Reconstructed covalent organic frameworks.

Covalent organic frameworks (COFs) are distinguished from other organic polymers by their crystallinity1-3, but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions are poorly reversible4,5. More reversible chemistry can improve crystallinity6-9, but this typically yields COFs with poor physicochemical stability and limited application scope5. Here we report a general and scalable protocol to prepare robust, highly crystalline imine COFs, based on an unexpected framework reconstruction. In contrast to standard approaches in which monomers are initially randomly aligned, our method involves the pre-organization of monomers using a reversible and removable covalent tether, followed by confined polymerization. This reconstruction route produces reconstructed COFs with greatly enhanced crystallinity and much higher porosity by means of a simple vacuum-free synthetic procedure. The increased crystallinity in the reconstructed COFs improves charge carrier transport, leading to sacrificial photocatalytic hydrogen evolution rates of up to 27.98 mmol h-1 g-1. This nanoconfinement-assisted reconstruction strategy is a step towards programming function in organic materials through atomistic structural control.

Self-Assembly of Chiral Porous Metal-Organic Polyhedra from Trianglsalen Macrocycles.

Metal-organic polyhedra (MOPs) can exhibit tunable porosity and functionality, suggesting potential for applications such as molecular separations. MOPs are typically constructed by the bottom-up multicomponent self-assembly of organic ligands and metal ions, and the final functionality can be hard to program. Here, we used trianglsalen macrocycles as preorganized building blocks to assemble octahedral-shaped MOPs. The resultant MOPs inherit most of the preorganized properties of the macrocyclic ligands, including their well-defined cavities and chirality. As a result, the porosity in the MOPs could be tuned by modifying the structure of the macrocycle building blocks. Using this strategy, we could systematically enlarge the size of the MOPs from 26.3 to 32.1 Å by increasing the macrocycle size. The family of MOPs shows experimental surface areas of up to 820 m2/g, and they are stable in water. One of these MOPs can efficiently separate the rare gases Xe from Kr because the prefabricated macrocyclic windows of MOPs can be modified to sit at the Xe/Kr size cutoff range.

Soft Hydrogen-Bonded Organic Frameworks Constructed Using a Flexible Organic Cage Hinge.

Soft porous crystals combine flexibility and porosity, allowing them to respond structurally to external physical and chemical environments. However, striking the right balance between flexibility and sufficient rigidity for porosity is challenging, particularly for molecular crystals formed by using weak intermolecular interactions. Here, we report a flexible oxygen-bridged prismatic organic cage molecule, Cage-6-COOH, which has three pillars that exhibit "hinge-like" rotational motion in the solid state. Cage-6-COOH can form a range of hydrogen-bonded organic frameworks (HOFs) where the "hinge" can accommodate a remarkable 67° dihedral angle range between neighboring units. This stems both from flexibility in the noncovalent hydrogen-bonding motifs in the HOFs and the molecular flexibility in the oxygen-linked cage hinge itself. The range of structures for Cage-6-COOH includes two topologically complex interpenetrated HOFs, CageHOF-2α and CageHOF-2ß. CageHOF-2α is nonporous, while CageHOF-2ß has permanent porosity and a surface area of 458 m2 g-1. The flexibility of Cage-6-COOH allows this molecule to rapidly transform from a low-crystallinity solid into the two crystalline interpenetrated HOFs, CageHOF-2α and CageHOF-2ß, under mild conditions simply by using acetonitrile or ethanol vapor, respectively. This self-healing behavior was selective, with the CageHOF-2ß structure exhibiting structural memory behavior.

A smart and responsive crystalline porous organic cage membrane with switchable pore apertures for graded molecular sieving.

Membranes with high selectivity offer an attractive route to molecular separations, where technologies such as distillation and chromatography are energy intensive. However, it remains challenging to fine tune the structure and porosity in membranes, particularly to separate molecules of similar size. Here, we report a process for producing composite membranes that comprise crystalline porous organic cage films fabricated by interfacial synthesis on a polyacrylonitrile support. These membranes exhibit ultrafast solvent permeance and high rejection of organic dyes with molecular weights over 600 g mol-1. The crystalline cage film is dynamic, and its pore aperture can be switched in methanol to generate larger pores that provide increased methanol permeance and higher molecular weight cut-offs (1,400 g mol-1). By varying the water/methanol ratio, the film can be switched between two phases that have different selectivities, such that a single, 'smart' crystalline membrane can perform graded molecular sieving. We exemplify this by separating three organic dyes in a single-stage, single-membrane process.

Controlling the Crystallisation and Hydration State of Crystalline Porous Organic Salts.

