Postmodifizierung der Hohlräume poröser formstabiler organischer Käfigverbindungen

Schneider, Markus W.; Oppel, Iris M.; Griffin, Alexandra; Mastalerz, Michael

doi:10.1002/ange.201208156

Cited by 55 publications

(14 citation statements)

References 49 publications

(23 reference statements)

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“…NPMs can exhibit extrinsic and/or intrinsic porosity. Intrinsic porosity is associated with the structure of the single‐molecule‐containing voids, clefts, or cavities, as has been demonstrated for calixarenes,9 cucurbiturils,10 cyclodextrins,11 organic cage compounds,6, 7a,c or discrete small organic molecules 12. In contrast, materials with extrinsic porosity are those where individual molecules pack in the solid‐state to form structures with empty spaces between the individual molecules.…”

Section: Methodsmentioning

confidence: 88%

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Permanent Porosity Derived From the Self‐Assembly of Highly Luminescent Molecular Zinc Carbonate Nanoclusters

et al. 2013

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Over the past two decades, crystalline microporous materials have attracted major interest, owing to their applications in gas sorption, separation, catalysis, and sensing. [1] Microporous crystalline materials can be constructed from coordinatively or covalently linked building blocks where rigid or semi-rigid molecular scaffolds separate void spaces of different size and geometry. Prominent examples of porous materials showing polymeric structures include zeolites, [2] hybrid metal-organic frameworks (MOFs) or porous coordination polymers (PCPs), [3] covalent organic frameworks (COFs), [4] and Hbonded supramolecular organic frameworks (SOFs). [5] The formation of bonding interactions between building units is an important factor that defines and controls the stability and robustness of these porous polymeric materials. However, discrete molecules may also pack in the solid state to form 3D assemblies that exhibit high permanent porosity. [6] The resulting noncovalent porous materials (NPMs) are distinct from the above polymeric systems, as they are held together by weak noncovalent crystal-packing forces. Modifications of structure by cocrystallization of different building blocks [7] can tune the microcavities in the solid state, and the material can thus conform to the shape or functionality of guest molecules. Moreover, these materials can be highly solubile, an important advantage in their processing to form porous thin films. [7a, 8] NPMs can exhibit extrinsic and/or intrinsic porosity. Intrinsic porosity is associated with the structure of the single-molecule-containing voids, clefts, or cavities, as has been demonstrated for calixarenes, [9] cucurbiturils, [10] cyclodextrins, [11] organic cage compounds, [6, 7a,c] or discrete small organic molecules. [12] In contrast, materials with extrinsic porosity are those where individual molecules pack in the solid-state to form structures with empty spaces between the individual molecules. As discrete molecules tend to form close-packed solids with minimal void volume, extrinsic porosity in NPMs remains a rare phenomenon. [12a, 13] The rational design and preparation of NPMs showing extrinsic porosity based on molecular metal complexes is highly challenging and few examples have been reported. [14] We have demonstrated previously that alkylzinc hydroxides RZnOH can be efficiently transformed into multinuclear alkyzinc carbonate nanoclusters [15] or nanomaterials, such as discrete nanoparticulate zinc carbonate aerogels [15] and ZnO nanoparticles. [16] As shown in Scheme 1 a, the reactivity of the RZnOH species can be rationalized in terms of the presence of both a proton-reactive Zn À C bond and CO 2 -reactive Zn À OH groups. We argued that introduction of an additional auxiliary ligand L to the RZnOH system, followed by CO 2 fixation, could lead to the formation of novel molecular building blocks for new extrinsic NPMs. Herein, we report such a strategy in which the construction of a nanosized cluster [Zn 10 (m 6 -CO 3 ) 4 (L) 12 ] (WUT-1; WUT = War...

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Section: Methodsmentioning

confidence: 88%

“…Modifications of structure by cocrystallization of different building blocks7 can tune the microcavities in the solid state, and the material can thus conform to the shape or functionality of guest molecules. Moreover, these materials can be highly solubile, an important advantage in their processing to form porous thin films 7a. 8…”

Section: Methodsmentioning

confidence: 99%

Permanent Porosity Derived From the Self‐Assembly of Highly Luminescent Molecular Zinc Carbonate Nanoclusters

et al. 2013

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“…Currently, we are working on the synthesis of even larger porous cages to gain further insight into the scope and limitations of this new and fascinating class of porous materials. Received: October 13, 2013 Published online: January 8,2014 . Keywords: boronic acids · cage compounds · dynamic covalent chemistry · porosity · triptycene…”

