4.8 Article

Luminescence color switching of supramolecular assemblies of discrete molecular decanuclear gold(I) sulfido complexes

Publisher

NATL ACAD SCIENCES
DOI: 10.1073/pnas.1418824111

Keywords

luminescence; color switching; nanoaggregate; gold cluster

Funding

  1. University of Hong Kong
  2. University Research Committee (URC) Strategic Research Theme on New Materials
  3. University Grants Committee (UGC) Areas of Excellence Scheme [AoE/P-03/08]
  4. French National Research Agency (ANR)/Research Grants Council (RGC) [A-HKU704/12]
  5. General Research Fund (GRF) from the RGC of Hong Kong Special Administrative Region, People's Republic of China [HKU 7060/12P]

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A series of discrete decanuclear gold(I) mu(3)-sulfido complexes with alkyl chains of various lengths on the aminodiphosphine ligands, [Au-10{Ph2PN(CnH2n+1)PPh2}(4)(mu(3)-S)(4)](ClO4)(2), has been synthesized and characterized. These complexes have been shown to form supramolecular nanoaggregate assemblies upon solvent modulation. The photoluminescence (PL) colors of the nanoaggregates can be switched from green to yellow to red by varying the solvent systems from which they are formed. The PL color variation was investigated and correlated with the nanostructured morphological transformation from the spherical shape to the cube as observed by transmission electron microscopy and scanning electron microscopy. Such variations in PL colors have not been observed in their analogous complexes with short alkyl chains, suggesting that the long alkyl chains would play a key role in governing the supramolecular nanoaggregate assembly and the emission properties of the decanuclear gold(I) sulfido complexes. The long hydrophobic alkyl chains are believed to induce the formation of supramolecular nanoaggregate assemblies with different morphologies and packing densities under different solvent systems, leading to a change in the extent of Au(I)-Au(I) interactions, rigidity, and emission properties.

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