Crystalline porous organic salts (CPOS) are a subclass of molecular crystals. The low solubility of CPOS and their building blocks limits the choice of crystallisation solvents to water or polar alcohols, hindering the isolation, scale-up, and scope of the porous material. In this work, high throughput screening was used to expand the solvent scope, resulting in the identification of a new porous salt, CPOS-7, formed from tetrakis(4-sulfophenyl)methane (TSPM) and tetrakis(4-aminophenyl)methane (TAPM). CPOS-7 does not form with standard solvents for CPOS, rather a hydrated phase (Hydrate2920) previously reported is isolated. Initial attempts to translate the crystallisation to batch led to challenges with loss of crystallinity and Hydrate2920 forming favorably in the presence of excess water. Using acetic acid as a dehydrating agent hindered formation of Hydrate2920 and furthermore allowed for direct conversion to CPOS-7. To allow for direct formation of CPOS-7 in high crystallinity flow chemistry was used for the first time to circumvent the issues found in batch. CPOS-7 and Hydrate2920 were shown to have promise for water and CO2 capture, with CPOS-7 having a CO2 uptake of 4.3 mmol/g at 195 K, making it one of the most porous CPOS reported to date.

Functional materials discovery using energy-structure-function maps.

Molecular crystals cannot be designed in the same manner as macroscopic objects, because they do not assemble according to simple, intuitive rules. Their structures result from the balance of many weak interactions, rather than from the strong and predictable bonding patterns found in metal-organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail. Here we combine computational crystal structure prediction and property prediction to build energy-structure-function maps that describe the possible structures and properties that are available to a candidate molecule. Using these maps, we identify a highly porous solid, which has the lowest density reported for a molecular crystal so far. Both the structure of the crystal and its physical properties, such as methane storage capacity and guest-molecule selectivity, are predicted using the molecular structure as the only input. More generally, energy-structure-function maps could be used to guide the experimental discovery of materials with any target function that can be calculated from predicted crystal structures, such as electronic structure or mechanical properties.

Experimental Confirmation of a Predicted Porous Hydrogen-Bonded Organic Framework.

Hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure-property predictions to generate energy-structure-function (ESF) maps for a series of triptycene-based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low-energy HOF (TH5-A) with a remarkably low density of 0.374 g cm-3 and three-dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5-A polymorph experimentally. This material has a high accessible surface area of 3,284 m2 g-1 , as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date.

Analogy Powered by Prediction and Structural Invariants: Computationally Led Discovery of a Mesoporous Hydrogen-Bonded Organic Cage Crystal.

Mesoporous molecular crystals have potential applications in separation and catalysis, but they are rare and hard to design because many weak interactions compete during crystallization, and most molecules have an energetic preference for close packing. Here, we combine crystal structure prediction (CSP) with structural invariants to continuously qualify the similarity between predicted crystal structures for related molecules. This allows isomorphous substitution strategies, which can be unreliable for molecular crystals, to be augmented by a priori prediction, thus leveraging the power of both approaches. We used this combined approach to discover a rare example of a low-density (0.54 g cm-3) mesoporous hydrogen-bonded framework (HOF), 3D-CageHOF-1. This structure comprises an organic cage (Cage-3-NH2) that was predicted to form kinetically trapped, low-density polymorphs via CSP. Pointwise distance distribution structural invariants revealed five predicted forms of Cage-3-NH2 that are analogous to experimentally realized porous crystals of a chemically different but geometrically similar molecule, T2. More broadly, this approach overcomes the difficulties in comparing predicted molecular crystals with varying lattice parameters, thus allowing for the systematic comparison of energy-structure landscapes for chemically dissimilar molecules.

A Pyrene-4,5,9,10-Tetraone-Based Covalent Organic Framework Delivers High Specific Capacity as a Li-Ion Positive Electrode.

Electrochemically active covalent organic frameworks (COFs) are promising electrode materials for Li-ion batteries. However, improving the specific capacities of COF-based electrodes requires materials with increased conductivity and a higher concentration of redox-active groups. Here, we designed a series of pyrene-4,5,9,10-tetraone COF (PT-COF) and carbon nanotube (CNT) composites (denoted as PT-COFX, where X = 10, 30, and 50 wt % of CNT) to address these challenges. Among the composites, PT-COF50 achieved a capacity of up to 280 mAh g-1 as normalized to the active COF material at a current density of 200 mA g-1, which is the highest capacity reported for a COF-based composite cathode electrode to date. Furthermore, PT-COF50 exhibited excellent rate performance, delivering a capacity of 229 mAh g-1 at 5000 mA g-1 (18.5C). Using operando Raman microscopy the reversible transformation of the redox-active carbonyl groups of PT-COF was determined, which rationalizes an overall 4 e-/4 Li+ redox process per pyrene-4,5,9,10-tetraone unit, accounting for its superior performance as a Li-ion battery electrode.

