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New heterometallic antenna terephthalate MOFs, namely, (EuxM1−x)2bdc3·4H2O (M = Y, La, Gd) (x = 0.001–1), were synthesized by a one-step method from aqueous solutions. The resulting compounds are isomorphic to each other; the crystalline phase corresponds to Ln2bdc3∙4H2O. Upon 300 nm excitation to the singlet excited state of terephthalate ions, all compounds exhibit a bright red emission corresponding to the of 5D0–7FJ (J = 0–4) f-f transitions of Eu3+ ions. The Eu(III) concentration dependence of the photophysical properties was carefully studied. We revealed that Gd-doping results in photoluminescence enhancement due to the heavy atom effect. To quantitatively compare the antenna effect among different compounds, we proposed the new approach, where the quantum yield of the 5D0 formation is used to characterize the efficiency of energy transfer from the ligand antenna to the Eu3+ emitter.

The bright luminescence of silver clusters in glass have potential applications in solid-state lighting, optical memory, and spectral converters. In this work, luminescent silver clusters were formed in the bulk of photo-thermo-refractive glass (15Na2O-5ZnO-2.9Al2O3-70.3SiO2-6.5F, mol.%) doped with different Ag2O concentrations from 0.01 to 0.05 mol.%. The spontaneous formation of plasmonic nanoparticles during glass synthesis was observed at 0.05 mol.% of Ag2O in the glass composition, limiting the silver concentration range for cluster formation. The luminescence of silver clusters was characterized by steady-state and time-resolved spectroscopy techniques. The rate constants of fluorescence, phosphorescence, intersystem crossing, and nonradiative deactivation were estimated on the basis of an experimental study. A comparison of the results obtained for the photophysical properties of luminescent silver clusters formed in the ion-exchanged layers of photo-thermo-refractive glass is provided.

In this work, three series of micro-sized heterometallic europium-containing terephthalate MOFs, (Eu1-xLnx)2bdc3·nH2O (Ln = La, Gd, Lu), are synthesized via an ultrasound-assisted method in an aqueous medium. La3+ and Gd3+-doped terephthalates are isostructural to Eu2bdc3·4H2O. Lu3+-doped compounds are isostructural to Eu2bdc3·4H2O with Lu contents lower than 95 at.%. The compounds that are isostructural to Lu2bdc3·2.5H2O are formed at higher Lu3+ concentrations for the (Eu1-xLux)2bdc3·nH2O series. All materials consist of micrometer-sized particles. The particle shape is determined by the crystalline phase. All the synthesized samples demonstrate an “antenna” effect: a bright-red emission corresponding to the 5D0-7FJ transitions of Eu3+ ions is observed upon 310 nm excitation into the singlet electronic excited state of terephthalate ions. The fine structure of the emission spectra is determined by the crystalline phase due to the different local symmetries of the Eu3+ ions in the different kinds of crystalline structures. The photoluminescence quantum yield and 5D0 excited state lifetime of Eu3+ are equal to 11 ± 2% and 0.44 ± 0.01 ms, respectively, for the Ln2bdc3·4H2O structures. For the (Eu1-xLux)2bdc3·2.5H2O compounds, significant increases in the photoluminescence quantum yield and 5D0 excited state lifetime of Eu3+ are observed, reaching 23% and 1.62 ms, respectively.

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 (TbxLu1−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, (Tb0.1Lu0.9)2bdc3·1.4H2O, had one of the highest PLQY among Tb-based MOFs, 95%.

The series of luminescent NaYF4:Sm3+ nano- and microcrystalline materials co-doped by La3+, Gd3+, and Lu3+ ions were synthesized by hydrothermal method using rare earth chlorides as the precursors and citric acid as a stabilizing agent. The phase composition of synthesized compounds was studied by PXRD. All synthesized materials except ones with high La3+ content (where LaF3 is formed) have a β-NaYF4 crystalline phase. SEM images demonstrate that all particles have shape of hexagonal prisms. The type and content of doping REE significantly effect on the particle size. Upon 400 nm excitation, phosphors exhibit distinct emission peaks in visible part of the spectrum attributed to 4G5/2→6HJ transitions (J = 5/2–11/2) of Sm3+ ion. Increasing the samarium (III) content results in concentration quenching by dipole–dipole interactions, the optimum Sm3+concentration is found to be of 2%. Co-doping by non-luminescent La3+, Gd3+ and Lu3+ ions leads to an increase in emission intensity. This effect was explained from the Sm3+ local symmetry point of view.

