Shedding Light on Eu(III) β-Diketonate Compounds with 1,2-Bis(diphenylphosphino)ethane Oxide Ligand: an Optical Study

abstract

A series of novel lanthanide beta-diketonate coordination compounds containing the ancillary ligand bis(diphenylphosphino) oxide (dppeO(2)) have been synthesized, characterized, and studied spectroscopically. The compounds of formulas Ln(beta-dik)(3)(dppeO(2)), where Ln: Eu and Gd and beta-dik ligands as tta (Ln-1), btf (Ln-2), bzac (Ln-5) and tfac (Ln-4), and Ln(2)(beta-dik)(6)(dppeO(2)) with ligand dbm (Ln-3) and fod (Ln-6). Their photophysical properties were investigated from the Judd-Ofelt intensity parameters (Omega(lambda)), radiative (A(rad)) and non-radiative (A(nrad)) rates, intrinsic (Q(Eu)(Eu)) and overall (Q(Eu)(L)) quantum yields, and CIE (x,y) color coordinates. The Eu-5 and Eu-6 compounds have the first excited triplet states T-1 (around 18802 and 18976 cm(-1), respectively) almost resonant with the Eu3+ 5D0 emission level, whereas the complexes Eu-1, Eu-2, Eu-3, and Eu-4 exhibited higher T-1 energies. The A(rad) values were predominantly driven by the intensity parameter , suggesting more pronounced angular changes in the first coordination sphere of the Eu3+ ion. The A(nrad) values also exhibited significant changes with the beta-diketonate ligands. Eu-1 showed the highest value of Q(Eu)(L)(60 %), indicating a more efficient intramolecular energy transfer process. On the other hand, Eu-5 and Eu-6 compounds showed Q(Eu)(L )values equal to 18.7 % and 16.5 %, respectively, which indicates the presence of luminescence quencher channels.

keywords

INTRAMOLECULAR ENERGY-TRANSFER; CHARGE-TRANSFER; COMPLEXES; EUROPIUM; PHOTOLUMINESCENCE; TRANSITIONS; STATES

subject category

Chemistry

authors

Santos, PRS; Jesus, AASS; Lima, WB; Arruda, JG; Faustino, WM; Felinto, MCFC; Sabino, JR; Brito, HF; Costa, IF; Moura, RT; Neto, ANC; Malta, OL; Terraschke, H; Teotonio, EES

our authors

acknowledgements

This work was funded by the Universidade Federal da Paraiba (PRODUTIVIDADE UFPB 03/2020, PVA13345-2020). The authors also thank Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPQ: 313195/2018-8) and Coordenac & atilde;o de Aperfeicoamento de Pessoal de Nivel Superior (CAPES/DAAD: 88887.647236/2021-00 and 88887.371434/2019-00) and Fundac & atilde;o de Amparo a Pesquisa do Estado de S & atilde;o Paulo (FAPESP: 2021/08111-2). This work was developed within the scope of the project CICECO- Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020 and Shape of Water (PTDC/NAN-PRO/3881/2020) financed by Portuguese funds through the FCT/MEC (PIDDAC).

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