TY - JOUR
T1 - [Ag9(1,2-BDT)6]3–: How Square-Pyramidal Building Blocks Self-Assemble into the Smallest Silver Nanocluster
AU - Alamer, Badriah Jaber
AU - Bootharaju, Megalamane S.
AU - Kozlov, Sergey M.
AU - Cao, Zhen
AU - Shkurenko, Aleksander
AU - Nematulloev, Saidkhodzha
AU - Maity, Partha
AU - Mohammed, Omar F.
AU - Eddaoudi, Mohamed
AU - Cavallo, Luigi
AU - Basset, Jean-Marie
AU - Bakr, Osman
N1 - 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.
PY - 2021/3/17
Y1 - 2021/3/17
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/668193
UR - https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00334
U2 - 10.1021/acs.inorgchem.1c00334
DO - 10.1021/acs.inorgchem.1c00334
M3 - Article
C2 - 33726492
SN - 0020-1669
JO - Inorganic Chemistry
JF - Inorganic Chemistry
ER -