Function-led design of new porous materials

Slater, Anna G.; Cooper, Andrew I.

doi:10.1126/science.aaa8075

Cited by 1,380 publications

(969 citation statements)

References 127 publications

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“…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).…”

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

et al. 2016

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“…It is well established that increasing the rigidity of polymers used for gas separation membranes enhances their selectivity for one gas over another [12]. This prompted the recent development of PIMs derived from highly rigid bridged bicyclic structural units such as triptycene [13e16], ethanoanthracene [17] and the amine-based bicyclic system 6H, 12H-5,11-methanodibenzo[b,f ] [1,5] diazocine [17], which is more commonly known as Troger's€ base (TB). The V-shaped TB unit is used in numerous applications including making components for supramolecular chemistry [18].…”

Section: Introductionmentioning

confidence: 99%

“…Over recent years there has been increasing interest in the preparation of new microporous materials using organic compo-nents [1]. For example, there are a number of different types of porous organic polymers including structurally ordered Covalent-Organic-Frameworks (COFs) [2] and amorphous network poly-mers such as Hypercrosslinked Polymers (HCPs) [3], Microporous Conjugated Polymers (MCPs) [4] and Porous Aromatic Frameworks (PAFs) [5].…”

Section: Introductionmentioning

confidence: 99%

Polymers of Intrinsic Microporosity derived from a carbocyclic analogue of Tröger's base

Carta

Bezzu

Vile

et al. 2017

Polymer

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a b s t r a c tTroger's€ base (TB) is often used as a building block for the synthesis of Polymers of Intrinsic Micropo-rosity (PIMs) due to its rigid bicyclic V-shaped structure. In this study the TB component in the structure of a PIM is replaced by 2,3:6,7-dibenzobicyclo[3.3.1]nonane, a purely carbocyclic analogue of TB. This modification results in only a slightly reduced amount of microporosity as determined using nitrogen adsorption. Further comparisons with previously reported PIMs indicate that this building unit (and therefore TB) is significantly less effective for the generation of intrinsic microporosity than spirobisindane, a commonly used structural unit for PIM synthesis. It appears that the V-shape of the 2,3:6,7-dibenzobicyclo[3.3.1]nonane and TB units allows closer contact between polymer chains thereby enhancing packing efficiency.

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“…12 Porous molecular materials, which are studied in this work, are a form of porous materials that, unlike network materials such as zeolites and MOFs, are formed from the packing of discrete molecular units into solid state materials that demonstrate permanent porosity. [13][14][15][16][17][18] The porosity exhibited can be categorised as either a result of intrinsic porosity (where the molecule itself contains an internal void) or extrinsic porosity (where inefficient packing of the molecular units results in voids between them), or a combination of the two. Examples include "cage compounds", which are polycyclic compounds with the shape of a cage that have 3-dimensional structures with multiple possible entry and exit routes through molec-ular windows.…”

Section: Introductionmentioning

confidence: 99%

Computational Screening of Porous Organic Molecules for Xenon/Krypton Separation

et al. 2017

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1 AbstractWe performed a computational screening of previously reported porous molecular materials, including porous organic cages, cucurbiturils, cyclodextrins and cryptophanes, for Xe/Kr separation. Our approach for rapid screening through analysis of single host molecules, rather than the solid state structure of the materials, is evaluated.We use a set of tools including in-house software for structural evaluations, electronic structure calculations for guest binding energies and molecular dynamics and metadynamics simulations to study the effect of the hosts' flexibility upon guest diffusion. Our final results confirm that the CC3 cage molecule, previously reported as high performing for Xe/Kr separation, is the most promising of this class of materials reported to date. The Noria molecule was also found to be promising and we therefore synthesised two related Noria molecules and tested their performance for Xe/Kr separation in the laboratory.

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Function-led design of new porous materials

Cited by 1,380 publications

References 127 publications

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

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

Polymers of Intrinsic Microporosity derived from a carbocyclic analogue of Tröger's base

Computational Screening of Porous Organic Molecules for Xenon/Krypton Separation

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