Sky-Blue Luminescent Au-I-Ag-I Alkynyl-Phosphine Clusters

Igor O. Koshevoy*, Antti J. Karttunen, Ilya S. Kritchenkou, Dmitrii V. Krupenya, Stanislav I. Selivanov, Alexei S. Melnikov, Sergey P. Tunik, Matti Haukka, Tapani A. Pakkanen

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

Abstract

Treatment of the (AuC2R)(n) acetylides with phosphine ligand 1,4-bis(diphenylphosphino)butane (PbuP)) and Ag+ ions results in self-assembly of the heterobimetallic clusters of three structural types depending on the nature of the alkynyl group. The hexadecanuclear complex [Au12Ag4(C2R)(12)(PbuP)(6)](4+) (1) is formed for R = Ph, and the octanuclear species [Au6Ag2(C2R)(6)(PbuP)(3)](2+) adopting two structural arrangements in the solid state were found for the aliphatic alkynes (R = Bu-t (2), 2-propanolyl (3), 1-cyclo-hexanolyl (4), diphenylmethanolyl (5), 2-borneolyl (6)). The structures of the compounds 1-4 and 6 were determined by single crystal X-ray diffraction analysis. The NMR spectroscopic studies revealed complicated dynamic behavior of 1-3 in solution. In particular, complexes 2 and 3 undergo reversible transformation, which involves slow interconversion of two isomeric forms. The luminescence behavior of the titled clusters has been studied. All the compounds exhibit efficient sky-blue room-temperature phosphorescence both in solution and in the solid state with maximum quantum yield of 76%. The theoretical DFT calculations of the electronic structures demonstrated the difference in photophysical properties of the compounds depending on their structural topology.

Original languageEnglish
Pages (from-to)3663-3673
Number of pages11
JournalInorganic Chemistry
Volume52
Issue number7
DOIs
Publication statusPublished - 1 Apr 2013
MoE publication typeA1 Journal article-refereed

Keywords

  • DENSITY-FUNCTIONAL METHODS
  • GOLD(I)-SILVER(I) CLUSTER
  • AUROPHILIC INTERACTIONS
  • BASIS-SETS
  • COMPLEXES
  • GOLD(I)-COPPER(I)
  • GOLD
  • LIGANDS
  • CHEMISTRY
  • DESIGN

Cite this

Koshevoy, I. O., Karttunen, A. J., Kritchenkou, I. S., Krupenya, D. V., Selivanov, S. I., Melnikov, A. S., ... Pakkanen, T. A. (2013). Sky-Blue Luminescent Au-I-Ag-I Alkynyl-Phosphine Clusters. Inorganic Chemistry, 52(7), 3663-3673. https://doi.org/10.1021/ic302105a