Water-Soluble and Highly Luminescent Europium(III) Complexes with Favorable Photostability and Sensitive pH Response Behavior

Inorg Chem. 2016 Oct 17;55(20):10645-10653. doi: 10.1021/acs.inorgchem.6b01897. Epub 2016 Sep 26.

Abstract

Two highly luminescent and water-soluble Eu(III) complexes, Eu1 and Eu2, based on novel carboxyl-functionalized 1,5-naphthyridine derivatives 8-hydroxy-1,5-naphthyridine-2-carboxylic acid (H2L1) and 7-cyano-8-hydroxy-1,5-naphthyridine-2-carboxylic acid (H2L2), respectively, are designed and synthesized. The crystal structure of Eu2 indicates that the central Eu(III) ion is nine-coordinated by three tridentate ligands (O^N^O). Both Eu1 and Eu2 show strong luminescence in aqueous solution with quantum yields (lifetimes) of 28% (1.1 ms) and 14% (0.76 ms), respectively. The chelates display unique UV-light stability in solution and remain highly emissive after 100 min of strong UV irradiation (∼300 W·m-2 at 345 nm). Moreover, they exhibit reversible luminescence intensity changes with varied pH values, and the response mechanism is investigated. "Turn-on" of the Eu(III) emission upon increasing pH is realized by ligand structure change from keto to enol anion form, resulting in red-shifted absorption band and suppressed quenching from solvents and N-H vibration upon deprotonating. The results show that these novel Eu(III) complexes are quite intriguing for potential application as bioimaging agents and pH probes.

MeSH terms

  • Coordination Complexes / chemical synthesis
  • Coordination Complexes / chemistry
  • Coordination Complexes / radiation effects*
  • Europium / chemistry
  • Europium / radiation effects*
  • Hydrogen-Ion Concentration
  • Ligands
  • Luminescence
  • Naphthyridines / chemical synthesis
  • Naphthyridines / chemistry
  • Naphthyridines / radiation effects*
  • Photobleaching
  • Solubility
  • Ultraviolet Rays
  • Water / chemistry

Substances

  • Coordination Complexes
  • Ligands
  • Naphthyridines
  • Water
  • Europium