Issue 25, 2013

Engineering highly efficient Eu(iii)-based tri-ureasil hybrids toward luminescent solar concentrators

Abstract

Following a computational-experimental approach, a highly luminescent β-diketonate-europium(III) complex containing 2-thenoyltrifluoracetonate (tta) and 5,6-epoxy-5,6-dihydro-[1,10] phenanthroline (ephen) ligands, Eu(tta)3ephen (II), was theoretically studied by DFT/TD-DFT calculations, synthesized from Eu(tta)3(H2O)2(I) and fully characterized by high resolution mass spectrometry, TGA analysis, vibrational, UV-Vis and photoluminescence spectroscopy. For intramolecular energy transfer analysis purpose, Ln(NO3)3(ephen)2 [Ln = Eu (III), Gd (IV)] complexes were also synthesized and complexes I and III were theoretically studied. The organic–inorganic tri-ureasil matrix was used as a support for the immobilization of complex II and two hybrid samples were synthesized as a monolith (MtU5Eu-II) and as a thin film (FtU5Eu-II), characterized and its photoluminescence properties were compared with those of complex II. The photophysical properties of complex II benefit from the synergy between the excited-states of both ligands that create efficient energy transfer pathways to optimize the Eu3+ sensitization contributing to the large emission quantum yield (82 ± 8%), which is one of the highest so far reported for solid lanthanide β-diketonate complexes. Moreover, although the incorporation of complex II into the hybrid matrix is disadvantageous from the quantum yield point of view, MtU5Eu-II and FtU5Eu-II exhibit the highest emission quantum yields reported so far for Eu3+-containing hybrids (63 ± 6% and 48 ± 5%, respectively). Additionally, a significant improvement in the photostability under UV irradiation of the incorporated complex II is observed. The possibility of FtU5Eu-II to be used as a luminescent solar concentrator was evaluated and an optical conversion efficiency of ∼9% as well as an ability to boost up the Si-photovoltaic cell output to 0.5% were verified.

Graphical abstract: Engineering highly efficient Eu(iii)-based tri-ureasil hybrids toward luminescent solar concentrators

Supplementary files

Article information

Article type
Paper
Submitted
11 avr. 2013
Accepted
29 avr. 2013
First published
29 avr. 2013

J. Mater. Chem. A, 2013,1, 7339-7350

Engineering highly efficient Eu(III)-based tri-ureasil hybrids toward luminescent solar concentrators

M. M. Nolasco, P. M. Vaz, V. T. Freitas, P. P. Lima, Paulo. S. André, R. A. S. Ferreira, P. D. Vaz, P. Ribeiro-Claro and L. D. Carlos, J. Mater. Chem. A, 2013, 1, 7339 DOI: 10.1039/C3TA11463E

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