Predicting Inclusion Behaviour and Framework Structures in Organic Crystals

Cruz‐Cabeza, Aurora J.; Day, Graeme M.; Jones, William

doi:10.1002/chem.200901703

Cited by 63 publications

(65 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…It has been shown before that stable inclusion structures tend to be located along the low energy edge of crystal structure landscapes, where structures occupy their lowest energy configuration for a given packing 11 density. 41 Here, we observe that the calculated energy of the highly porous TCC1-R structure stands out on the landscape (Fig. 5a) as unusually stable for such a low density packing mode of this molecule.…”

mentioning

confidence: 59%

“…25) where the nanotubes are preserved, but where collapse of the cage occurs. The bulk TCC2-R/TCC2-S material was insufficiently crystalline to determine whether the loss of porosity was due to this cage collapse, to a loss of crystallinity, or to both.We also calculated the landscapes of possible crystal structures of enantiopure and racemic TCC1-TCC3 using crystal structure prediction (CSP) 21,39,40,41,42 methods (Fig. 5, Supplementary Information, Section 4.6).…”

mentioning

confidence: 99%

“…We also calculated the landscapes of possible crystal structures of enantiopure and racemic TCC1-TCC3 using crystal structure prediction (CSP) 21,39,40,41,42 methods (Fig. 5, Supplementary Information, Section 4.6).…”

mentioning

confidence: 99%

See 2 more Smart Citations

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

et al. 2016

View full text Add to dashboard Cite

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 (...

show abstract

mentioning

confidence: 59%

mentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2016

View full text Add to dashboard Cite

show abstract

“…J (339_ P 4 2 / n , Z ′ = 2) and tetr. I (22_ P 4 2 / n , Z ′ = 2), have voids 79 of a size that could accommodate more water, but this void space is mainly surrounded by hydrophobic regions and so seem unlikely to be a hydrate framework.…”

Section: Resultsmentioning

confidence: 99%

Absorbing a Little Water: The Structural, Thermodynamic, and Kinetic Relationship between Pyrogallol and Its Tetarto-Hydrate

Braun

Bhardwaj

Arlin

et al. 2013

Crystal Growth & Design

View full text Add to dashboard Cite

The anhydrate and the stoichiometric tetarto-hydrate of pyrogallol (0.25 mol water per mol pyrogallol) are both storage stable at ambient conditions, provided that they are phase pure, with the system being at equilibrium at aw (water activity) = 0.15 at 25 °C. Structures have been derived from single crystal and powder X-ray diffraction data for the anhydrate and hydrate, respectively. It is notable that the tetarto-hydrate forms a tetragonal structure with water in channels, a framework that although stabilized by water, is found as a higher energy structure on a computationally generated crystal energy landscape, which has the anhydrate crystal structure as the most stable form. Thus, a combination of slurry experiments, X-ray diffraction, spectroscopy, moisture (de)sorption, and thermo-analytical methods with the computationally generated crystal energy landscape and lattice energy calculations provides a consistent picture of the finely balanced hydration behavior of pyrogallol. In addition, two monotropically related dimethyl sulfoxide monosolvates were found in the accompanying solid form screen.

show abstract

“…However, Cruz-Cabeza and co-workers demonstrated that the observed frameworks of inclusion crystals are also located on predicted crystal energy landscapes, at higher energies, but along the lowenergy edge of energy-density distribution of crystal structures. 45 The identification of stable, low density structures among CSP structures has the promise of predicting clathrate structures, 46 but also of desolvatable extrinsically porous crystals. Indeed, CSP was recently used to computationally assess a series of awkwardly-shaped benzimidazolones and imides for likely porous structures, finding that some molecules featured 'spikes' of unusually low energy structures in the low density region of their structural landscapes.…”

Section: 37mentioning

confidence: 99%

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

et al. 2017

View full text Add to dashboard Cite

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.

show abstract

Predicting Inclusion Behaviour and Framework Structures in Organic Crystals

Abstract: Day, (2010) Modelling organic crystal structures using distributed multipole and polarizability-based model intermolecular potentials. Physical

Cited by 63 publications

References 40 publications

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

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

Absorbing a Little Water: The Structural, Thermodynamic, and Kinetic Relationship between Pyrogallol and Its Tetarto-Hydrate

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

Contact Info

Product

Resources

About