Luminescent zinc(II) complexes of fluorinated benzothiazol-2-yl substituted phenoxide and enolate ligands

Inorg Chem. 2013 Feb 4;52(3):1379-87. doi: 10.1021/ic302063u. Epub 2013 Jan 14.

Abstract

Zn(II) complexes of the following new, fluorine-containing, benzothiazole-derived ligands have been synthesized and characterized crystallographically: 2-(3,3,3-trifluoro-2-oxopropyl)benzothiazole (3), 4,5,6,7-tetrafluoro-2-(3,3,3-trifluoro-2-oxopropyl)benzothiazole (4), 4,5,6,7-tetrafluoro-2-(2-hydroxyphenyl)benzothiazole (12), 2-(3,4,5,6-tetrafluoro-2-hydroxyphenyl)-4,5,6,7-tetrafluorobenzothiazole (13), and 2-(3,4,5,6-tetrafluoro-2-hydroxyphenyl)benzothiazole (16); the Cu(II) complex of ligand 4 is also reported. These are analogs of the important photo- and electroluminescent material [Zn(BTZ)(2)](2), where H-BTZ = 2-(2-hydroxyphenyl)benzothiazole. DFT calculations indicate that HOMO and LUMO energy levels in these materials are substantially lowered by fluorination. The fluorinated ZnL(2) complexes are mononuclear (in contrast to the dinuclear, nonfluorinated material [Zn(BTZ)(2)](2)). They easily sublime and show broad visible photoluminescence. A common crystallographic feature is the existence of pairs of fluorinated ZnL(2) molecules related by inversion centers, with their π systems facing one another.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aldehydes / chemistry*
  • Benzothiazoles / chemistry*
  • Ligands
  • Luminescence*
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Oxides / chemistry*
  • Quantum Theory
  • Zinc / chemistry*

Substances

  • Aldehydes
  • Benzothiazoles
  • Ligands
  • Organometallic Compounds
  • Oxides
  • benzothiazole
  • Zinc