Section: Methodsmentioning

confidence: 99%

“…[5] The solubility of porous organic molecules offers some advantages in comparison to insoluble network materials: [6] porous molecules are miscible in solution enabling adjustment of the properties of the material; [7] an exhaustive post-functionalization by chemical reactions in the inner cavities of the cage molecules allows the functional groups on the surface, and hence the gas sorption properties of the porous materials, to be changed. [8] Furthermore, processing of porous molecules into functional devices such as quartz crystal microbalances for the sensing of volatile analytes has been reported, [9] as has embedding them into membranes. [10] When aiming for organic cages with very large pores, especially in the mesopore regime (> 2 nm), the prevention of a structural collapse of the molecules upon desolvation is one of the major obstacles one has to face.…”

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confidence: 99%

A Permanent Mesoporous Organic Cage with an Exceptionally High Surface Area

Zhang¹,

Presly²,

White³

et al. 2014

Angew Chem Int Ed

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392

312

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Recently, porous organic cage crystals have become a real alternative to extended framework materials with high specific surface areas in the desolvated state. Although major progress in this area has been made, the resulting porous compounds are restricted to the microporous regime, owing to the relatively small molecular sizes of the cages, or the collapse of larger structures upon desolvation. Herein, we present the synthesis of a shape-persistent cage compound by the reversible formation of 24 boronic ester units of 12 triptycene tetraol molecules and 8 triboronic acid molecules. The cage compound bears a cavity of a minimum inner diameter of 2.6 nm and a maximum inner diameter of 3.1 nm, as determined by single-crystal X-ray analysis. The porous molecular crystals could be activated for gas sorption by removing enclathrated solvent molecules, resulting in a mesoporous material with a very high specific surface area of 3758 m(2) g(-1) and a pore diameter of 2.3 nm, as measured by nitrogen gas sorption.

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“…However, these cage molecules were efficiently synthesized by Williamson post-functionalization reaction of (38) 6 (41) 4 with the corresponding alkyl halides. [66] Similar [4+6] cages bearing different substituents on the phenyl ring (i.e., aldehydes 39 in Figure 10) oriented toward the exterior of the cage were also obtained in reaction with amine 41 ( Figure 10) [67] and were studied as permanent porous materials. A larger [8 + 12] cuboctahedral molecular cage (38) 12 (42) 8 obtained from aldehyde 38 and amine 42 was recently reported [68] to have an internal cavity volume of about 2679 3 (as estimated from the X-ray molecular structure).…”

Section: Imine Exchange Reactionmentioning

confidence: 99%

Selective Host Molecules Obtained by Dynamic Adaptive Chemistry

Matache

Bogdan

Hădade

2014

Chemistry A European J

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Up till 20 years ago, in order to endow molecules with function there were two mainstream lines of thought. One was to rationally design the positioning of chemical functionalities within candidate molecules, followed by an iterative synthesis-optimization process. The second was the use of a "brutal force" approach of combinatorial chemistry coupled with advanced screening for function. Although both methods provided important results, "rational design" often resulted in time-consuming efforts of modeling and synthesis only to find that the candidate molecule was not performing the designed job. "Combinatorial chemistry" suffered from a fundamental limitation related to the focusing of the libraries employed, often using lead compounds that limit its scope. Dynamic constitutional chemistry has developed as a combination of the two approaches above. Through the rational use of reversible chemical bonds together with a large plethora of precursor libraries, one is now able to build functional structures, ranging from quite simple molecules up to large polymeric structures. Thus, by introduction of the dynamic component within the molecular recognition processes, a new perspective of deciphering the world of the molecular events has aroused together with a new field of chemistry. Since its birth dynamic constitutional chemistry has continuously gained attention, in particular due to its ability to easily create from scratch outstanding molecular structures as well as the addition of adaptive features. The fundamental concepts defining the dynamic constitutional chemistry have been continuously extended to currently place it at the intersection between the supramolecular chemistry and newly defined adaptive chemistry, a pivotal feature towards evolutive chemistry.

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Postmodifizierung der Hohlräume poröser formstabiler organischer Käfigverbindungen

Cited by 55 publications

References 49 publications

Permanent Porosity Derived From the Self‐Assembly of Highly Luminescent Molecular Zinc Carbonate Nanoclusters

Permanent Porosity Derived From the Self‐Assembly of Highly Luminescent Molecular Zinc Carbonate Nanoclusters

A Permanent Mesoporous Organic Cage with an Exceptionally High Surface Area

Selective Host Molecules Obtained by Dynamic Adaptive Chemistry

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