Chirality-assisted synthesis (CAS) is a general approach to control the shapes of large molecular strips. CAS is based on enantiomerically pure building blocks that are designed to strictly couple in a single geometric orientation. Fully shape-persistent structures can thus be created, even in the form of linear chains. With CAS, selective recognition between large host and guest molecules can reliably be designed de novo. To demonstrate this concept, three C-shaped strips that can embrace a pillar[5]arene macrocycle were synthesized. The pillar[5]arene bound to the strips was a better host for electron-deficient guests than the free macrocycle. Experimental and computational evidence is provided for these unique cooperative interactions to illustrate how CAS could open the door towards the precise positioning of functional groups for regulated supramolecular recognition and catalysis.

Chirality-assisted synthesis (CAS) is ag eneral approach to control the shapes of large molecular strips. CASisbased on enantiomerically pure building blocks that are designed to strictly couple in as ingle geometric orientation. Fully shape-persistent structures can thus be created, even in the form of linear chains.W ithC AS,s elective recognition between large host and guest molecules can reliably be designed de novo.T od emonstrate this concept, three C-shaped strips that can embrace ap illar[5]arene macrocycle were synthesized. The pillar [5]arene bound to the strips was ab etter host for electron-deficient guests than the free macrocycle.E xperimental and computational evidence is provided for these unique cooperative interactions to illustrate how CAS could open the door towards the precise positioning of functional groups for regulated supramolecular recognition and catalysis.

Chirality-assisted synthesis (CAS) embodies a powerful strategy for the creation of chiral molecules with well-defined shapes and large cavities. In this communication, we show that C-shaped molecular receptors created with this approach bind to stacks of amphipathic perylenediimide (PDI) dyes. Evidence from 1 H NMR titrations, DOSY-NMR studies, and all-atom molecular dynamics simulations indicates that -in the preferred supramolecular binding mode -such polyaromatic strips specifically recognize stacked PDI dimers in solution. These results represent a key step toward the controlled self-assembly of dye molecules inside chiral cavities of shape-persistent, polyaromatic strips.

Pillararene macrocycles are embraced by C‐shaped molecular strips in a manner analogous to the way a five‐sided bolt head fits into a pentagonal wrench. In their Communication on S. T. Schneebeli, J. Li et al. describe the synthesis of these large, shape‐persistent molecular tweezers as single enantiomers by using chirality‐assisted synthesis. In the presence of pillararenes and viologens, the molecular strips form ternary complexes that are stabilized by cooperative supramolecular interactions.

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