Supramolecular synthesis is a powerful strategy for assembling complex molecules, but to do this by targeted design is challenging. This is because multicomponent assembly reactions have the potential to form a wide variety of products. High-throughput screening can explore a broad synthetic space, but this is inefficient and inelegant when applied blindly. Here we fuse computation with robotic synthesis to create a hybrid discovery workflow for discovering new organic cage molecules, and by extension, other supramolecular systems. A total of 78 precursor combinations were investigated by computation and experiment, leading to 33 cages that were formed cleanly in one-pot syntheses. Comparison of calculations with experimental outcomes across this broad library shows that computation has the power to focus experiments, for example by identifying linkers that are less likely to be reliable for cage formation. Screening also led to the unplanned discovery of a new cage topology—doubly bridged, triply interlocked cage catenanes.

An in-depth study of porous liquids using measurement techniques, molecular simulations, and control experiments to advance their quantitative understanding.

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Computationally inspired and rationalised discovery of a completely unsymmetrical organic cage, which was both porous and highly soluble.

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.

Triplet–triplet annihilation upconversion (TTA-UC) is a process by which a lower energy photon can be upconverted to a higher energy state. The incorporation of TTA-UC materials into solid-state hosts has enabled advances in solar energy and many other applications. The choice of host system is, however, far from trivial and often calls for a careful compromise between characteristics such as high molecular mobility, low oxygen diffusion, and high material stability, factors that often contradict one another. Here, we evaluate these challenges in the context of the state-of-the-art of primarily polymer hosts and the advantages they hold in terms of material selection and tunability of their diffusion or mechanical or thermal properties. We encourage more collaborative research between polymer scientists and photophysicists in order to further optimize the current systems and outline our thoughts for the future direction of the field.

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.

Organic-inorganic hybrid polymers based on ureasils have found application as waveguides in luminescent solar concentrators and visible light communications. The mechanical properties, and thus processability of ureasils, has previously been qualitatively linked to the chemical structure, but has not yet been studied in detail. In this study, a series of low molecular weight ureasil polymers has been synthesised, and the correlation between the chemical structure and the optical and mechanical properties investigated. A wide-range of techniques are employed to investigate this relationship, including steady-state photoluminescence and Fourier-transform infrared spectroscopy, 4-point flexural testing, and uniaxial tensile testing.