Guest inclusion by Borromean weave coordination networks

Reaction of N,Nʺ-ethylene-1,2-diylbis(3-pyridin-3-ylurea) (L) with AgNO3 in a variety of solvents gives a total of five 2-D Borromean weave coordination polymer networks that adopt three structural types depending on the interactions to the solvent pocket. The Borromean network is of formula [Ag2(L)3](NO3)2 ·solvent where the solvent is either a cluster of water molecules, mixtures of water and acetonitrile, water and methanol or chloroform and methanol. The Borromean structure is a thermodynamic sink and under fast crystallization conditions an alternative 2 + 2 metallomacrocycle forms that can result in metallogel formation. The metallogel structure transforms into the crystalline Borromean network over time

Mechanochemical Synthesis of N-Aryl Amides from O-Protected Hydroxamic Acids

Two robust and efficient mechanochemical protocols for the synthesis of an array of N-arylamides have been developed. This was achieved by a C-N cross-coupling between O-pivaloyl hydroxamic acids and aryl iodides or aryl boronic acids, in the presence of a stoichiometric amount of a copper mediator. The effectiveness of this method is highlighted by the high-yielding (up to 94%), scalable (up to 8 mmol), and rapid (20 minutes) synthesis of N-aryl amides (15 examples), using a variety of deactivated and sterically encumbered substrates, whilst employing mild conditions and in the absence of solvents. In addition, it was determined that whilst the O-pivaloyl hydroxamic acid precursors can be synthesised mechanochemically, iron contamination originating from the steel jars was found to occur which can hinder the efficacy of this process. Furthermore, 3D printing was used to produce custom milling jars that could successfully accommodate a scaled-up version of the two protocols

Targetable Mechanical Properties by Switching between Self-Sorting and Co-assembly with In Situ Formed Tripodal Ketoenamine Supramolecular Hydrogels

A new family of supramolecular hydrogelators are introduced in which self-sorting and co-assembly can be utilised in the tuneability of the mechanical properties of the materials, a property closely tied to the nanostructure of the gel network. The in situ reactivity of the components of the gelators allows for system chemistry concepts to be applied to the formation of the gels and shows that molecular properties, and not necessarily the chemical identity, determines some gel properties in these family of gels

Phase Transitions in Zeolitic Imidazolate Framework 7: The Importance of Framework Flexibility and Guest-Induced Instability

A study of the phase transitions in ZIF-7 (zeolitic imidazolate frameworks- (Zn(PhIm)2, PhIm = benzimidazolate)) as a function of guest occupancy and temperature was reported. Raman spectra of an as-synthesized sample were collected in air between 297 and 421 K. The major contributions of the spectra come from the vibrational modes of the benzimidazolate ligand. Upon heating, most of the Raman bands remain similar and keep the same frequencies until 357 K, indicating that the structure of ZIF-7 seems to be stable in this temperature range. Above 357 K, strong modifications are observed in the regions corresponding to the lattice modes. The formation of ZIF-7-II is attributed to the loss of dimethylformamide (DMF) solvent molecules from the ZIF-7-I framework. This can be confirmed by the differential scanning calorimetry and thermogravimetric analysis traces of ZIF-7-I. The highly-distorted and locally-strained nature of ZIF-7-II leads to its poor crystallinity, reflected by X-ray powder diffraction and scanning electron microscope

Molecular Interactions behind the Self-Assembly and Microstructure of Mixed Sterol Organogels

