Synthesis and characterisation of copper(I) complexes with relevance to intramolecular Ullmann O,S-arylation.

Copper-catalysed intramolecular Ullman arylation has been frequently used to synthesise benzoxazoles and benzothiazoles. Despite widespread use, investigations into the mechanism and speciation of copper-containing complexes relevant to the catalytic pathway have remained relatively limited. Accordingly, this study aims to elucidate the structural details of potential copper(I) intermediates through the analysis of their solid-state structures using X-ray crystallography, while also investigating the reactivities of these complexes. Five novel copper complexes are reported which are formed prior to the aryl halide activation step and feature distinct aggregation modes based on either Cu4N4O4C4 or Cu4N4S4C4 clusters.

Harnessing Maxwell's demon to establish a macroscale concentration gradient.

Maxwell's demon describes a thought experiment in which a 'demon' regulates the flow of particles between two adjoining spaces, establishing a potential gradient without appearing to do work. This seeming paradox led to the understanding that sorting entails thermodynamic work, a foundational concept of information theory. In the past centuries, many systems analogous to Maxwell's demon have been introduced in the form of molecular information, molecular pumps and ratchets. Here we report a functional example of a Maxwell's demon that pumps material over centimetres, whereas previous examples operated on a molecular scale. In our system, this demon drives directional transport of o-fluoroazobenzene between the arms of a U-tube apparatus upon light irradiation, transiting through an aqueous membrane containing a coordination cage. The concentration gradient thus obtained is further harnessed to drive naphthalene transport in the opposite direction.

Light-Powered Reversible Guest Release and Uptake from Zn4L4 Capsules.

A strategy for light-powered guest release from a tetrahedral capsule has been developed by incorporating azobenzene units at its vertices. A new Zn4L4 tetrahedral capsule bearing 12 diazo moieties at its metal-ion vertices was prepared from a phenyldiazenyl-functionalized subcomponent and a central trialdehyde panel. Ultraviolet irradiation caused isomerization of the peripheral diazo groups from the thermodynamically preferred trans configuration to the cis form, thereby generating steric clash and resulting in cage disassembly and concomitant guest release. Visible-light irradiation drove cage re-assembly following re-isomerization of the diazo groups to the trans form, resulting in guest re-uptake. A detailed 19F NMR study elucidated how switching led to guest release: each metal vertex tolerated only one cis-azobenzene moiety, with further isomerization leading to cage disassembly.

Transformation networks of metal-organic cages controlled by chemical stimuli.

The flexibility of biomolecules enables them to adapt and transform as a result of signals received from the external environment, expressing different functions in different contexts. In similar fashion, coordination cages can undergo stimuli-triggered transformations owing to the dynamic nature of the metal-ligand bonds that hold them together. Different types of stimuli can trigger dynamic reconfiguration of these metal-organic assemblies, to switch on or off desired functionalities. Such adaptable systems are of interest for applications in switchable catalysis, selective molecular recognition or as transformable materials. This review highlights recent advances in the transformation of cages using chemical stimuli, providing a catalogue of reported strategies to transform cages and thus allow the creation of new architectures. Firstly we focus on strategies for transformation through the introduction of new cage components, which trigger reconstitution of the initial set of components. Secondly we summarize conversions triggered by external stimuli such as guests, concentration, solvent or pH, highlighting the adaptation processes that coordination cages can undergo. Finally, systems capable of responding to multiple stimuli are described. Such systems constitute composite chemical networks with the potential for more complex behaviour. We aim to offer new perspectives on how to design transformation networks, in order to shed light on signal-driven transformation processes that lead to the preparation of new functional metal-organic architectures.

Coordination Cages Selectively Transport Molecular Cargoes Across Liquid Membranes.

Chemical purifications are critical processes across many industries, requiring 10-15% of humanity's global energy budget. Coordination cages are able to catch and release guest molecules based upon their size and shape, providing a new technological basis for achieving chemical separation. Here, we show that aqueous solutions of FeII4L6 and CoII4L4 cages can be used as liquid membranes. Selective transport of complex hydrocarbons across these membranes enabled the separation of target compounds from mixtures under ambient conditions. The kinetics of cage-mediated cargo transport are governed by guest binding affinity. Using sequential transport across two consecutive membranes, target compounds were isolated from a mixture in a size-selective fashion. The selectivities of both cages thus enabled a two-stage separation process to isolate a single compound from a mixture of physicochemically similar molecules.

Kinetics of Toehold-Mediated DNA Strand Displacement Depend on FeII4L4 Tetrahedron Concentration.

The toehold-mediated strand displacement reaction (SDR) is a powerful enzyme-free tool for molecular manipulation, DNA computing, signal amplification, etc. However, precise modulation of SDR kinetics without changing the original design remains a significant challenge. We introduce a new means of modulating SDR kinetics using an external stimulus: a water-soluble FeII4L4 tetrahedral cage. Our results show that the presence of a flexible phosphate group and a minimum toehold segment length are essential for FeII4L4 binding to DNA. SDRs mediated by toehold ends in different lengths (3-5) were investigated as a function of cage concentration. Their reaction rates all first increased and then decreased as cage concentration increased. We infer that cage binding on the toehold end slows SDR, whereas the stabilization of intermediates that contain two overhangs accelerates SDR. The tetrahedral cage thus serves as a versatile tool for modulation of SDR kinetics.

Heat Engine Drives Transport of an FeII 4 L4 Cage and Cargo.

The directed motion of species against a chemical potential gradient is a fundamental feature of living systems, underpinning processes that range from transport through cell membranes to neurotransmission. The development of artificial active cargo transport could enable new modes of chemical purification and pumping. Here, a heat engine is described that drives chemical cargo between liquid phases to generate a concentration gradient. The heat engine, composed of a functionalized FeII 4 L4 coordination cage, is grafted with oligoethylene glycol imidazolium chains. These chains undergo a conformational change upon heating, causing the cage and its cargo to reversibly transfer between aqueous and organic phases. Furthermore, sectional heating and cooling allow for the cage to traverse multiple phase boundaries, allowing for longer-distance transport than would be possible using a single pair of phases.