Hydrogen-bond-mediated supramolecular polyhedra
Viral capsids exemplify icosahedral polyhedral architectures formed via spontaneous self-assembly of identical protein subunits through non-covalent interactions governed by symmetry-matching rules. Mimicking this biological strategy, hydrogen-bond-directed supramolecular polyhedra have emerged as a focal point in supramolecular chemistry, offering dynamic responsiveness, reversible assembly, and structural designability. However, these systems face persistent challenges in structural stability and geometric precision control, particularly under competitive solvent conditions and thermal stress. This review systematically categorizes hydrogen-bonded supramolecular polyhedra by structural type and building block characteristics, including calix[4]resorcinarene cavitands, resorcin[4]arenes, pyrogallol[4]arenes, and peptidic containers. Key experimental milestones are highlighted: encapsulation-induced stabilization of heterocapsules (Chem Eur J, 2013, 19: 3685–3692), guest rotation within self-assembled heterocapsules (Proc Natl Acad Sci USA, 2009, 106: 10444–10448), and mechanochemical encapsulation of fullerenes in peptidic containers via dynamic chiral self-sorting (Chem Eur J, 2016, 22: 3148–3152). These constructs demonstrate tunable capsule spaces through hydrogen-bonding linkers (J Org Chem, 2006, 71: 8800–8806) and hybrid hydrogen-bonded/metal-ligand coordination capsules with dual guest-exchange control (Chem – An Asian J, 2014, 9: 1076–1082). The review identifies critical scientific bottlenecks—including solvent-dependent disassembly, limited cavity size, and trade-offs between reversibility and mechanical robustness—and outlines future trends toward precision functionalization. Establishing a theoretical framework for controlled assembly, this work provides methodological guidance for advancing bioinspired hydrogen-bonded polyhedral structures in synthetic chemistry and materials science.