One new aminopyrazole, 1,3-di(pyridin-2-yl)-1H-pyrazol-5-amine (2), and three new thiourea-functionalized compounds, 1-(4-methoxyphenyl)-3-(3-phenyl-1-(pyridin-2-yl)-1H-pyrazol-5-yl)thiourea (3), 1-(4-methoxyphenyl)-3-(3-pyridinyl-1-(pyridin-2-yl)-1H-pyrazol-5-yl)thiourea (4), and 1-(3-methoxyphenyl)-3-(3-pyridinyl-1-(pyridin-2-yl)-1H-pyrazol-5-yl)thiourea (5) were synthesized and characterized. The crystal structures of all four aminopyrazole-based frameworks, as well as a minor side-product, O-ethyl(3-phenyl-1-(pyridin-2-yl)-1H-pyrazol-5-yl)carbamothioate (6), and the zinc(II) chloride complex with 4, were determined. For each pyrazolylthiourea, all strong hydrogen-bond donors are utilized, while the pyrazole nitrogen hydrogen-bond acceptors are unengaged. This is attributed in part due to the formation of intermolecular R 2 2(8) N-HS hydrogen-bonded rings that incorporate the weaker sulfur acceptor, leaving an open Lewis base site available for metal coordination. Excitation and emission properties were evaluated in both solution and solid-state for the three methoxyphenyl-substituted ligands (3, 4, and 5) revealing bright solid-state fluorescence for 3 and 4. Enhanced solid-state fluorescence was observed for 4 relative to 3 (Phi solid-state = 7.63 vs 4.28%) consistent with increased molecular rigidity and a higher proportion of NH/HN interactions (9.7 vs 5.0% of the Hirshfeld surfaces). Upon coordination to Zn(II), fluorescence from 4 was quenched, demonstrating its potential as a metal-responsive sensor. DFT and TD-DFT calculations indicate that quenching likely arises from a diminished transition dipole associated with the ligand-ligand charge-transfer S1 state of the Zn(II) complex.

Fluoride anions (F-) are commonly found in everyday items and are known to have positive medicinal uses. Despite their importance, overconsumption can lead to dental and skeletal fluorosis, among other health issues. In pursuit of a more effective method to detect trace amounts of anions in aqueous media, we synthesized two triarylborane-functionalized lanthanide metal-organic frameworks (LnBMOFs) to act as solid-state luminescent sensors. The LnBMOFs, EuBMOF and TbBMOF, use europium and terbium, respectively, as these metal ions display strong luminescent properties. The electrophilic nature of the triarylborane ligand makes it an ideal candidate for sensing high affinity F-, while also providing steric bulk to enhance the selectivity and stability of the LnBMOFs. We further demonstrate that LnBMOFs are capable of sensing other small anions including CN- and OH- but also a wider scope of anions including PO4 3-, SO4 2-, NO3 -, and Cl-, while maintaining a high degree of sensitivity. The structural design of these LnBMOFs provides a turn-on/off effect with some anions, where the luminescence is regenerated and maintains stability through several cycles upon washing with water.

Targeting mitochondrial function offers a compelling route for selective cancer therapy. We report the design, synthesis, and biological assessment of three novel biguanide-iridium(iii) complexes as potent mitochondrial disruptors in pancreatic cancer cells. These complexes demonstrate markedly enhanced cytotoxicity compared to their parent biguanide ligands. Confocal imaging confirms rapid mitochondrial localization within 30 minutes, with subsequent impairment of the respiratory chain, suggesting a direct mechanism of mitochondrial dysfunction. These results highlight the therapeutic potential of iridium-based metallodrugs in targeting metabolic vulnerabilities of pancreatic cancer.

