Single-Chain Folding of a Synthetic Macromolecule and Two Metal Atoms Provides a Precise Globular Tertiary Structure
Year: 2026
Type: preprint
Abstract: Macromolecular folding underlies function in biological systems, yet analogous compact, globular tertiary structures remain rare in synthetic chemistry. Although shape-persistent foldamers and metal-templated knots have been realized, crystallographically resolved globular architectures arising from intramolecular folding of single non-peptidic macromolecules are unknown. Here we introduce metal–organic knedels (MOKs): compact single-chain globules formed by intramolecular folding of single synthetic macromolecules around multiple metal centers. Specifically, a uniform 2.6 kDa oligomer bearing eight pyridyl donors and three naphthyl linkers undergoes diastereoselective assembly with two Pd(II) centers to afford a discrete complex, MOK-1, where covalent tethering enforces a unique low-symmetry fold and cavity shape not typically accessible in conventional high-symmetry assemblies, as confirmed by NMR spectroscopy, mass spectrometry and single-crystal X-ray diffraction. These findings define a new class of metal–organic architectures and establish intramolecular folding as a strategy for constructing globular synthetic systems.
Source: ChemRxiv
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7154276348
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