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Ag 29 (BDT) 12 (TPP) 4 : A Tetravalent Nanocluster

2015; American Chemical Society; Volume: 137; Issue: 37 Linguagem: Inglês

10.1021/jacs.5b04547

1943-2984

Lina G. AbdulHalim, Megalamane S. Bootharaju, Qing Tang, Silvano Del Gobbo, Rasha G. AbdulHalim, Mohamed Eddaoudi, De‐en Jiang, Osman M. Bakr,

Advanced Nanomaterials in Catalysis

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.