Aluminium MOFs have gained researchers attention for their applications in gas sequestration, water harvesting, drug delivery and chemical storage. Current synthetic methods, however, rely on a variety of aluminium salts for synthesis of MOFs within the same family and are not the most efficient sources of aluminium. Herein, we demonstrate a robust synthetic pathway to MOFs CAU-9, CAU-10 (-NO2,-NH2,-N3), CAU-10-py, CAU-15, CAU-21, MIL-53(Al)-TCD, MOF-303 and Al-Fum from aluminium formate, a compound that we have previously synthesized from industrial aluminium waste. We replace commercial aluminium salts with sustainably sourced aluminium, reducing the amount of waste and harmful byproducts, all by using a common aluminium precursor.

In the pursuit of a stable hydrogen evolution photosensitiser, we demonstrate the incorporation of a series of our H-bond rich guanidine-styled iridium (III) complexes into a catalytic system. Using automation accelerated catalysis screening techniques we optimised our system quickly and effectively to observe how these strongly H-bonding complexes may perform. Proven to be photo-electronically suitable, and with effective electron transfer abilities evidenced by Stern-Volmer mechanistic studies, the complexes showed modest levels of H2 evolution in comparison to previously investigated photosensitisers with general formula [Ir(C^N)2(N^N)].

Giant unilamellar vesicles (GUVs) are ideal for studying cellular mechanisms due to their cell-mimicking morphology and size. The formation, stability, and immobilization of these vesicles are crucial for drug delivery and bioimaging studies. Separately, metal-organic frameworks (MOFs) are actively researched owing to their unique and varied properties, yet little is known about the interaction between MOFs and phospholipids. This study investigates the influence of the metal-phosphate interface on the formation, size distribution, and stability of GUVs with different lipid compositions. GUVs were electroformed in the presence of a series of MOFs. The results show Al, Zn, Cu, Fe, Zr, and Ca metal centers of MOFs can coordinate to phospholipids on the surface of GUVs, leading to the formation of functional GUV@MOF constructs, with stablilities over 12 hours. Macroscopically, society has seen biology (people, plants, microbes) interacting with inorganic materials regularly. We now explore how microscopic biological models behave in the presence of inorganic constructs. This research opens new avenues for advanced biomedical applications interacting tailored frameworks with liposomes.

Despite the increased use of mechanochemistry for chemical reactions few options for reaction monitoring or solid state analysis are available. This work explores using T1 T2* 1H NMR to monitor the reaction between benzil or 4,4’ dimethybenzil with o phenylenediamine. For both reactions, the T1 T2* correlation plots show differences in relaxation times throughout the reaction. This work demonstrates using two different strageties to monitor the reaction progression. In the first case the reaction is monitered by the appearance of signals corresponding to the product, and side product water. In the second case the reaction is monitored by the replacement of the signals corresponding to the starting material, by signals corresponding to the product. This magnetic resonance correlation measurement provides an excellent option for whole sample solid state analysis by virtue of its simplicity and versatility.

Novel H-bond-rich iridium(iii) complexes with different systems of cyclometalating ligands bearing the general formula [Ir(C<^>N)2(N<^>N)] were synthesised, characterised and their photophysical properties determined. The incorporated guanidine moieties allow us to introduce a hydrogen-bonding array for the formation of self-assembled iridium-bound hydrogen-bonded systems. Through a series of experimental and computational studies we demonstrated the host-guest chemistry of these systems. These hydrogen-bonding interactions were shown to have significant impacts on chromaticity, quantum yields and lifetimes with emphasis on energy transfer studies based on this second-sphere coordination approach.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A library of cyclometallated iridium (III) complexes with a strong H-bonding motif in their ancillary ligand was synthesized, characterized and their photophysical properties measured. Demonstrated herein is a general synthetic high yield procedure for these compounds. We ascribe these yields to the use of an intermediary primer ligand. This de novo strategy circumnavigates the standard synthetic issues of H-bond rich ligand precursors (self-aggregation and poor solubility in organic solvents). Alternative and greener synthetic pathways were also explored to realize the intermediate iridium primer complex.

To write this article, Emily Draper and Jennifer Leigh from the International Women in Supramolecular Chemistry (WISC) network again joined forces with David Smith and asked dads working within the field of supramolecular chemistry to share experiences around parental leave.

