Europium(III) coordination chemistry: structure, spectra and hypersensitivity

abstract

The red or orange emission spectra of tripositive europium have led to thousands of publications and to phosphor applications. The orange emission mainly arises from the 5 D 0 -> 7 F 1 transition (A), whereas in other cases, the red emission is due to the 5 D 0 -> 7 F 2 transition (B), with a different mechanism. The intensity ratio B/A, which is commonly labelled R 2, has been termed the asymmetry ratio and has been used as a probe of europium site symmetry in a material. We demonstrate that R 2 is not an exclusive indicator of site symmetry, although it does vary if there is change in the structural symmetry of the coordination environment. We propose the new term 'hypersensitivity ratio' to replace 'asymmetry ratio'. The concepts of crystallographic and spectroscopic site symmetry are reviewed, together with the theoretical basis of the electronic spectra of Eu3+. 3+ . Structures of europium complexes with coordination numbers between 6 and 12 are illustrated and previous interpretations of hypersensitivity are discussed. A tabulation of spectroscopic and crystallographic data is given and analyzed for 262 europium compounds. Moreover, new calculations of the ratio R 2 are presented for selected examples from the table, and these possess good agreement with the experimental data. Other factors which can affect the value of R 2 are discussed.

keywords

CRYSTAL-FIELD ANALYSIS; F-F TRANSITIONS; LIGAND-POLARIZATION CONTRIBUTIONS; INTRAMOLECULAR ENERGY-TRANSFER; RARE-EARTH COMPLEXES; FRAMEWORKS MIL-N; LUMINESCENCE PROPERTIES; LANTHANIDE COMPLEXES; PHOTOPHYSICAL PROPERTIES; SPECTROSCOPIC PROPERTIES

subject category

Science Citation Index Expanded (SCI-EXPANDED)

authors

Thor, W; Neto, ANC; Moura, RT Jr; Wong, KL; Tanner, PA

our authors

acknowledgements

Portuguese funds through the FCT/MEC (PIDDAC) [UIDB/50011/2020, UIDP/50011/2020, LA/P/0006/2020, PTDC/NAN-PRO/3881/2020]; Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq); Hong Kong Research Grants Council [12300021]; NSFC/RGC Joint Research Scheme [PolyU209/21]

Share this project:

Related Publications

We use cookies for marketing activities and to offer you a better experience. By clicking “Accept Cookies” you agree with our cookie policy. Read about how we use cookies by clicking "Privacy and Cookie Policy".