Participation of electronic excited states in the positronium formation mechanism in the Gd(III) pentakis (picrate) complexes with imidazolium countercations

• Published in: Journal of luminescence Vol. 170; pp. 491 - 496
• Main Authors: Fulgêncio, F., Borges, A.S., Araújo, M.H., Brito, H.F., Oliveira, F.C., Ribeiro, T., Windmöller, D., Magalhães, W.F.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-02-2016
• Subjects: Excited states; Lanthanide complexes; Luminescence; Positronium formation; Positronium formation; Excited states; Lanthanide complexes; Luminescence
• ISSN: 0022-2313; 1872-7883
• DOI: 10.1016/j.jlumin.2015.05.032

In this work, positron annihilation lifetime (PALS) and optical spectroscopies measurements were performed on [Gd(pic)2(H2O)6](pic)·6H2O and on complexes of general formula C2[Gd(pic)5], where pic corresponds to picrate ligands and C to the countercations butyl-methyl, hexyl-methyl, butyl-ethyl and butyl-butyl imidazoles. Since all of these complexes have high energy ligand-to-metal charge transfer states (LMCTS) but form low amounts of Positronium (Ps), the LMCTS do not act here as a mechanism that suppress luminescence nor prevents Ps formation. This result suggests that, besides LMCTS, other effects should also contribute to prevent Ps formation. The results indicate that the electron withdrawing –NO2 groups in the picrate ligand are responsible by the effect that prevents Ps formation. Also, a rough correlation between the ligands' triplet states lifetimes and Ps formation was observed. The insertion of electron donor groups (the imidazolium countercations) increased the ligands' first triplet excited states (3π⁎) lifetimes and Ps formation, indicating that these two spectroscopic parameters are correlated. Also, it is demonstrated that there is no clear correlation between Ps formation probability and the excitation energy of the ligands' first triplet excited states. The results were discussed in terms of the recently proposed Ps formation mechanism, named cybotactic correlated system kinetic mechanism (CCSKM), showing that the Ps formation process involves molecular excited states and is kinetically controlled.
•PALS and optical spectroscopies measurements performed on Gd3+ complexes.•A correlation was obtained between the ligands' 3π⁎ lifetimes and Ps formation.•Electronegative groups increased the ligands' 3π⁎ lifetimes and Ps formation.•Results discussed in terms of a new Ps formation mechanism (ccskm).