Hydrogen Isotope Separation Using a Metal-Organic Cage Built from Macrocycles.

Porous materials that contain ultrafine pore apertures can separate hydrogen isotopes via kinetic quantum sieving (KQS). However, it is challenging to design materials with suitably narrow pores for KQS that also show good adsorption capacities and operate at practical temperatures. Here, we investigate a metal-organic cage (MOC) assembled from organic macrocycles and ZnII ions that exhibits narrow windows (<3.0 Å). Two polymorphs, referred to as 2α and 2ß, were observed. Both polymorphs exhibit D2 /H2 selectivity in the temperature range 30-100 K. At higher temperature (77 K), the D2 adsorption capacity of 2ß increases to about 2.7 times that of 2α, along with a reasonable D2 /H2 selectivity. Gas sorption analysis and thermal desorption spectroscopy suggest a gate-opening effect of the MOCs pore aperture. This promotes KQS at temperatures above liquid nitrogen temperature, indicating that MOCs hold promise for hydrogen isotope separation in real industrial environments.

A Cubic 3D Covalent Organic Framework with nbo Topology.

The synthesis of three-dimensional (3D) covalent organic frameworks (COFs) requires high-connectivity polyhedral building blocks or the controlled alignment of building blocks. Here, we use the latter strategy to assemble square-planar cobalt(II) phthalocyanine (PcCo) units into the nbo topology by using tetrahedral spiroborate (SPB) linkages that were chosen to provide the necessary 90° dihedral angles between neighboring PcCo units. This yields a porous 3D COF, SPB-COF-DBA, with a noninterpenetrated nbo topology. SPB-COF-DBA shows high crystallinity and long-range order, with 11 resolved diffraction peaks in the experimental powder X-ray diffraction (PXRD) pattern. This well-ordered crystal lattice can also be imaged by using high-resolution transmission electron microscopy (HR-TEM). SPB-COF-DBA has cubic pores and exhibits permanent porosity with a Brunauer-Emmett-Teller (BET) surface area of 1726 m2 g-1.

Inherent Ethyl Acetate Selectivity in a Trianglimine Molecular Solid.

Ethyl acetate is an important chemical raw material and solvent. It is also a key volatile organic compound in the brewing industry and a marker for lung cancer. Materials that are highly selective toward ethyl acetate are needed for its separation and detection. Here, we report a trianglimine macrocycle (TAMC) that selectively adsorbs ethyl acetate by forming a solvate. Crystal structure prediction showed this to be the lowest energy solvate structure available. This solvate leaves a metastable, "templated" cavity after solvent removal. Adsorption and breakthrough experiments confirmed that TAMC has adequate adsorption kinetics to separate ethyl acetate from azeotropic mixtures with ethanol, which is a challenging and energy-intensive industrial separation.

3D Cage COFs: A Dynamic Three-Dimensional Covalent Organic Framework with High-Connectivity Organic Cage Nodes.

Three-dimensional (3D) covalent organic frameworks (COFs) are rare because there is a limited choice of organic building blocks that offer multiple reactive sites in a polyhedral geometry. Here, we synthesized an organic cage molecule (Cage-6-NH2) that was used as a triangular prism node to yield the first cage-based 3D COF, 3D-CageCOF-1. This COF adopts an unreported 2-fold interpenetrated acs topology and exhibits reversible dynamic behavior, switching between a small-pore (sp) structure and a large-pore (lp) structure. It also shows high CO2 uptake and captures water at low humidity (<40%). This demonstrates the potential for expanding the structural complexity of 3D COFs by using organic cages as the building units.

An Expandable Hydrogen-Bonded Organic Framework Characterized by Three-Dimensional Electron Diffraction.

A molecular crystal of a 2-D hydrogen-bonded organic framework (HOF) undergoes an unusual structural transformation after solvent removal from the crystal pores during activation. The conformationally flexible host molecule, ABTPA, adapts its molecular conformation during activation to initiate a framework expansion. The microcrystalline activated phase was characterized by three-dimensional electron diffraction (3D ED), which revealed that ABTPA uses out-of-plane anthracene units as adaptive structural anchors. These units change orientation to generate an expanded, lower density framework material in the activated structure. The porous HOF, ABTPA-2, has robust dynamic porosity (SABET = 1183 m2 g-1) and exhibits negative area thermal expansion. We use crystal structure prediction (CSP) to understand the underlying energetics behind the structural transformation and discuss the challenges facing CSP for such flexible molecules.

Organic Cage Dumbbells.

Molecular dumbbells with organic cage capping units were synthesised via a multi-component imine condensation between a tri-topic amine and di- and tetra-topic aldehydes. This is an example of self-sorting, which can be rationalised by computational modelling.

Inducing Social Self-Sorting in Organic Cages To Tune The Shape of The Internal Cavity.

