A Cationic Catechol Derivative Binds Anions in Competitive Aqueous Media.

A simple dihydroxy isoquinolinium molecule (3+) was prepared by a modification of a literature procedure. Interestingly, during optimisation of the synthesis a small amount of the natural product pseudopalmatine was isolated, and characterised for the first time by X-ray crystallography. Compound 3+ contains a catechol motif and positive charge on the same scaffold and was found to be a potent anion receptor, binding sulfate strongly in 8 : 2 d6-acetone:D2O and 7 : 3 d6-acetone:D2O (Ka>104 and 2,100 M-1, respectively). Unsurprisingly, chloride binding was much weaker, even in the less polar solvent mixture 9 : 1 d6-acetone:D2O. The sulfate binding is remarkably strong for such a simple molecule, however anion binding studies were complicated by the tendency of the molecule to react with BPh4 - or BF4 - species during anion metathesis reactions. This gave two unusual zwitterions containing tetrahedral boronate centres, which were both characterised by X-ray crystallography.

Stereoselective Single Step Cyclization to Give Belt-Functionalized Pillar[6]arenes.

Two macrocycles were synthesized through cyclization reactions of secondary benzylic alcohols, giving pillar[6]arenes with a methyl substituent at each belt position. These macrocycles form stereoselectively with only the rtctct isomer with alternating up and down orientations of the belt methyl groups definitively identified. Isolated yields were modest (7 and 9%), but the macrocycles are prepared in a single step from either a commercially available alcohol or a very readily prepared precursor. X-ray crystal structures of the macrocycles indicate they have a capsule-like structure, which is far from the conventional pillar shape. Density functional theory calculations reveal that the energy barrier required to obtain the pillar conformation is significantly higher for these belt-functionalized macrocycles than for conventional belt-unfunctionalized pillar[6]arenes.

Hydrogen-bonded frameworks containing aliphatic 3D linkers show high-capacity water vapour sorption.

Hydrogen-bonded frameworks were prepared from a tetra-amidinium component and three-dimensional cubane and bicyclopentane dicarboxylate linkers. Despite the incorporation of aliphatic components, the frameworks demonstrate strong and reversible uptake of water vapour, with one of the frameworks showing water uptake at very low relative humidity.

Hydrogen atoms in supramolecular chemistry: a structural perspective. Where are they, and why does it matter?

Hydrogen bonding interactions are ubiquitous across the biochemical and chemical sciences, and are of particular interest to supramolecular chemists. They have been used to assemble hydrogen bonded polymers, cages and frameworks, and are the functional motif in many host-guest systems. Single crystal X-ray diffraction studies are often used as a key support for proposed structures, although this presents challenges as hydrogen atoms interact only weakly with X-rays. In this Tutorial Review, we discuss the information that can be gleaned about hydrogen bonding interactions through crystallographic experiments, key limitations of the data, and emerging techniques to overcome these limitations.

Balancing on a Knife's Edge: Studies on the Synthesis of Pillar[6]arene Derivatives.

Pillar[6]arenes are established as crucial building blocks in supramolecular chemistry; however, they can be difficult to synthesize, particularly in the absence of large solubilizing substituents. In this work, we explore variability in literature syntheses of pillar[6]arene derivatives and suggest that the outcome is dependent on whether oligomeric intermediates stay in solution long enough for the thermodynamically favorable macrocyclization to occur. We demonstrate that in a previously capricious BF3·OEt2-mediated procedure, ≤5 mol % of a Brønsted acid can slow down the reaction to favor macrocycle formation.

Charge "mis-matched" hydrogen bonded frameworks for cation exchange and dye sorption.

Anionic hydrogen bonded frameworks were synthesised from di or tetra-amidinium hydrogen bond donor components and a charge "mis-matched" tecton possessing a 5- charge but only four hydrogen bond accepting groups. The net negative charge on the framework skeletons necessitates the presence of a cation in the framework channel. In one of the frameworks, the initially incorporated organic cation was rapidly displaced by smaller inorganic cations, or the cationic dye methylene blue. This facilitated the effective and selective removal of this dye from water.

Supramolecular chemistry of two new bis(1,2,3-triazolyl)pyridine macrocycles: metal complexation, self-assembly and anion binding.

Two new macrocycles containing the bis(1,2,3-triazolyl)pyridine (btp) motif were prepared in high yields from a btp diazide precursor (1). Solution 1H NMR studies show that this diazide undergoes self-assembly with divalent transition metal ions to form ML2 complexes with pendant azide groups, apparently suitable for conversion into metal-templated catenanes; however attempts to form these catenanes were unsuccessful. Instead a new macrocycle containing two btp motifs was prepared, which forms a nanotube structure in the solid state. Reduction of the azide groups to amines followed by amide bond formation was used to convert 1 into macrocycle 8 containing btp and isophthalamide functionalities. This macrocycle binds halide and oxalate anions in acetonitrile solely through the isophthalamide motif, and binds aromatic dicarboxylates very strongly through both the isophthalamide amide donors and the btp triazole donors. The macrocycle was complexed with Pd(II) and the resulting complexes were shown to bind strongly to halide anions. The solid state structures of [Pd·8·X]BF4 (X = Cl-, Br-, I-) were investigated by X-ray crystallography, which showed that [Pd·8·Br] forms an unusual "chain of dimers" structure assembled by metal complexation, N-H⋯Br- hydrogen bonding and short Pd⋯Pd contacts.

