Optical properties of trinuclear citrate complexes containing 4f and 5f block metals

Aoyagi, Noboru; Palladino, G.*; Nagasaki, Shinya*; Kimura, Takaumi

Bulletin of the Chemical Society of Japan, 91(6), p.882 - 890, 2018/06

https://doi.org/10.1246/bcsj.20170419

The speciation and coordination geometries of M(III)-citrate complexes in aqueous solutions, where M denotes Eu, Tb, Lu, or Cm, are studied using potentiometric titration, nuclear magnetic resonance spectroscopies. Their photophysical properties are also characterized by time-resolved fluorescence spectra. The formation constants of mononuclear, dinuclear, and trinuclear Lu-citrate species were determined by potentiometric titration in 3.00 M NaClO aqueous media. Terminal carboxylic conformation in trinuclear complexes comprised both the five- and six-membered rings at different exchanging rates. Hydration states evaluated for Eu ions are the chemical formula of [Eu(Cit) (H O) ] and [Eu(OH)(Cit)(HO)]. These complexes in aqueous solution have geometrical similarity to the crystal structures in the literature. Furthermore, the entity of the hetero-trinuclear complex induces the intramolecular energy transfer from Tb to Eu. The incorporation of Cm into these homo/hetero-trinuclear citrate complexes proved to be a successful trial to probe the formation of actinide polymer at a trace level.