Luminescent Triphosphine Cyanide d10 Metal Complexes

Research output: Contribution to journalArticleScientificpeer-review

Researchers

  • Gomathy Chakkaradhari
  • Yi-Ting Chen
  • Antti Karttunen

  • Minh Thuy Dau
  • Janne Jänis
  • Sergey P. Tunik
  • Pi Tai Chou
  • Mei Lin Ho
  • Igor O. Koshevoy

Research units

  • University of Eastern Finland
  • National Taiwan University
  • St. Petersburg State University
  • Soochow University, Taipei

Abstract

Coinage metal cyanides efficiently react with a triphosphine. PPh2C6H4-PPh-C6H4PPh2 (P3). to give the complexes M(P3)CN, where M = Cu (1), Ag (2), and Au (3), which can further interact with coordinatively unsaturated metal centers [M(P3)]+ to give the homobimetallic [(P3)M-CN-M(P3)]+X- [M = Cu (4a with X- = CF3SO3 - and 4b with X- = BF4 -), Ag (5)] or heterometallic [(P3)Au-CN-Ag(P3)]+ (6) species. Extension of this approach also provided the trinuclear complex [(P3)Cu-NC-Au-CN-Cu(P3)]+ (7). Compounds 1-5 were characterized in the solid state by X-ray crystallography. The NMR spectroscopic studies revealed that all of the complexes except 6 retain their structures in solution. The title compounds are luminescent in the solid state, with quantum yields ranging from 8 to 87%. The observed photoemission originates mainly from the metal-to-ligand charge-transfer states according to time-dependent density functional theory computational studies. The crystalline bimetallic Cu complexes 4a/4b demonstrate extremely high sensitivity of the emission intensity to molecular O2 (KSV1 = 639 atm-1 and LOD = 0.010% for 3 times the signal-to-noise ratio).

Details

Original languageEnglish
Pages (from-to)2174-2184
Number of pages11
JournalInorganic Chemistry
Volume55
Issue number5
Publication statusPublished - 2016
MoE publication typeA1 Journal article-refereed

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