From Concept to Crystals via Prediction: Multi‐Component Organic Cage Pots by Social Self‐Sorting

Abstract

We describe the a priori computational prediction and realization of multi‐component cage pots, starting with molecular predictions based on candidate precursors through to crystal structure prediction and synthesis using robotic screening. The molecules were formed by the social self‐sorting of a tri‐topic aldehyde with both a tri‐topic amine and di‐topic amine, without using orthogonal reactivity or precursors of the same topicity. Crystal structure prediction suggested a rich polymorphic landscape, where there was an overall preference for chiral recognition to form heterochiral rather than homochiral packings, with heterochiral pairs being more likely to pack window‐to‐window to form two‐component capsules. These crystal packing preferences were then observed in experimental crystal structures.

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

“…We previously used density functional theory (DFT) formation energies to explain the thermodynamically preferred cage topologies in the dynamic imine-based selfassembly processes. [41,[57][58][59] Comparing the thermodynamic stabilities of potential cage products can be ag ood guide to selectivity,b ut the reaction outcome can also be affected by factors,s uch as reaction kinetics, [39,[60][61][62][63][64] solvent effects, [65][66][67][68] and the solubilities of the species involved in the equilibrium. [33,40,47] In parallel with the synthetic efforts,w eu sed computational techniques to predict the stability of the different homo-and heteroleptic structures originating from aldehydes B1-B2 and L1-L4.T he experimentally observed outcomes agreed with the relative gas-phase formation energies of the possible Tet 3 Di 6 products,s howing the predictive power of the simple model for the self-sorting behaviour of imine-based organic cages.…”

High‐Throughput Approaches for the Discovery of Supramolecular Organic Cages

“…[44][45][46] We recently combined the whole workflow of structure prediction, from reaction outcome, molecular structure to crystal packing for the first time. [47] With a computational model of the molecular or solid-state structure, it is then possible to perform a variety of calculations to determine the properties of the material, such as poretopology, surface area, guest uptake and selectivity. [48] In the solid-state, these are standard simulations that have been widely applied in the field of porous framework simulations.…”

Philip‐Leverhulme‐Preise in Chemie 2019

“…Die Gewinner sind Silvia Vignolini (University of Cambridge), die kürzlich in einer Advanced‐Materials ‐Zuschrift über chiral‐nematische photonische Filme auf Cellulosebasis berichtete, sowie Kim Jelfs (Imperial College London) und Daniele Leonori (University of Manchester) die 2018 je einen Harrison‐Meldola‐Preis der Royal Society of Chemistry gewannen . Beide waren jüngst in der Angewandten Chemie vertreten: Jelfs berichtete in einem Forschungsartikel über organische Mehrkomponentenkäfige durch soziale Selbtsortierung, und Leonori beschrieb in einer Zuschrift nickelkatalysierte Reaktionen von Stickstoffradikalen mit Organometallspezies . Die beiden verbleibenden Preisträger sind neu in dieser Rubrik.…”