β-NaYF₄ microcrystals co-doped with Yb³⁺, Er³⁺/Tm³⁺, and Gd³⁺ ions were synthesized via a hydrothermal method using rare-earth chlorides as the precursors. The SEM and XRD data show that the doped β-NaYF₄ form uniform hexagonal prisms with an approximate size of 600–800 nm. The partial substitution of Y by Gd results in size reduction of microcrystals. Upconversion luminescence spectra of microcrystals upon 980 nm excitation contain characteristic intra-configurational ff bands of Er³⁺/Tm³⁺ ions. An addition of Gd³⁺ ions leads to a significant enhancement of upconversion luminescence intensity with maxima at 5 mol % of dopant.

Two series of β-NaYF₄:Ln³⁺ nanoparticles (Ln = La–Nd, Sm–Lu) containing 20 at. % and 40 at. % of Ln³⁺ with well-defined morphology and size were synthesized via a facile citric-acid-assisted hydrothermal method using rare-earth chlorides as the precursors. The materials were composed from the particles that have a shape of uniform hexagonal prisms with an approximate size of 80–1100 nm. The mean diameter of NaYF₄:Ln³⁺ crystals non-monotonically depended on the lanthanide atomic number and the minimum size was observed for Gd³⁺-doped materials. At the same time, the unit cell parameters decreased from La to Lu according to XRD data analysis. The diameter-to-length ratio increased from La to Lu in both studied series. The effect of the doping lanthanide(III) ion nature on particle size and shape was explained in terms of crystal growth dynamics. This study reports the correlation between the nanoparticle morphologies and the type and content of doping lanthanide ions. The obtained results shed light on the understanding of intrinsic factors’ effect on structural features of the nanocrystalline materials.

A new series of luminescent heterometallic europium(III)–lutetium(III) terephthalate metal–organic frameworks, namely (Eu_xLu_1−x)₂bdc₃·nH₂O, was synthesized using a direct reaction in a water solution. At the Eu³⁺ concentration of 1–40 at %, the MOFs were formed as a binary mixture of the (Eu_xLu_1−x)₂bdc₃ and (Eu_xLu_1−x)₂bdc₃·4H₂O crystalline phases, where the Ln₂bdc₃·4H₂O crystalline phase was enriched by europium(III) ions. At an Eu³⁺ concentration of more than 40 at %, only one crystalline phase was formed: (Eu_xLu_1−x)₂bdc₃·4H₂O. All MOFs containing Eu³⁺ exhibited sensitization of bright Eu³⁺-centered luminescence upon the 280 nm excitation into a ¹ππ* excited state of the terephthalate ion. The fine structure of the emission spectra of Eu^{3+ 5}D₀-⁷F_J (J = 0–4) significantly depended on the Eu³⁺ concentration. The luminescence quantum yield of Eu³⁺ was significantly larger for Eu-Lu terephthalates containing a low concentration of Eu³⁺ due to the absence of Eu-Eu energy migration and the presence of the Ln₂bdc₃ crystalline phase with a significantly smaller nonradiative decay rate compared to the Ln₂bdc₃·4H₂O.

The luminescent coarse-, micro- and nanocrystalline europium(III) terephthalate tetrahydrate (Eu₂bdc₃·4H₂O) metal-organic frameworks were synthesized by the ultrasound-assisted wet-chemical method. Electron micrographs show that the europium(III) terephthalate microparticles are 7 μm long leaf-like plates. According to the dynamic light scattering technique, the average size of the Eu₂bdc₃·4H₂O nanoparticles is equal to about 8 ± 2 nm. Thereby, the reported Eu₂bdc₃·4H₂O nanoparticles are the smallest nanosized rare-earth-based MOF crystals, to the best of our knowledge. The synthesized materials demonstrate red emission due to the ⁵D₀–⁷F_J transitions of Eu³⁺ upon 250 nm excitation into ¹ππ* state of the terephthalate ion. Size reduction results in broadened emission bands, an increase in the non-radiative rate constants and a decrease in both the quantum efficiency of the ⁵D₀ level and Eu³⁺ and the luminescence quantum yields. Cu²⁺, Cr³⁺, and Fe³⁺ ions efficiently and selectively quench the luminescence of nanocrystalline europium(III) terephthalate, which makes it a prospective material for luminescent probes to monitor these ions in waste and drinking water.

Luminescent, heterometallic terbium(III)–lutetium(III) terephthalate metal-organic frameworks (MOFs) were synthesized via direct reaction between aqueous solutions of disodium terephthalate and nitrates of corresponding lanthanides by using two methods: synthesis from diluted and concentrated solutions. For (Tb_xLu_1−x)₂bdc₃·nH₂O MOFs (bdc = 1,4-benzenedicarboxylate) containing more than 30 at. % of Tb³⁺, only one crystalline phase was formed: Ln₂bdc₃·4H₂O. At lower Tb³⁺ concentrations, MOFs crystallized as the mixture of Ln₂bdc₃·4H₂O and Ln₂bdc₃·10H₂O (diluted solutions) or Ln₂bdc₃ (concentrated solutions). All synthesized samples that contained Tb³⁺ ions demonstrated bright green luminescence upon excitation into the ¹ππ* excited state of terephthalate ions. The photoluminescence quantum yields (PLQY) of the compounds corresponding to the Ln₂bdc₃ crystalline phase were significantly larger than for Ln₂bdc₃·4H₂O and Ln₂bdc₃·10H₂O phases due to absence of quenching from water molecules possessing high-energy O-H vibrational modes. One of the synthesized materials, namely, (Tb_0.1Lu_0.9)₂bdc₃·1.4H₂O, had one of the highest PLQY among Tb-based MOFs, 95%.