[Ag9(1,2-BDT)6]3–: How Square-Pyramidal Building Blocks Self-Assemble into the Smallest Silver Nanocluster

Badriah Jaber Alamer, Megalamane S. Bootharaju, Sergey M. Kozlov, Zhen Cao, Aleksander Shkurenko, Saidkhodzha Nematulloev, Partha Maity, Omar F. Mohammed, Mohamed Eddaoudi, Luigi Cavallo, Jean-Marie Basset, Osman Bakr

Research output: Contribution to journalArticlepeer-review

16 Scopus citations


The 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: [Ag9(1,2-BDT)6]3- (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 Ag9 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.
Original languageEnglish (US)
JournalInorganic Chemistry
StatePublished - Mar 17 2021

Bibliographical note

KAUST Repository Item: Exported on 2021-03-23
Acknowledgements: This work was supported by KAUST. Computational time was afforded by the resources of the Supercomputing Laboratory at KAUST in Thuwal, Saudi Arabia.

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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