In this work, we have employed docking and atomistic molecular dynamics (MD) simulations supported by complementary experiments using atomic force microscopy, rheology and spectroscopy to investigate the self-assembled structure of β-sitosterol and γ-oryzanol molecules into cylindrical tubules in a non-aqueous solvent. Docking models of several phytosterols, including sitosterol, with oryzanol and other sterol-esters demonstrate that for systems to form tubules, the phytosterol sterane group must be stacked in a wedge shape with the esters sterane group, and a hydrogen bond must form between the hydroxyl group of the phytosterol and the carbonyl group of the ester. Molecular dynamics of the self-assembled structure were initiated with the molecules in a roughly cylindrical configuration, as suggested from previous experimental studies, and the configurations were found to be stable during 50 ns simulations. We performed MD simulations of two tubules in proximity to better understand the aggregation of these fibrils and how the fibrils interact in order to stick together. We found that an interfibril network of non-covalent bonds, in particular van der Waals and π-π contacts, which is formed between the ferulic acid groups of oryzanol through the hydroxyl, methoxy and aromatic groups, is responsible for the surface-to-surface interactions between fibrils; an observation supported by molecular spectroscopy. We believe these interactions are of primary importance in creating a strong organogel network

Supramolecular Amino Acid Based Hydrogels: Probing the Contribution of Additive Molecules using NMR Spectroscopy

Supramolecular hydrogels are composed of self-assembled solid networks that restrict the flow of water. l-Phenylalanine is the smallest molecule reported to date to form gel networks in water, and it is of particular interest due to its crystalline gel state. Single and multi-component hydrogels of l-phenylalanine are used herein as model materials to develop an NMR-based analytical approach to gain insight into the mechanisms of supramolecular gelation. Structure and composition of the gel fibres were probed using PXRD, solid-state NMR experiments and microscopic techniques. Solution-state NMR studies probed the properties of free gelator molecules in an equilibrium with bound molecules. The dynamics of exchange at the gel/solution interfaces was investigated further using high-resolution magic angle spinning (HR-MAS) and saturation transfer difference (STD) NMR experiments. This approach allowed the identification of which additive molecules contributed in modifying the material properties

Halogen effects on the solid-state packing of phenylalanine derivatives and the resultant gelation properties

Phenylalanine is an important amino acid both biologically, essential to human health, and industrially, as a building block of artificial sweeteners. Our interest in this particular amino acid and its derivatives lies with its ability to form gels in a number of solvents. We present here the studies of the influence of halogen addition to the aromatic ring on the gelation properties and we analyse the crystal structures of a number of these materials to elucidate the trends in their behaviour based on the halogen addition to the aromatic group and the interactions that result

Polymer-Supported Photosensitizers for Oxidative Organic Transformations in Flow and under Visible Light Irradiation

A 2,1,3-benzothiadiazole (BTZ)–based vinyl crosslinker was synthesized and copolymerized with large excesses of styrene using free radical polymerization to deliver heterogeneous triplet photosensitizers in three distinct physical formats: gels, beads and monoliths. These photosensitizers were employed for the production of singlet oxygen (1O2) and for the aerobic hydroxylation of aryl boronic acids via superoxide radical anion (O2˙-) whereby the materials demonstrated good chemical and photo stability. BTZ-containing beads and monoliths were exploited as photosensitizers in a commercial flow reactor, and 1O2 production was also demonstrated using direct sunlight irradiation, with a conversion rate comparable to the rates achieved when using a 420 nm LED module as the source of photons

Supramolecular assembly in a Janus-type urea system

A pyrazolyl urea ligand adopts two possible conformations with the urea NH groups directed either outward or inward. Metal coordination enforces the outward conformation resulting in either anion complexation or self-association and hence extended supramolecular assemblies including a hexameric barrel that persists in solution

The Plot Thickens: Gelation by Phenylalanine in Water and Dimethyl Sulfoxide

Phenylalanine (Phe) is an amino acid of great interest as coupling of an aromatic group with a chiral hydrophilic region imparts a number of unique properties. Recently there has been an increased interest in the crystalline and gel forms of this compound, part as a result of the complex and undetermined structures of the resulting materials and the relationship of the solid forms of Phe with the disease phenylketonuria. In this report, we highlight the relationship between gelation, crystallization, and the dynamics of self-assembly processes of Phe. We do this by describing the gelation of the amino acid, the gel to crystal relationship, crystal structure predictions for this relatively simple compound, and the dynamics of assembly as determined by NMR in both water and dimethyl sulfoxide. This will provide guidance to future research into Phe assemblies, possible treatments for phenylketonuria, and diseases related to formation of amyloid-like fibers