Tuning the Thermometric Features in 1D Luminescent EuIII and TbIII Coordination Polymers through Different Bridge Phosphine Oxide Ligands.

TbIII and EuIII systems have been investigated as ratiometric luminescent temperature probes in luminescent coordination polymers due to TbIII → EuIII energy transfer (ET). To help understand how ion-ion separation, chain conformation as well as excitation channel impact their thermometric properties, herein, [Eu(tfaa)3(µ-L)Tb(tfaa)3]n one-dimensional (1D) coordination polymers (tfaa- = trifluoroacetylacetonate, and L = [(diphenylphosphoryl)R](diphenyl)phosphine oxide, R = ethyl - dppeo - or butyl - dppbo) were synthesized. The short µ-dppeo bridge ligand leads to a more linear 1D polymeric chain, while the longer µ-dppbo bridge leads to tighter packed chains. As the temperature rises from 80 K, upon direct TbIII excitation at 488 nm, the TbIII emission intensity decreases, while the EuIII emission intensity increases after 160 and 200 K when L = dppeo or dppbo, respectively. The temperature-dependent emission intensities, due to TbIII → EuIII ET, enable the development of ratiometric luminescent temperature probes featuring maximum relative thermal sensitivity up to 3.8% K-1 (250 K, L = dppbo, excitation at 488 nm). On the other hand, the same system displays maximum thermal sensitivity up to 3.5% K-1 (323 K) upon ligand excitation at 300 nm. Thus, by changing the excitation channel and bridge ligand that leads to modification of the polymer conformations, the maximum relative thermal sensitivity can be tuned.

PMMA or PVDF films blended with ß-diketonate tetrakis EuIII or TbIII complexes used as downshifting coatings of near-UV LEDs.

Luminescent LnIII complexes incorporated in polymeric films exhibit narrow emission bands and absorption within the near-UV/blue spectral range, and enhanced phostability, which qualify them to be explored for solid-state lighting. Herein, (C26H56N)[Eu(dbm)4] and Na[Tb(acac)4], (C26H56N+ = didodecyldimethylammonium, dbm- =1,3-diphenyl-1,3-propanedionate, acac- = acetylacetonate), were dispersed in PMMA or PVDF films to protect them from degradation, and the obtained blends were applied as downshifting coatings on near-UV emitter LEDs. Upon such excitation, both EuIII and TbIII complexes emit red or green light with absolute emission quantum yields of 6.4 and 99%, respectively. The complex amount within films influences the photophysical parameters due to multiphotonic deactivation, and formation of agglomerates. For the PMMA-based LED prototypes, the LnIII emission is well-observed while for the PVDF ones, only a poor LnIII emission is detected due to their opacity. Therefore, the PMMA-based systems are better candidates to be used as luminescent coatings of near-UV LEDs for solid-state lighting.

Sensitization of lanthanide complexes through direct spin-forbidden singlet → triplet excitation.

LnIII complexes may display luminescence within the ultraviolet-visible-near-infrared spectral window and although they render bright emissions mainly due to the classical singlet-triplet-state-assisted ligand sensitization, which would be the photophysical parameters if they could be excited through direct spin-forbidden singlet → triplet transitions? Herein, we report the sensitization of Ln complexes through spin-forbidden S0 → T transitions in a series of homobimetallic EuIII, TbIII, ErIII, and YbIII complexes with halogen-substituted benzoate ligands. As halogens and LnIII atomic numbers increase, intense singlet → triplet absorption/excitation bands and relative quantum yields up to 18% were achieved due to an increased spin-orbit coupling effect. Moreover, the near-UV-shifted excitation may enable application in luminescent solar concentrators where YbIII near-infrared luminescence matches the maximum efficiency of the crystalline Si photovoltaic cell. Therefore, the spin-relaxed excitation channel provides new opportunities to improve the LnIII complex luminescence and potential within the energy conversion field.

Red-Emitting Hybrid Based on Eu3+-dbm Complex Anchored on Silica Nanoparticles Surface by Carboxylic Acid for Biomarker Application.

Luminescent organic-inorganic hybrids containing lanthanides (Ln3+) have been prominent for applications such as luminescent bio-probes in biological assays. In this sense, a luminescent hybrid based on dense silica (SiO2) nanospheres decorated with Eu3+ ß-diketonate complexes using dibenzoylmethane (Hdbm) as a luminescent antenna was developed by using a hierarchical organization in four steps: (i) anchoring of 3-aminopropyltriethoxysilane (APTES) organosilane on the SiO2 surface, (ii) formation of a carboxylic acid ligand, (iii) coordination of Eu3+ to the carboxylate groups and (iv) coordination of dbm- to Eu3+. The hybrid structure was elucidated through the correlation of thermogravimetry, silicon nuclear magnetic resonance and photoluminescence. Results indicate that the carboxylic acid-Eu3+-dbm hybrid was formed on the surface of the particles with no detectable changes on their size or shape after all the four steps (average size of 32 ± 7 nm). A surface charge of -27.8 mV was achieved for the hybrid, assuring a stable suspension in aqueous media. The Eu3+ complex provides intense red luminescence, characteristic of Eu3+5D0→7FJ electronic transitions, with an intrinsic emission quantum yield of 38%, even in an aqueous suspension. Therefore, the correlation of luminescence, structure, particle morphology and fluorescence microscopy images make the hybrid promising for application in bioimaging.

Eu3+ -tetrakis ß-diketonate complexes for solid-state lighting application.

Eu3+ -ß-diketonate complexes are used, for example, in solid-state lighting (SSL) or light-converting molecular devices. However, their low emission quantum efficiency due to water molecules coordinated to Eu3+ and low photostability are still problems to be addressed. To overcome such challenges, we synthesized Eu3+ tetrakis complexes based on [Q][Eu(tfaa)4 ] and [Q][Eu(dbm)4 ] (Q1 = C26 H56 N+ , Q2 = C19 H42 N+ , and Q3 = C17 H38 N+ ), replacing the water molecules in the tris stoichiometry. The tetrakis ß-diketonates showed desirable thermal stability for SSL and, under excitation at 390 nm, they displayed the characteristic Eu3+ emission in the red spectral region. The quantum efficiencies of the dbm complexes achieved values as high as 51%, while the tfaa complexes exhibited lower quantum efficiencies (28-33%), but which were superior to those reported for the tris complexes. The structures were evaluated using the Sparkle/PM7 model and comparing the theoretical and the experimental Judd-Ofelt parameters. [Q1][Eu(dbm)4 ] was used to coat a near-UV light-emitting diode (LED), producing a red-emitting LED prototype that featured the characteristic emission spectrum of [Q1][Eu(dbm)4 ]. The emission intensity of this prototype decreased only 7% after 30 h, confirming its high photostability, which is a notable result considering Eu3+ complexes, making it a potential candidate for SSL.