Computationally-inspired discovery of an unsymmetrical porous organic cage

Berardo, Enrico; Greenaway, Rebecca L.; Turcani, Lukas; Alston, Ben M.; Bennison, Michael J.; Miklitz, Marcin; Clowes, Rob; Briggs, Michael E.; Cooper, Andrew I.; Jelfs, Kim E.

doi:10.1039/c8nr06868b

Cited by 49 publications

(53 citation statements)

References 48 publications

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“…[38][39][40][41] Ar ecent study showed that low-symmetry cages can be formed using al ower-symmetry aldehyde precursor,b ut the presence of multiple structural isomers precluded the unambiguous characterisation of the cage products. [42] We sought to avoid these problems by designing an alternative single-step route to low-symmetry imine-based cages.W eused mixtures of multiple aldehyde precursors with different geometries to investigate their self-sorting behaviour,s creening for combinations that led to the selective formation of low-symmetry cages.…”

Section: Introductionmentioning

confidence: 99%

Inducing Social Self‐Sorting in Organic Cages To Tune The Shape of The Internal Cavity

et al. 2020

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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.

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Section: Introductionmentioning

confidence: 99%

Inducing Social Self‐Sorting in Organic Cages To Tune The Shape of The Internal Cavity

et al. 2020

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“…This includes the use of flow reactors, [68] microwaves, [69] mechanochemistry including ball-milling [70] and twin-screw extrusion, [71] and automated robotic platforms. [16,39,47,72] The latter, in particular, is useful for high-throughput screening, with the former methods suitable for scale-up.…”

Section: Experimental Toolkitmentioning

confidence: 99%

“…Overall, this high-throughput experimental workflow has been successfully applied to the synthesis of two-component binary organic cages of differing topologies (Figure 3), [39,72] the formation of three-component statistical distributions of vertexdisordered cage mixtures, [73] and multi-component self-sorted structures. [47] Additionally, this workflow could have other techniques incorporated at each stage, and be developed to link with property screening, such as crystal packing, porosity, and solubility (Figure 2a, bottom box).…”

Section: Experimental Toolkitmentioning

confidence: 99%

“…This led to the discovery of the first example of a porous organic cage that lacked any symmetry elements (Figure 4b). [72] However, experimental characterisation alone could not identify the formed cage isomer. Therefore, we returned to computation to narrow down the 162 possible structural isomers of this cage to the most plausible candidate.…”

Section: A Priori Prediction and A Posteriori Rationalisationmentioning

confidence: 99%

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High‐Throughput Approaches for the Discovery of Supramolecular Organic Cages

Greenaway

Jelfs

2020

ChemPlusChem

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The assembly of complex molecules, such as organic cages, can be achieved through supramolecular and dynamic covalent strategies. Their use in a range of applications has been demonstrated, including gas uptake, molecular separations, and in catalysis. However, the targeted design and synthesis of new species for particular applications is challenging, particularly as the systems become more complex. High‐throughput computation‐only and experiment‐only approaches have been developed to streamline the discovery process, although are still not widely implemented. Additionally, combined hybrid workflows can dramatically accelerate the discovery process and lead to the serendipitous discovery and rationalisation of new supramolecular assemblies that would not have been designed based on intuition alone. This Minireview focuses on the advances in high‐throughput approaches that have been developed and applied in the discovery of supramolecular organic cages.

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“…Jelfs and co‐workers have shown that computational modeling could be very helpful from design to a synthesis of unusual cage structures through a self‐selection method . A planar C 2V symmetric trialdehyde can produce nine unique [4+6] isomeric cages upon reaction with cyclohexane diamine.…”

Section: Self‐sorting/self‐selection In Oicsmentioning

confidence: 99%

Organic Imine Cages: Molecular Marriage and Applications

Acharyya

Mukherjee

2019

Angewandte Chemie

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Imine condensation has been known to chemists for more than a century and is used extensively to synthesize large organic cages of defined shapes and sizes. Surprisingly, in the context of the synthetic methods for organic imine cages (OICs), a self‐sorting/self‐selection (molecular marriage) process has been overlooked over the years. Such processes are omnipresent in nature, from the creation of galaxies to the formation of the smallest building blocks of life (the cell). Such processes have the incredible ability to guide a system toward the formation of a specific product or products out of a collection of equally probable multiple possibilities. This Minireview sheds light on new opportunities in cage design offered by the self‐sorting/self‐selection protocol in OICs. Recent efforts to explore organic cages for various exciting new applications are discussed; for example, for detection of harmful small organic molecules, as templates for nucleation of metal nanoparticles (MNPs), and as proton‐conducting materials.

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Computationally-inspired discovery of an unsymmetrical porous organic cage

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

Cited by 49 publications

References 48 publications

Inducing Social Self‐Sorting in Organic Cages To Tune The Shape of The Internal Cavity

Inducing Social Self‐Sorting in Organic Cages To Tune The Shape of The Internal Cavity

High‐Throughput Approaches for the Discovery of Supramolecular Organic Cages

Organic Imine Cages: Molecular Marriage and Applications

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