[Ag9(1,2-BDT)6]3–: How Square-Pyramidal Building Blocks Self-Assemble into the Smallest Silver Nanocluster
AuthorsAlamer, Badriah Jaber
Bootharaju, Megalamane S.
Kozlov, Sergey M.
Mohammed, Omar F.
KAUST DepartmentAdvanced Membranes and Porous Materials Research Center
Biological and Environmental Sciences and Engineering (BESE) Division
Chemical Science Program
Functional Materials Design, Discovery and Development (FMD3)
Functional Nanomaterials Lab (FuNL)
KAUST Catalysis Center (KCC)
KAUST Solar Center (KSC)
Material Science and Engineering Program
Physical Science and Engineering (PSE) Division
Ultrafast Laser Spectroscopy and Four-dimensional Electron Imaging Research Group
Embargo End Date2022-03-17
Permanent link to this recordhttp://hdl.handle.net/10754/668193
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AbstractThe emerging promise of few-atom metal catalysts has driven the need for developing metal nanoclusters (NCs) with ultrasmall core size. However, the preparation of metal NCs with single-digit metallic atoms and atomic precision is a major challenge for materials chemists, particularly for Ag, where the structure of such NCs remains unknown. In this study, we developed a shape-controlled synthesis strategy based on an isomeric dithiol ligand to yield the smallest crystallized Ag NC to date: [Ag<sub>9</sub>(1,2-BDT)<sub>6</sub>]<sup>3-</sup> (1,2-BDT = 1,2-benzenedithiolate). The NC's crystal structure reveals the self-assembly of two Ag square pyramids through preferential pyramidal vertex sharing of a single metallic Ag atom, while all other Ag atoms are incorporated in a motif with thiolate ligands, resulting in an elongated body-centered Ag<sub>9</sub> skeleton. Steric hindrance and arrangement of the dithiolated ligands on the surface favor the formation of an anisotropic shape. Time-dependent density functional theory based calculations reproduce the experimental optical absorption features and identify the molecular orbitals responsible for the electronic transitions. Our findings will open new avenues for the design of novel single-digit metal NCs with directional self-assembled building blocks.
CitationAlamer, B. J., Bootharaju, M. S., Kozlov, S. M., Cao, Z., Shkurenko, A., Nematulloev, S., … Bakr, O. M. (2021). [Ag9(1,2-BDT)6]3–: How Square-Pyramidal Building Blocks Self-Assemble into the Smallest Silver Nanocluster. Inorganic Chemistry. doi:10.1021/acs.inorgchem.1c00334
SponsorsThis work was supported by KAUST. Computational time was afforded by the resources of the Supercomputing Laboratory at KAUST in Thuwal, Saudi Arabia.
PublisherAmerican Chemical Society (ACS)
CollectionsArticles; Biological and Environmental Sciences and Engineering (BESE) Division; Advanced Membranes and Porous Materials Research Center; Physical Science and Engineering (PSE) Division; Functional Materials Design, Discovery and Development (FMD3); Functional Materials Design, Discovery and Development (FMD3); Chemical Science Program; Material Science and Engineering Program; KAUST Catalysis Center (KCC); KAUST Solar Center (KSC)
Except where otherwise noted, this item's license is described as This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00334.
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