Facile synthesis and optical properties of magic-number Au13 clusters

Nanoscale Pub Date: 2012-04-23 DOI: 10.1039/C2NR30675A

Abstract

Synthesis of molecular gold clusters through a post-synthetic scheme involving HCl-promoted nuclearity convergence was examined with various phosphine ligands. Systematic studies with a series of bis(diphenylphosphino) ligands (Ph2P-(CH2)m-PPh2) using electrospray ionization mass spectrometry (ESI-MS) and electronic absorption spectroscopy demonstrated that the use of dppp (m = 3), dppb (m = 4) and dpppe (m = 5) as the ligands resulted in the formation of [Au13P8Cl4]+ type clusters, whereas the [Au13P10Cl2]3+ type cluster was formed with dppe (m = 2). The cluster species did not survive the HCl treatment step when monophosphines PPh3, PMe2Ph, and POct3 were employed, but [Au13(POct3)8Cl4]+ was isolated as a minor product in the NaBH4 reduction of Au(POct3)Cl in aqueous THF. Electronic absorption and photoluminescence studies of a series of Au13 clusters revealed that their optical properties are highly dependent on the phosphine/chloride composition ratio, but are far less so on the phosphine structure.

Graphical abstract: Facile synthesis and optical properties of magic-number Au13 clusters
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