Selective Removal of Sulfate from Water by Precipitation with a Rigid Bis-amidinium Compound.

A simple, readily prepared biphenyl bis-amidinium compound (1⋅Cl2 ) is able to selectively precipitate sulfate from water. The precipitant is effective at concentrations as low as 1 mM and shows complete selectivity against monovalent anions, and high selectivity even against CO3 2- and HPO4 2- . It is highly effective (>90 % sulfate removed) in both seawater and highly acidic conditions relevant to mining waste-streams. X-ray crystallography reveals that 1⋅SO4 forms a tightly packed, anhydrous, structure where each sulfate anion receives eight hydrogen bonds from amidinium N-H hydrogen bond donors.

Correspondence on "Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System".

In a recent Research Article, Ben and co-workers reported a hydrogen-bonded framework prepared from a 4+ tetra-amidinium component and a 4- tetra-sulfonate component, termed CPOS-6. They showed that CPOS-6 could reversibly adsorb and desorb water over a narrow humidity window, and that this material offered potential for applications in atmospheric water harvesting. This conclusion was supported by experiments that showed the material was stable over 50 adsorption/desorption cycles and that the kinetics of these cycles were very rapid. In this Correspondence we present additional structural data regarding this framework in both its hydrated and dehydrated states and thus discern the mechanism of water binding. These data do not disagree with Ben and co-workers' findings: rather they emphasise how remarkable the cyclability and rapid kinetics of adsorption/desorption are, as these processes involve a complete crystal-to-crystal rearrangement of the framework.

Post-Synthetic Modification of a Porous Hydrocarbon Cage to Give a Discrete Co24 Organometallic Complex.

A new alkyne-based hydrocarbon cage was synthesized in high overall yield using alkyne-alkyne coupling in the cage forming step. The cage is porous and displays a moderately high BET surface area (546 m2 g-1 ). The cage loses crystallinity on activation and thus is porous in its amorphous form, while very similar cages have been either non-porous, or retained crystallinity on activation. Reaction of the cage with Co2 (CO)8 results in exhaustive metalation of its 12 alkyne groups to give the Co24 (CO)72 adduct of the cage in good yield.

Water Sorption Controls Extreme Single-Crystal-to-Single-Crystal Molecular Reorganization in Hydrogen Bonded Organic Frameworks.

As hydrogen bonded frameworks are held together by relatively weak interactions, they often form several different frameworks under slightly different synthesis conditions and respond dynamically to stimuli such as heat and vacuum. However, these dynamic restructuring processes are often poorly understood. In this work, three isoreticular hydrogen bonded organic frameworks assembled through charge-assisted amidinium⋅⋅⋅carboxylate hydrogen bonds (1C/C , 1Si/C and 1Si/Si ) are studied. Three distinct phases for 1C/C and four for 1Si/C and 1Si/Si are fully structurally characterized. The transitions between these phases involve extreme yet recoverable molecular-level framework reorganization. It is demonstrated that these transformations are related to water content and can be controlled by humidity, and that the non-porous anhydrous phase of 1C/C shows reversible water sorption through single crystal to crystal restructuring. This mechanistic insight opens the way for the future use of the inherent dynamism present in hydrogen bonded frameworks.

Vibrational mode analysis of hydrogen-bonded organic frameworks (HOFs): synchrotron infrared studies.

Hydrogen-bonded organic frameworks (HOFs) are a promising class of porous crystalline materials for gas sorption and gas separation technologies that can be constructed under mild synthetic conditions. In forming three-dimensional networks of flexible hydrogen bonds between donor/acceptor subunits, these materials have displayed high stability at elevated temperature and under vacuum. Although the structural properties of HOFs are commonly characterized by diffraction techniques, new complimentary methods to elucidate phase behaviour and host-guest interactions at the molecular level are sought, particularly those that can be applied under changing physical conditions or solvent environment. To this end, this study has applied synchrotron far-IR and mid-IR spectroscopy to probe the properties of two known and one new HOF system assembled from tetrahedral amidinium and carboxylate building blocks. All three frameworks produce feature-rich and resolved infrared profiles from 30 to 4000 cm-1 that provide information on hydrogen-bonded water solvent networks and the HOF channel topography via lattice and torsional bands. Comparison of experimental peaks to frequencies and atomic displacements (eigenvectors) predicted by high-level periodic DFT calculations have allowed for the assignment of vibrational modes associated with the aforementioned physicochemical properties. Now compiled, the specific vibrational modes identified as common to charge-assisted hydrogen-bonding motifs, as well as low frequency lattice and torsional bands attributed to HOF pore morphology and water-of-hydration networks, can act as diagnostic features in future spectroscopic investigations of HOF properties, such as those toward the design and tuning of host-guest properties for targeted applications.

