Large Self‐Assembled Chiral Organic Cages: Synthesis, Structure, and Shape Persistence

Jelfs, Kim E.; Wu, Xiao‐Feng; Schmidtmann, Marc; Jones, James T. A.; Warren, John E.; Adams, Dave J.; Cooper, Andrew I.

doi:10.1002/anie.201105104

Cited by 141 publications

(165 citation statements)

References 46 publications

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“…However, even this can fail, for example we reported a change from a cyclohexane diamine to a cyclopentane diamine resulting in a larger [8 + 12] molecule, with an underlying topology of a cube, forming in place of a [4 + 6] molecule. 33 Worse still, whilst the [4 + 6] molecule formed a porous solid state material, with a BET surface area of >1300 m 2 g −1 , the [8 + 12] molecule was found to lack shape persistence in the absence of a solvent and hence to form an amorphous, non-porous material. Thus, a very subtle difference in the reaction precursors had an enormous effect on the reaction outcome and therefore properties of the molecular cage material.…”

Section: Topological Control?mentioning

confidence: 99%

“…To reproduce explicit solvent interactions, we would firstly have to greatly increase the number of atoms in our simulations due to the necessity of including hundreds of solvent molecules; in previous work we found a single cage molecule to be solvated by ∼80 dichloromethane molecules (400 atoms) even in the solid state solvate structure. 33 Secondly, we would then need to sample the conformations of these molecules surrounding the cage molecule to consider the dynamic nature of the solvation. Combined, these simulations are not currently tractable for these systems.…”

Section: Computational Challengesmentioning

confidence: 99%

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Topological landscapes of porous organic cages

et al. 2017

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We define a nomenclature for the classification of porous organic cage molecules, enumerating the 20 most probable topologies, 12 of which have been synthetically realised to date. We then discuss the computational challenges encountered when trying to predict the most likely topological outcomes from dynamic covalent chemistry (DCC) reactions of organic building blocks. This allows us to explore the extent to which comparing the internal energies of possible reaction outcomes is successful in predicting the topology for a series of 10 different building block combinations.

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Section: Topological Control?mentioning

confidence: 99%

Section: Computational Challengesmentioning

confidence: 99%

Topological landscapes of porous organic cages

et al. 2017

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“…In some cases the topology can be designed by chemical intuition, but there are also reports of emergent behaviour thwarting this, where small changes in the precursor have had a large effect on both topology and properties. 114 The fact that the thermodynamic product should dominate opens the possibility of comparing the relative energies of low energy conformations of different topological outcomes, typically using electronic structure calculations. This approach has predicted, for example, odd-even alternation in topology with increasing alkane chain length of precursors, illustrated in Fig.…”

Section: Computational Designmentioning

confidence: 99%

Application of computational methods to the design and characterisation of porous molecular materials

et al. 2017

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Composed from discete units, porous molecular materials (PMMs) possess unique properties not observed for conventional, extended, solids, such as solution processibility and permanent porosity in the liquid phase. However, identifying the origin of porosity is not a trivial process, especially for amorphous or liquid phases. Furthermore, the assembly of molecular components is typically governed by a subtle balance of weak intermolecular forces that makes structure prediction challenging. Accordingly, in this review we canvass the crucial role of molecular simulations in the characterisation and design of PMMs. We will outline strategies for modelling porosity in crystalline, amorphous and liquid phases and also describe the state-of-the-art methods used for high-throughput screening of large datasets to identify materials that exhibit novel performance characteristics.

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“…In the case of CC13, a large increase in porosity is achieved by solvent-directed control over crystal packing, rather than by increasing the size of the cage modules themselves, as in other recent reports for organic cages with large pore volumes. 30,31,46,47 …”

Section: Introductionmentioning

confidence: 99%

Controlling the Crystallization of Porous Organic Cages: Molecular Analogs of Isoreticular Frameworks Using Shape-Specific Directing Solvents

et al. 2014

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Small structural changes in organic molecules can have a large influence on solid-state crystal packing, and this often thwarts attempts to produce isostructural series of crystalline solids. For metal-organic frameworks and covalent organic frameworks, this has been addressed by using strong, directional intermolecular bonding to create families of isoreticular solids. Here we show that an organic directing solvent, 1,4-dioxane, has a dominant effect on the lattice energy for a series of organic cage molecules. Inclusion of dioxane directs the crystal packing for these cages away from their lowest-energy polymorphs to form isostructural, 3-dimensional diamondoid pore channels. This is a unique function of the size, chemical function, and geometry of 1,4-dioxane, and hence a non-covalent auxiliary interaction assumes the role of directional coordination bonding or covalent bonding in extended crystalline frameworks. For a new cage, CC13, a dual, interpenetrating pore structure is formed which doubles the gas uptake and the surface area in the resulting dioxanedirected crystals.

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Large Self‐Assembled Chiral Organic Cages: Synthesis, Structure, and Shape Persistence

Cited by 141 publications

References 46 publications

Topological landscapes of porous organic cages

Topological landscapes of porous organic cages

Application of computational methods to the design and characterisation of porous molecular materials

Controlling the Crystallization of Porous Organic Cages: Molecular Analogs of Isoreticular Frameworks Using Shape-Specific Directing Solvents

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