Synthesis of biomimetic multimetallic clusters is sought after for applications such as efficient storage of solar energy and utilization of greenhouse gases. However, synthetic efforts are hampered by a dearth of ligands that are developed for multimetallic clusters due to current limitations in rational design and organic synthesis. Peptoids, a synthetic sequence-defined oligomer, enable a biomimetic strategy to rapidly synthesize and optimize large, multifunctional ligands by structural design and combinatorial screening. Here we discover peptoid oligomers (≤7 residues) that fold into a single conformation to provide unprecedented tetra- and hexadentate chelation by carboxylates to a [CoO] cubane cluster. The structures of peptoid-bound cubanes were determined by 2D NMR spectroscopy, and their structures reveal key steric and side-chain-to-main chain interactions that work in concert to rigidify the peptoid ligand. This efficient ligand design strategy holds promise for creating new scaffolds for the abiotic synthesis and manipulation of multimetallic clusters.
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http://dx.doi.org/10.1039/c8sc04240c | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, University of California Berkeley, Berkeley, California 94720, United States.
In Nature, the four-electron reduction of O is catalyzed at preorganized multimetallic active sites. These complex active sites often feature low-coordinate, redox-active metal centers precisely positioned to facilitate rapid O activation processes that obviate the generation of toxic, partially reduced oxygen species. Very few biomimetic constructs simultaneously recapitulate the complexity and reactivity of these biological cofactors.
View Article and Find Full Text PDFJ Phys Chem A
October 2024
National Research Council Canada, Clean Energy Innovation (CEI) Research Centre, Mississauga, Ontario L5K 1B4, Canada.
Nat Commun
September 2024
School of Materials Science and Engineering, Tianjin University, Tianjin, China.
Nanoscale
August 2024
University of Minnesota - Twin Cities, Minneapolis, MN 55455, USA.
Copper chalcogenide nanoclusters (Cu-S/Se/Te NCs) are a broad and diverse class of atomically precise nanomaterials that have historically been studied for potential applications in luminescent devices and sensors, and for their beautiful, mineral-like crystal structures. By the "cluster-surface" analogy, Cu-S/Se NCs are prime candidates for the development of nanoscale multimetallic catalysts with atomic precision. However, the majority of studies conducted to date have focused exclusively on their solid-state structures and physical properties, leaving open questions as to their solution stability, dynamics, and reactivity.
View Article and Find Full Text PDFEur J Inorg Chem
January 2024
School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA.
A cluster-ligand is disclosed in the form of [Ru(CN)(CO)] ([]). Produced by simple reaction of [Ru(CO)] with cyanide, [] serves as a precursor to a series of μ-CN cages. When treated with [Ru(CO)], it readily forms the prism [Ru(μ-CN)(CO)].
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