Open Access[Ag9(1,2-BDT)6]3–: How Square-Pyramidal Building Blocks Self-Assemble into the Smallest Silver Nanocluster
Author(s) -
Badriah Alamer,
Megalamane S. Bootharaju,
Sergey M. Kozlov,
Zhen Cao,
Aleksander Shkurenko,
Saidkhodzha Nematulloev,
Partha Maity,
Omar F. Mohammed,
Mohamed Eddaoudi,
Luigi Cavallo,
JeanMarie Basset,
Osman M. Bakr
Publication year - 2021
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.1c00334
Subject(s) - chemistry , nanoclusters , square pyramidal molecular geometry , crystallography , steric effects , metal , atom (system on chip) , square pyramid , electronic structure , nanotechnology , atomic orbital , single crystal , crystal structure , stereochemistry , computational chemistry , physics , materials science , organic chemistry , computer science , embedded system , quantum mechanics , electron
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: [Ag 9 (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 Ag 9 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.