We present a new approach to monitoring mechanochemical transformations, using a magnetic resonance (MR) method in which relaxation time correlation maps are used to follow the formation of metal–organic frameworks (MOFs) Zn-MOF-74 and ZIF-8.

Hydrogen-bonding has been reported as a smart strategy in electrochemiluminescence (ECL) mechanism stud-ies and sensing applications. However, the insights into the hydrogen-bonding effect on ECL behavior have never been clearly demonstrated. This work reports ECL of complex 1 center dot 3 based on the hydrogen-bonding inter-action between an IrIII complex (1) and pyrimido-[4,5-c]isoquinolin-3-amine (3). In their cyclic voltammo-grams (CVs), both complex 1 and compound 3 did not show any reductions; however, the hydrogen -bonding complex 1 center dot 3 displayed a new reduction upon the mixture of 1 and 3, which could be significantly weakened by the addition of DMF. In a co-reactant ECL pathway with BPO, exciplex [PhCO2.center dot 1] and excimer [3 center dot 3] were produced, which were demonstrated by PL and ECL spectroscopies. Furthermore, benzoate radical PhCO2. could also react with the hydrogen-bonding complex 1 center dot 3 to form [PhCO2.center dot 1 center dot 3] and generate the same ECL emission as [PhCO2.-1]. Our report provides insights into the ECL processes of this hydrogen -bond-ing complex.

Guanidine-and thiourea-based complexes have been the subject of extensive study due to their wide range of potential applications, including but not limited to anti-cancer drugs, ion transporters, and sensors. Building upon previous work done in this group, we aimed to demonstrate a new series of organometallic complexes based on functionally diverse guanidine and thiourea ligands. Herein, the synthesis and characterization of new platinum, rhodium, and cobalt complexes is presented. While most of these complexes conformed to properties and behaviours in line with previous work, one complex based on a Pt(II) and guanidine derivative exhibited unusual supramolecular properties, demonstrating a larger self-assembled dimer consisting of six Pt(II) cations.

This work reports absolute electrochemiluminescence (ECL) quantum efficiencies (QEs) of two iridium(III) complexes, fac-Ir(ppy)3 (Ir-1) and [Ir(ppy)2(dtbubpy)]+ ([Ir-2]+) in annihilation and coreactant pathways. With potentiodynamic scans and potential pulsing, ECL mechanisms were investigated by means of ECL-voltage curves, ECL-time curves and ECL spectroscopy. It was demonstrated that the radical stability and reactivity are the two main factors affecting ECL efficiencies in various processes, while intermediate charges have little effect. Considering the difference of such radical behaviors between [Ru(bpy)3]2+ and other luminophores, absolute ECL QEs are more applicable compared with the ones relative to [Ru(bpy)3]2+ as a standard.

Lipid bilayer vesicles have provided a window into the function and fundamental properties of cells. Vesicles, however, do not remain still, requiring some microscopy experiments to include a preparatory fixation step. Here, we describe a straightforward method to immobilise giant unilamellar vesicles (GUVs) using a zirconium-based metal-organic framework (MOF) and demonstrate that they stay in position on a timescale of minutes- to hours. Furthermore, immobilising GUVs in this way has no discernible adverse effect on GUV stability and permeability. These findings indicate that this strategy may be a powerful tool for future studies into lipid membrane function and dynamics.

We present two iridium complexes 1H+ and 2H+ 9 that contain cationic ligands to extend the knowledge 10 of charge-assisted hydrogen bonding (CAHB), which counts among the strongest non-covalent 11 bonding interactions. Upon protonation, both complexes were converted into new hydrogen-bonding 12 arrays with various selectivity for respective H-bonding partners. This study compares the association 13 strengths of four hydrogen-bonding co-systems, emphasizing the roles of CAHB in supramolecular systems. We determined that the cationic charge in these systems contributed up to 2.7 kJ mol-1 14 in the 15 H-bonding complexation processes