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J Am Chem Soc. 2015 Sep 23;137(37):11970-5. doi: 10.1021/jacs.5b04547. Epub 2015 Jul 7.

Ag29(BDT)12(TPP)4: A Tetravalent Nanocluster.

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Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Saudi Arabia.
Department of Chemistry, University of California , Riverside, California 92508, United States.
Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center, Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.


The bottom-up assembly of nanoparticles into diverse ordered solids is a challenge because it requires nanoparticles, which are often quasi-spherical, to have interaction anisotropy akin to atoms and molecules. Typically, anisotropy has been introduced by changing the shape of the inorganic nanoparticle core. Here, we present the design, self-assembly, optical properties, and total structural determination of Ag29(BDT)12(TPP)4, an atomically precise tetravalent nanocluster (NC) (BDT, 1,3-benzenedithiol; TPP, triphenylphosphine). It features four unique tetrahedrally symmetrical binding surface sites facilitated by the supramolecular assembly of 12 BDT (wide footprint bidentate thiols) in the ligand shell. When each of these sites was selectively functionalized by a single phosphine ligand, particle stability, synthetic yield, and the propensity to self-assemble into macroscopic crystals increased. The solid crystallized NCs have a substantially narrowed optical band gap compared to that of the solution state, suggesting strong interparticle electronic coupling occurs in the solid state.


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