Many interesting target guest molecules have low symmetry, yet most methods for synthesising hosts result in highly symmetrical capsules. Methods of generating lower symmetry pores are thus required to maximise the binding affinity in host-guest complexes. Herein, we use mixtures of tetraaldehyde building blocks with cyclohexanediamine to access low-symmetry imine cages. Whether a low-energy cage is isolated can be correctly predicted from the thermodynamic preference observed in computational models. The stability of the observed structures depends on the geometrical match of the aldehyde building blocks. One bent aldehyde stands out as unable to assemble into high-symmetry cages-and the same aldehyde generates low-symmetry socially self-sorted cages when combined with a linear aldehyde. We exploit this finding to synthesise a family of low-symmetry cages containing heteroatoms, illustrating that pores of varying geometries and surface chemistries may be reliably accessed through computational prediction and self-sorting.

Control of conformation in α-helix mimicking aromatic oligoamide foldamers through interactions between adjacent side-chains.

The design, synthesis and structural characterization of non-natural oligomers that adopt well-defined conformations, so called foldamers, is a key objective in developing biomimetic 3D functional architectures. For the aromatic oligoamide foldamer family, use of interactions between side-chains to control conformation is underexplored. The current manuscript addresses this objective through the design, synthesis and conformational analyses of model dimers derived from 3-O-alkylated para-aminobenzoic acid monomers. The O-alkyl groups on these foldamers are capable of adopting syn- or anti-conformers through rotation around the Ar-CO/NH axes. In the syn-conformation this allows the foldamer to act as a topographical mimic of the α-helix whereby the O-alkyl groups mimic the spatial orientation of the i and i + 4 side-chains from the α-helix. Using molecular modelling and 2D NMR analyses, this work illustrates that covalent links and hydrogen-bonding interactions between side-chains can bias the conformation in favour of the α-helix mimicking syn-conformer, offering insight that may be more widely applied to control secondary structure in foldamers.

From Concept to Crystals via Prediction: Multi-Component Organic Cage Pots by Social Self-Sorting.

We describe the a priori computational prediction and realization of multi-component cage pots, starting with molecular predictions based on candidate precursors through to crystal structure prediction and synthesis using robotic screening. The molecules were formed by the social self-sorting of a tri-topic aldehyde with both a tri-topic amine and di-topic amine, without using orthogonal reactivity or precursors of the same topicity. Crystal structure prediction suggested a rich polymorphic landscape, where there was an overall preference for chiral recognition to form heterochiral rather than homochiral packings, with heterochiral pairs being more likely to pack window-to-window to form two-component capsules. These crystal packing preferences were then observed in experimental crystal structures.

Near-Ideal Xylene Selectivity in Adaptive Molecular Pillar[ n]arene Crystals.

The energy-efficient separation of alkylaromatic compounds is a major industrial sustainability challenge. The use of selectively porous extended frameworks, such as zeolites or metal-organic frameworks, is one solution to this problem. Here, we studied a flexible molecular material, perethylated pillar[ n]arene crystals ( n = 5, 6), which can be used to separate C8 alkylaromatic compounds. Pillar[6]arene is shown to separate para-xylene from its structural isomers, meta-xylene and ortho-xylene, with 90% specificity in the solid state. Selectivity is an intrinsic property of the pillar[6]arene host, with the flexible pillar[6]arene cavities adapting during adsorption thus enabling preferential adsorption of para-xylene in the solid state. The flexibility of pillar[6]arene as a solid sorbent is rationalized using molecular conformer searches and crystal structure prediction (CSP) combined with comprehensive characterization by X-ray diffraction and 13C solid-state NMR spectroscopy. The CSP study, which takes into account the structural variability of pillar[6]arene, breaks new ground in its own right and showcases the feasibility of applying CSP methods to understand and ultimately to predict the behavior of soft, adaptive molecular crystals.

Computational modelling of solvent effects in a prolific solvatomorphic porous organic cage.

Crystal structure prediction methods can enable the in silico design of functional molecular crystals, but solvent effects can have a major influence on relative lattice energies, sometimes thwarting predictions. This is particularly true for porous solids, where solvent included in the pores can have an important energetic contribution. We present a Monte Carlo solvent insertion procedure for predicting the solvent filling of porous structures from crystal structure prediction landscapes, tested using a highly solvatomorphic porous organic cage molecule, CC1. Using this method, we can understand why the predicted global energy minimum structure for CC1 is never observed from solvent crystallisation. We also explain the formation of three different solvatomorphs of CC1 from three structurally-similar chlorinated solvents. Calculated solvent stabilisation energies are found to correlate with experimental results from thermogravimetric analysis, suggesting a future computational framework for a priori materials design that factors in solvation effects.