial Area ◽  
Intermolecular Hydrogen Bonding ◽  
Two Dimensional ◽  
Salt Hydrate ◽  
Anion Layer ◽  
Cation Layer ◽  
Layer Structures ◽  
Solvent Molecules

The spiroborate anion, namely, 2,3,7,8-tetracarboxamido-1,4,6,9-tetraoxa-5λ4-boraspiro[4.4]nonane, [B(TarNH2)2]−, derived from the diol L-tartramide TarNH2, [CH(O)(CONH2)]2, shows a novel self-assembly into two-dimensional (2D) layer structures in its salts with alkylammonium cations, [NR 4]+ (R = Et, Pr and Bu), and sparteinium, [HSpa]+, in which the cations and anions are segregated. The structures of four such salts are reported, namely, the tetrapropylazanium salt, C12H28N+·C8H12BN4O8 −, the tetraethylazanium salt hydrate, C8H20N+·C8H12BN4O8 −·6.375H2O, the tetrabutylazanium salt as the ethanol monosolvate hemihydrate, C16H36N+·C8H12BN4O8 −·C2H5OH·0.5H2O, and the sparteinium (7-aza-15-azoniatetracyclo[7.7.1.02,7.010,15]heptadecane) salt as the ethanol monosolvate, C15H27N2 +·C8H12BN4O8 −·C2H5OH. The 2D anion layers have preserved intermolecular hydrogen bonding between the amide groups and a typical metric repeat of around 10 × 15 Å. The constraint of matching the interfacial area organizes the cations into quite different solvated arrangements, i.e. the [NEt4] salt is highly hydrated with around 6.5H2O per cation, the [NPr4] salt apparently has a good metric match to the anion layer and is unsolvated, whilst the [NBu4] salt is intermediate and has EtOH and H2O in its cation layer, which is similar to the arrangement for the chiral [HSpa]+ cation. This family of salts shows highly organized chiral space and offers potential for the resolution of both chiral cations and neutral chiral solvent molecules.

scholarly journals Molecular self-assembly of nylon-12 nanorods cylindrically confined to nanoporous alumina

IUCrJ ◽  
2014 ◽  
Vol 1 (6) ◽  
pp. 439-445 ◽  
Author(s):  
Yan Cao ◽  
Hui Wu ◽  
Yuji Higaki ◽  
Hiroshi Jinnai ◽  
Atsushi Takahara
Keyword(s):  
Hydrogen Bonding ◽  
Self Assembly ◽  
Growth Direction ◽  
Two Dimensional ◽  
Nanoporous Alumina ◽  
Self Organized ◽  
Selected Area Electron Diffraction ◽  
Transmission Electron ◽  
Nylon 12 ◽  
Different Diameters

Molecular self-assembly of nylon-12 rods in self-organized nanoporous alumina cylinders with two different diameters (65 and 300 nm) is studied with transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) in symmetrical reflection mode. In a rod with a 300 nm diameter, the tendency of the hydrogen-bonding direction of a γ-form crystal parallel to the long axis of the rod is not clear because of weak two-dimensional confinement. In a rod with a diameter of 65 nm, the tendency of the hydrogen-bonding direction of a γ-form crystal parallel to the long axis of the rod is more distinct because of strong two-dimensional confinement. For the first time, selected-area electron diffraction (SAED) is applied in a transmission electron microscope to a polymer nanorod in order to determine the hydrogen-bond sheet and lamellar orientations. Results of TEM–SAED and WAXD showed that the crystals within the rod possess the γ-form of nylon-12 and that thebaxis (stem axis) of the γ-form crystals is perpendicular to the long axis of the rod. These results revealed that only lamellae with 〈h0l〉 directions are able to grow inside the nanopores and the growth of lamellae with 〈hkl〉 (k≠ 0) directions is stopped owing to impingements against the cylinder walls. The dominant crystal growth direction of the 65 nm rod in stronger two-dimensional confinement is in between the [−201] and [001] directions due to the development of a hydrogen-bonded sheet restricted along the long axis of the rod.

The self-assembly of single-walled metal–organic nanotubes constructed from CuCl2 chains and ditetrazoles

CrystEngComm ◽  
2011 ◽  
Vol 13 (22) ◽  
pp. 6610 ◽  
Author(s):  
Bing Li ◽  
Shun-Wei Chen ◽  
Zheng Chen ◽  
Jie Chen ◽  
Jian-Zhong Guo ◽  
...  
Keyword(s):  
Self Assembly ◽  
The Self ◽  
Metal Organic ◽  
Organic Nanotubes

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.

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

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 Self-assembly synthesis of precursors to potential open framework alkali earth metal–organic complexes

2014 ◽  
Vol 38 (5) ◽  
pp. 2135-2143 ◽  
Author(s):  
Louise B. Hamdy ◽  
Paul R. Raithby ◽  
Lynne H. Thomas ◽  
Chick C. Wilson
Keyword(s):  
Hydrogen Bonding ◽  
Dicarboxylic Acid ◽  
Self Assembly ◽  
Earth Metal ◽  
Alkali Earth Metal ◽  
Open Framework ◽  
Framework Materials ◽  
Organic Complexes ◽  
Metal Organic ◽  
Metal Ligand

A series of magnesium pyridinecarboxylic–dicarboxylic acid complexes, synthesised as precursors to potential framework materials, show a range of metal ligand and hydrogen bonding geometries. The pyridinedicarboxylic complexes show most promise as precursors for further syntheses.

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.

Meso-Helicates with Rigid Angular Tetradentate Ligand: Design, Molecular Structures, and Progress Towards Self-Assembly of Metal–Organic Nanotubes

2013 ◽  
Vol 52 (22) ◽  
pp. 13042-13047 ◽  
Author(s):  
Rodrigue Djeda ◽  
Christophe Desmarets ◽  
Lise-Marie Chamoreau ◽  
Yanling Li ◽  
Yves Journaux ◽  
...  
Keyword(s):  
Self Assembly ◽  
Ligand Design ◽  
Molecular Structures ◽  
Tetradentate Ligand ◽  
Metal Organic ◽  
Organic Nanotubes
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