authors |
Nolasco, MM; Vaz, PM; Freitas, VT; Lima, PP; Andre, PS; Ferreira, RAS; Vaz, PD; Ribeiro-Claro, P; Carlos, LD |
nationality |
International |
journal |
JOURNAL OF MATERIALS CHEMISTRY A |
keywords |
INTRAMOLECULAR ENERGY-TRANSFER; ORGANIC-INORGANIC HYBRIDS; BETA-DIKETONATE COMPLEX; EMISSION QUANTUM YIELD; RARE-EARTH COMPLEX; SPECTROSCOPIC PROPERTIES; EUROPIUM COMPLEXES; AROMATIC LIGANDS; EU-III; SILICA |
abstract |
Following a computational-experimental approach, a highly luminescent beta-diketonate-europium(III) complex containing 2-thenoyltrifluoracetonate (tta(-)) and 5,6-epoxy-5,6-dihydro-[1,10] phenanthroline (ephen) ligands, Eu(tta)(3)ephen (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 beta-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 similar to 9% as well as an ability to boost up the Si-photovoltaic cell output to 0.5% were verified. |
publisher |
ROYAL SOC CHEMISTRY |
issn |
2050-7488 |
year published |
2013 |
volume |
1 |
issue |
25 |
beginning page |
7339 |
ending page |
7350 |
digital object identifier (doi) |
10.1039/c3ta11463e |
web of science category |
Chemistry, Physical; Energy & Fuels; Materials Science, Multidisciplinary |
subject category |
Chemistry; Energy & Fuels; Materials Science |
unique article identifier |
WOS:000319886500008
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ciceco authors
impact metrics
journal analysis (jcr 2019):
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journal impact factor |
11.301 |
5 year journal impact factor |
10.694 |
category normalized journal impact factor percentile |
91.814 |
dimensions (citation analysis):
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altmetrics (social interaction):
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