No abstract

Metal‐coordinated frameworks derived from small peptidic ligands have received much attention thanks to peptides’ vast structural and functional diversity. Various peptides with partial conformational preferences have been used to build metal–peptide frameworks, however, the use of conformationally constrained β‐peptide foldamers has not been explored yet. Herein we report the first metal‐coordination‐mediated assembly of β‐peptide foldamers with 12‐helical folding propensity. The coordination of Ag+ to the terminal pyridyl moieties afforded a set of metal–peptide frameworks with unique entangled topologies. Interestingly, formation of the network structures was accompanied by notable conformational distortions of the foldamer ligands. As the first demonstration of new metal–peptide frameworks built from modular β‐peptide foldamers, we anticipate that this work will be an important benchmark for further structural evolution and mechanistic investigation.

Metal‐coordinated frameworks derived from small peptidic ligands have received much attention thanks to peptides’ vast structural and functional diversity. Various peptides with partial conformational preferences have been used to build metal–peptide frameworks, however, the use of conformationally constrained β‐peptide foldamers has not been explored yet. Herein we report the first metal‐coordination‐mediated assembly of β‐peptide foldamers with 12‐helical folding propensity. The coordination of Ag+ to the terminal pyridyl moieties afforded a set of metal–peptide frameworks with unique entangled topologies. Interestingly, formation of the network structures was accompanied by notable conformational distortions of the foldamer ligands. As the first demonstration of new metal–peptide frameworks built from modular β‐peptide foldamers, we anticipate that this work will be an important benchmark for further structural evolution and mechanistic investigation.

Coordination polymers from α-amino acids are promising organic-inorganic hybrid composites with chirality and biocompatibility. However, coordination polymers from unnatural amino acids are rarely studied. Here, we report the transition metal complexes from an unnatural β-amino acid, (1S,2S)-2-aminocyclopentanecarboxylic acid, affording two possible coordination modes from the conformationally rigid cyclopentane ring. X-ray crystallographic analysis revealed that Zn(II) formed a two-dimensional (2D) coordination polymer via N,O-bridging mode. In contrast, Cu(II) formed a discrete complex via N,Ochelating mode and then constructed a 2D supramolecular network stabilized by hydrogen bonding between water and the ligands.

Metal‐peptide networks (MPNs), which are assembled from short peptides and metal ions, are considered one of the most fascinating metal‐organic coordinated architectures because of their unique and complicated structures. Although MPNs have considerable potential for development into versatile materials, they have not been developed for practical applications because of several underlying limitations, such as designability, stability, and modifiability. In this review, we summarise several important milestones in the development of crystalline MPNs and thoroughly analyse their structural features, such as peptide sequence designs, coordination geometries, cross‐linking types, and network topologies. In addition, potential applications such as gas adsorption, guest encapsulation, and chiral recognition are introduced. We believe that this review is a useful survey that can provide insights into the development of new MPNs with more sophisticated structures and novel functions.