Hydroxy Groups Enhance [2]Rotaxane Anion Binding Selectivity.

We report the synthesis of two [2]rotaxanes containing an interlocked three dimensional binding cavity formed from a pyridinium bis(amide) axle component containing two phenol donors, and an isophthalamide based macrocycle. In the competitive solvent mixture 1 : 1 CDCl3 : CD3 OD, one of the receptors exhibits a much higher selectivity preference for chloride than an analogous rotaxane without the hydroxy groups. X-ray crystal structures reveal the chloride anion guest encapsulated within the interlocked binding cavity, though not all of the hydrogen bond donors are utilised. Computational semi-empirical simulations indicate that secondary intermolecular interactions occur between the axle hydroxy hydrogen bond donors and the [2]rotaxane macrocycle components, contributing to a more preorganised binding pocket, which may be responsible for the observed enhanced selectivity.

Use of modulators and light to control crystallisation of a hydrogen bonded framework.

The effect of concentration, organic co-solvent, and salt modulators on the crystallisation of a hydrogen bonded framework was studied. The framework contains ∼1.4 nm wide channels and contains a diazobenzene based dicarboxylate anion. Light-induced cis/trans switching of this anion was also used to control crystallisation.

Amidinium⋯carboxylate frameworks: predictable, robust, water-stable hydrogen bonded materials.

In the last few years, the amidinium⋯carboxylate interaction has emerged as a powerful tool for the relatively predictable construction of families of three dimensional hydrogen bonded organic frameworks. These frameworks can be prepared in water and are surprisingly stable, including to heating in polar organic solvents and water. This feature article describes the design and synthesis of these materials, discusses their structures and stability, and highlights their recent applications for enzyme encapsulation and as precursors for the synthesis of molecularly thin hydrogen bonded 2D nanosheets.

Room Temperature Hydrolysis of Benzamidines and Benzamidiniums in Weakly Basic Water.

Benzamidinium compounds have found widespread use in both medicinal and supramolecular chemistry. In this work, we show that benzamidiniums hydrolyze at room temperature in aqueous base to give the corresponding primary amide. This reaction has a half-life of 300 days for unsubstituted benzamidinium at pH 9, but is relatively rapid at higher pH's (e.g., t1/2 = 6 days at pH 11 and 15 h at pH 13). Quantum chemistry combined with first-principles kinetic modeling can reproduce these trends and explain them in terms of the dominant pathway being initiated by attack of HO- on benzamidine. Incorporation of the amidinium motif into a hydrogen bonded framework offers a substantial protective effect against hydrolysis.

Monolayer nanosheets formed by liquid exfoliation of charge-assisted hydrogen-bonded frameworks.

Hydrogen-bonded organic frameworks (HOFs) are a diverse and tunable class of materials, but their potential as free-standing two-dimensional nanomaterials has yet to be explored. Here we report the self-assembly of two layered hydrogen-bonded frameworks based on strong, charge-assisted hydrogen-bonding between carboxylate and amidinium groups. Ultrasound-assisted liquid exfoliation of both materials readily produces monolayer hydrogen-bonded organic nanosheets (HONs) with micron-sized lateral dimensions. The HONs show remarkable stability and maintain their extended crystallinity and monolayer structures even after being suspended in water at 80 °C for three days. These systems also exhibit efficient fluorescence quenching of an organic dye in organic solvents, superior to the quenching ability of the bulk frameworks. We anticipate that this approach will provide a route towards a diverse new family of molecular two-dimensional materials.

Simple acyclic molecules containing a single charge-assisted O-H group can recognize anions in acetonitrile : water mixtures.

Hydroxypyridinium and hydroxyquinolinium compounds containing acidic O-H groups attached to a cationic aromatic scaffold were synthesized, i.e. N-methyl-3-hydroxypyridinium (1+) and N-methyl-8-hydroxyquinolinium (2+). These very simple compounds are capable of binding to chloride very strongly in CD3CN and with moderate strength in 9 : 1 CD3CN : D2O. Comparison with known association constants reveals that 1+ and 2+ bind chloride in CD3CN or CD3CN : D2O with comparable affinities to receptors containing significantly more hydrogen bond donors and/or higher positive charges. Crystal structures of both compounds with coordinating anions were obtained, and feature short O-Hanion hydrogen bonds. A receptor containing two hydroxyquinolinium groups was also prepared. While the low solubility of this compound caused difficulties, we were able to demonstrate chloride binding in a competitive 1 : 1 CD3CN : CD3OD solvent mixture. Addition of sulfate to this compound results in the formation of a crystallographically-characterised solid state anion coordination polymer.

Anion Templated Supramolecular Structures Assembled using 1,2,3-Triazole and Triazolium motifs.

The use of 1,2,3-triazole and triazolium motifs to construct anion templated supramolecular structures has grown rapidly over the past decade and has enabled a range of complex structures to be synthesised. In this Minireview we highlight the significant advances that have been made in areas such as foldamers, polymers and interlocked systems.