A Metal−Organic Framework with a Covalently Prefabricated Porous Organic Linker

Swamy, Shashikala I.; Bacsa, John; Jones, James T. A.; Stylianou, Kyriakos C.; Steiner, Alexander; Ritchie, Lyndsey K.; Hasell, Tom; Gould, Jamie A.; Laybourn, Andrea; Khimyak, Yaroslav Z.; Adams, Dave J.; Rosseinsky, Matthew J.; Cooper, Andrew I.

doi:10.1021/ja104083y

Cited by 96 publications

(75 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The different conformations induced by different anions suggest that the anion template plays a leading role during the self-assembly process. [14] The presence of the coordinating NO 3 À ion in 1 + NO 3 À was further confirmed by solid-state 15 N NMR spectroscopy, which shows one low-intensity peak at d = 368.25 ppm that can be assigned to the encapsulated NO 3 À ion ( Figure S11). The IR spectra of H 2 L, 1, 2, and 1 + NO 3 À are shown in Figure S6.…”

mentioning

confidence: 79%

Multiple Lanthanide Helicate Clusters and the Effects of Anions on Their Configuration

et al. 2013

View full text Add to dashboard Cite

Helices are the central structural motif in biological molecules. [1] Except for some familiar helices (single, double, and triple), the plasmid DNA has a cyclic structure, [2] and the biologically significant multi-stranded nucleic acid configuration is quadruplex. [3] Helices and circular helices have been fundamental topological targets for chemical synthesis for the past two decades, and much effort has been made in the design and synthesis of artificial helical molecules. [4] Helicalmetal coordination compounds (helicates), have been extensively investigated; [5] however, the formation of the cyclic helicate, a higher nuclearity variant of the helicate, is conversely less well understood. [6] Controlling the structure of assemblies of helicates is one of the leading challenges for supramolecular chemists. The ingenuity of Lehn and coworkers occupies a prominent position, and they have reported a series of helicates/circular helicates, leading to further improvements in this field. [7] Although this challenging task has been quite successfully accomplished with transition metals, [8] the polynuclear helicates with lanthanides have not been developed to such an extent because of the fact that trivalent lanthanide ions display high kinetic lability and a lack of stereochemical preference. [9] Despite some evolution, the ability to predict and control supramolecular assembly is seriously restricted by the bewildering structuredirecting factors; [10] in particular, the anion-controlled selfassembly of lanthanide helicates is rare.Furthermore, it is necessary to investigate nitrates because of the importance of nitrate ions in environmental and biological systems. Primary nitrate response is the best known nitrate-induced response, in which genes encoding the nitrate assimilatory enzymes and nitrate transporters are rapidly induced by nitrate; moreover, transcriptomic studies have indicated that many other genes for diverse biological processes, including amino acid and nucleic acid metabolism, protein folding, RNA processing, and hormone biosynthesis, could also be rapidly induced or repressed by nitrate. [11] Herein, we discuss the design and synthesis of a flexible dentate-bridging ligand, H 2 L, which has two amide-containing NO 3 tetradentate chelators positioned at the two termini ( Figure 1). This linear amide-containing ligand is highly effective in the construction of supramolecular lanthanide complexes. The self-assembly process depends strongly on anion templates, tetrahedral ClO 4 À and trigonal-planar NO 3 À anions, to induce the formation of novel hexanuclear lanthanum circular helicate and tetranuclear quadruple-stranded helicate complexes, respectively. Moreover, the lanthanum complexes dynamically converted from a circular helicate structure into a quadruple-stranded helicate structure upon NO 3 À anion stimulus, which suggests that NO 3 À is the more potent structure regulator.Adding a solution of La(ClO 4 ) 3 ·6 H 2 O in methanol to a light yellow and transparent solution of H 2 L and LiOH (...

show abstract

mentioning

confidence: 79%

Multiple Lanthanide Helicate Clusters and the Effects of Anions on Their Configuration

et al. 2013

View full text Add to dashboard Cite

show abstract

“…104 To give one example, MOFs can be prepared from amine cages, where the amines act as metal coordination ligands and the cage linker provides a (limited) degree of intrinsic porosity. 102 …”

