Aromatic Amide and Hydrazide Foldamer-Based Responsive Host–Guest Systems

• Published in: Accounts of chemical research Vol. 47; no. 7; pp. 1961 - 1970
• Main Authors: Zhang, Dan-Wei, Zhao, Xin, Li, Zhan-Ting
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15.07.2014
• Subjects: Amides; Backbone; Chirality; Crown ethers; Design engineering; Helical; Holes; Molecular structure
• DOI: 10.1021/ar5000242
• ISSN: 0001-4842

Conspectus In host–guest chemistry, a larger host molecule selectively and noncovalently binds to a smaller guest molecule or ion. Early studies of host–guest chemistry focused on the recognition of spherical metal or ammonium ions by macrocyclic hosts, such as cyclic crown ethers. In these systems, preorganization enables their binding sites to cooperatively contact and attract a guest. Although some open-chain crown ether analogues possess similar, but generally lower, binding affinities, the design of acyclic molecular recognition hosts has remained challenging. One of the most successful examples was rigid molecular tweezers, acyclic covalently bonded preorganized host molecules with open cavities that bind tightly as they stiffen. Depending on the length of the atomic backbones, hydrogen bonding-driven aromatic amide foldamers can form open or closed cavities. Through rational design of the backbones and the introduction of added functional groups, researchers can regulate the shape and size of the cavity. The directionality of hydrogen bonding and the inherent rigidity of aromatic amide units allow researchers to predict both the shape and size of the cavity of an aromatic amide foldamer. Therefore, researchers can then design guest molecules with structure that matches the cavity shape, size, and binding sites of the foldamer host. In addition, because hydrogen bonds are dynamic, researchers can design structures that can adapt to outside stimuli to produce responsive supramolecular architectures. In this Account, we discuss how aromatic amide and hydrazide foldamers induced by hydrogen bonding can produce responsive host–guest systems, based on research by our group and others. First we highlight the helical chirality induced as binding occurs in solution, which includes the induction of helicity by chiral guests in oligomeric and polymeric foldamers, the formation of diastereomeric complexes between chiral foldamer hosts and guests, and the induction of helical chirality by chiral guests into inherently flexible backbones. In addition, molecular or ion-pair guests can produce supramolecular helical chirality in the organogel state. Such structures exhibit remarkable time-dependence and a “Sergeants and Soldiers” effect that are not observed for other two-component organogels that have been reported. We further illustrate that the reversible folding behavior of an aromatic amide foldamer segment can modulate the switching behavior of donor–acceptor interaction-based [2]­rotaxanes. Finally we show that a folded oligomer can induce folding in one or two attached intrinsically flexible oligomers, an example of a solvent-responsive intramolecular host–guest system.