Molecular shape sorting using molecular organic cages

Mitra, Tamoghna; Jelfs, Kim E.; Schmidtmann, Marc; Ahmed, Adham; Chong, Samantha Y.; Adams, Dave J.; Cooper, Andrew I.

doi:10.1038/nchem.1550

Cited by 337 publications

(276 citation statements)

References 26 publications

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“…10 Co-crystallization of TCC2-R and CC3-S in a 1:2 molar ratio from a CH 2 Cl 2 solution in the presence of 1,4-dioxane 21 produced a new crystalline phase, 2 •(1,4-dioxane) 17.75 (space group P6 3 22, Supplementary Information, Section 2.4, Supplementary Figs. 41-43).…”

Section: Racemic Co-crystals Of Tubular and Tetrahedral Cagesmentioning

confidence: 99%

“…3 POCs are rigid molecules with a permanent internal void that is accessible to guests via 'windows' in the cage. [17][18][19] Control of structure and function for POCs can be difficult, however, because slight changes in the molecular structure 19 or the crystallization solvent 20 can cause a profound change in the crystal packing. Chiral window-towindow interactions (Fig.…”

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confidence: 99%

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Reticular synthesis of porous molecular 1D nanotubes and 3D networks

et al. 2016

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Synthetic control over pore size and pore connectivity is the crowning achievement for porous metal-organic frameworks. The same level of control has not been achieved for molecular crystals, which are not defined by strong, directional intermolecular coordination bonds. Hence, molecular crystallization is inherently less controllable than framework crystallization, and there are fewer examples of 'reticular synthesis'-where multiple building blocks can be assembled according to a common assembly motif.Here, we apply a chiral recognition strategy to a new family of tubular covalent cages, to create both 1-D porous nanotubes and 3-D diamondoid pillared porous networks.The diamondoid networks are analogous to metal-organic frameworks prepared from tetrahedral metal nodes and linear, ditopic organic linkers. The crystal structures can be rationalized by computational lattice energy searches, which provide an in silico screening method to evaluate candidate molecular building blocks. These results are a blueprint for applying the 'node and strut' principles of reticular synthesis to molecular crystals.Despite many advances in supramolecular chemistry, it is still challenging to control molecular crystallization to create a specific, useful property. 1,2 This is important in the emerging area of porous molecular solids, 3 which have practical advantages such as solution processability. The crystal packing in porous molecular crystals defines the pore dimensions, which in turn define properties such as guest selectivity. 4,5 The same challenge-control over solid state structure-applies to all 2 functional molecular crystals because crystal packing defines physical properties such as electronic band gap and thermal or electrical conductivity.A central paradigm in crystal engineering is to synthesize building blocks, or 'tectons', with strong, directional interactions, such as hydrogen bonding 6 or metal-ligand binding, 7 which direct assembly into a targeted three-dimensional superstructure (Fig. 1). 1,2,8,9 For metal-organic frameworks (MOFs) and porous coordination polymers (PCPs), directional metal-ligand bonds are used to do this (Fig. 1a). [10][11][12][13][14] Likewise, hydrogen bonding can be used to create organic molecular crystals with defined network structures (Fig. 1b). 9,15,16 We have used chiral recognition to assemble porous organic cages 3 (POCs) into structures with 3-D pore channels (Fig. 1c). 3 POCs are rigid molecules with a permanent internal void that is accessible to guests via 'windows' in the cage. [17][18][19] Control of structure and function for POCs can be difficult, however, because slight changes in the molecular structure 19 or the crystallization solvent 20 can cause a profound change in the crystal packing. Chiral window-towindow interactions (Fig. 1e,f) can direct these POCs to assemble into 3-D pore networks in several cases, 19,21,22 but this is not ubiquitous. For example, some cages require specific solvents to template the window-to-window packing. 20 The chiral cage CC3-S (...

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Section: Racemic Co-crystals Of Tubular and Tetrahedral Cagesmentioning

confidence: 99%

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confidence: 99%

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

et al. 2016

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“…Please do not adjust margins predict solid state or solution properties, in particular separation 112 and sensing performance. 113 Although effects resulting from bulk structure can be expected to influence performance, simulations at the molecular level can be performed considerably quicker and thus allow a preliminary screening to narrow down the number of candidates.…”

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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“…Of particular scientific interest is the concept of the artificial enzyme, which can act as a catalyst for a specific substrate via cooperative recognition 1 . The importance of practical materials can be seen in solution-phase recognition, which allows efficient chemical separation despite very small structural differences 2 . The essential requirement for recognition is a shape-persistent cavitand generally made of covalent macrocycles [3][4][5] or supramolecular cages [6][7][8][9] .…”

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Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes

et al. 2013

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Molecular shape recognition for larger guest molecules (typically over 1 nm) is a difficult task because it requires cooperativity within a wide three-dimensional nanospace coincidentally probing every molecular aspect (size, outline shape, flexibility and specific groups). Although the intelligent functions of proteins have fascinated many researchers, the reproduction by artificial molecules remains a significant challenge. Here we report the construction of large, well-defined cavities in macromolecular hosts. Through the use of semi-rigid dendritic phenylazomethine backbones, even subtle differences in the shapes of large guest molecules (up to B2 nm) may be discriminated by the cooperative mechanism. A conformationally fixed complex with the best-fitting guest is supported by a three-dimensional model based on a molecular simulation. Interestingly, the simulated cavity structure also predicts catalytic selectivity by a ruthenium porphyrin centre, demonstrating the high shape persistence and wide applicability of the cavity.

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Molecular shape sorting using molecular organic cages

Cited by 337 publications

References 26 publications

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

Reticular synthesis of porous molecular 1D nanotubes and 3D networks

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

Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes

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