Section: Intrinsically Porous Framework Linkersmentioning

confidence: 99%

Porous Molecular Solids and Liquids

2017

Self Cite

View full text Add to dashboard Cite

Until recently, porous molecular solids were isolated curiosities with properties that were eclipsed by porous frameworks, such as metal–organic frameworks. Now molecules have emerged as a functional materials platform that can have high levels of porosity, good chemical stability, and, uniquely, solution processability. The lack of intermolecular bonding in these materials has also led to new, counterintuitive states of matter, such as porous liquids. Our ability to design these materials has improved significantly due to advances in computational prediction methods.

show abstract

“…[5b,c,d] Forexample,Cooper and co-workers have developed some powerful strategies,s uch as "mix-andmatch", [6] "cage scrambling reaction" [7] and "crystal retroengineering", [8] to control over crystal packing and pore connectivity.H owever,iti sstill highly challenging to predict the packing modes of small molecules in the crystalline materials because small alterations could make ahuge impact on the crystal packing in some cases. In this respect, Coopers [10] and Zhangsg roups [11] have reported two instances of porous networked cages containing reduced amine organic cage building blocks.One was azincmediated cage-MOF connected by the coordinative bonds, and the other was cage-based frameworks linked by covalent bonds.However,they both employed reduced amine cages as the building blocks to give cage-extended networks because of the dynamic reversible nature of imine bonds,which led to flexible structures and loss of internal cavities and pores and thus rendered the products unsuitable for the gas sorption. In this respect, Coopers [10] and Zhangsg roups [11] have reported two instances of porous networked cages containing reduced amine organic cage building blocks.One was azincmediated cage-MOF connected by the coordinative bonds, and the other was cage-based frameworks linked by covalent bonds.However,they both employed reduced amine cages as the building blocks to give cage-extended networks because of the dynamic reversible nature of imine bonds,which led to flexible structures and loss of internal cavities and pores and thus rendered the products unsuitable for the gas sorption.…”

mentioning

confidence: 99%

From Discrete Molecular Cages to a Network of Cages Exhibiting Enhanced CO₂ Adsorption Capacity

et al. 2017

View full text Add to dashboard Cite

We have adopted the concept of "cage to frameworks" to successfully produce a Na-N connected coordination networked cage Na-NC1 by using a [3+6] porous imine-linked organic cage NC1 (Nanjing Cage 1) as the precursor. It is found that Na-NC1 exhibits hierarchical porosity (inherent permanent voids and interconnected channel) and gas sorption measurements reveal a significantly enhanced CO uptake (1093 cm g at 23 bar and 273 K) than that of NC1 (162 cm g under the same conditions). In addition, Na-NC1 exhibits very low CO adsorption enthalpy making it a good candidate for porous materials with both high CO storage and low adsorption enthalpy.

show abstract

A Metal−Organic Framework with a Covalently Prefabricated Porous Organic Linker

Abstract: We report here the synthesis of a metal-organic framework comprising an organic cage linker with covalently prefabricated, intrinsic porosity. The network can be compared to a porous rock salt structure where the pores are partially filled by charge-balancing cations.

Cited by 96 publications

References 24 publications

Multiple Lanthanide Helicate Clusters and the Effects of Anions on Their Configuration

Multiple Lanthanide Helicate Clusters and the Effects of Anions on Their Configuration

Porous Molecular Solids and Liquids

From Discrete Molecular Cages to a Network of Cages Exhibiting Enhanced CO₂ Adsorption Capacity

Contact Info

Product

Resources

About

A Metal−Organic Framework with a Covalently Prefabricated Porous Organic Linker

Abstract: We report here the synthesis of a metal-organic framework comprising an organic cage linker with covalently prefabricated, intrinsic porosity. The network can be compared to a porous rock salt structure where the pores are partially filled by charge-balancing cations.

Cited by 96 publications

References 24 publications

Multiple Lanthanide Helicate Clusters and the Effects of Anions on Their Configuration

Multiple Lanthanide Helicate Clusters and the Effects of Anions on Their Configuration

Porous Molecular Solids and Liquids

From Discrete Molecular Cages to a Network of Cages Exhibiting Enhanced CO2 Adsorption Capacity

Contact Info

Product

Resources

About

From Discrete Molecular Cages to a Network of Cages Exhibiting Enhanced CO₂ Adsorption Capacity