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

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

Research output: Contribution to journalArticlepeer-review

233 Scopus citations

Abstract

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-benzenedithiols; 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 bandgap compared to that of the solution state, suggesting strong inter-particle electronic coupling occurs in the solid state.
Original languageEnglish (US)
Pages (from-to)11970-11975
Number of pages6
JournalJournal of the American Chemical Society
Volume137
Issue number37
DOIs
StatePublished - Jul 7 2015

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