In this paper, we present a new methodology for creating 3D ordered porous nanocomposites based on anodic aluminum oxide template with polyaniline (PANI) and silver NPs. The approach includes in situ synthesis of polyaniline on templates of anodic aluminum oxide nanomembranes and laser-induced deposition (LID) of Ag NPs directly on the pore walls. The proposed method allows for the formation of structures with a high aspect ratio of the pores, topological ordering and uniformity of properties throughout the sample, and a high specific surface area. For the developed structures, we demonstrated their effectiveness as non-enzymatic electrochemical sensors on glucose in a concentration range crucial for medical applications. The obtained systems possess high potential for miniaturization and were applied to glucose detection in real objects—laboratory rat blood plasma.

In this study, ZnTe crystal was applied to provide precise thermal sensing for cryogenic temperatures. Multiple techniques, namely Raman and photoluminescence spectroscopies, were used to broaden the operating temperature range and improve the reliability of the proposed thermometers. Raman-based temperature sensing could be applied in the range of 20–100 K, while luminescence-based thermometry could be utilized in a narrower range of 20–70 K. However, the latter strategy provides better relative thermal sensitivity and temperature resolution. The best thermal performances based on a single temperature-dependent parameter attain Sr = 3.82% K−1 and ΔT = 0.12 K at T = 50 K. The synergy between multiple linear regression and multiparametric thermal sensing demonstrated for Raman-based thermometry results in a ten-fold improvement of Sr and a two-fold enhancement of ΔT. All studies performed testify that the ZnTe crystal is a promising multimode contactless optical sensor for cryogenic thermometry.

Tertiary diethylpyridylphosphine was synthesized by the reaction of pyridylphosphine with bromoethane in a suberbasic medium. The reaction of phosphine with the copper(I) iodide led to the formation of a copper(I) coordination polymer, which, according to the X-ray diffraction data, has an intermediate structure with a copper-halide core between the octahedral and stairstep geometries of the Cu4I4 clusters. The obtained coordination polymer exhibits a green emission in the solid state, which is caused by the 3(M+X)LCT transitions. The heating up of the copper(I) coordination polymer to 138.5 °C results in its monomerization and the formation of a new solid-state phase. The new phase exhibits a red emission, with the emission band maximum at 725 nm. According to the experimental data and quantum chemical computations, it was concluded that depolymerization probably leads to a complex that is formed with the octahedral structure of the copper-halide core. The resulting solid-state phase can be backward-converted to the polymer phase via recrystallization from the acetone or DMF. Therefore, the obtained coordination polymer can be considered a sensor or detector for the overheating of processes that should be maintained at temperatures below 138 °C (e.g., engines, boiling liquids, solar heat systems, etc.).

We present an efficient and easily implemented approach for creating stable electrocatalytically active nanocomposites based on polyaniline (PANI) with metal NPs. The approach combines in situ synthesis of polyaniline followed by laser-induced deposition (LID) of Ag, Pt, and AgPt NPs. The observed peculiarity of LID of PANI is the role of the substrate during the formation of multi-metallic nanoparticles (MNP). This allows us to solve the problem of losing catalytically active particles from the electrode’s surface in electrochemical use. The synthesized PANI/Ag, PANI/Pt, and PANI/AgPt composites were studied with different techniques, such as SEM, EDX, Raman spectroscopy, and XPS. These suggested a mechanism for the formation of MNP on PANI. The MNP–PANI interaction was demonstrated, and the functionality of the nanocomposites was studied through the electrocatalysis of the hydrogen evolution reaction. The PANI/AgPt nanocomposites demonstrated both the best activity and the most stable metal component in this process. The suggested approach can be considered as universal, since it can be extended to the creation of electrocatalytically active nanocomposites with various mono- and multi-metallic NPs.

The dimeric gold(I) chloride and gold(I) iodide complexes ([L2Au]Cl2 and L2AuI2) on the scaffold of the cyclic bisphosphine, namely 1,5-diaza-3,7-diphosphacyclooctane containing α-phenylbenzyl (benzhydryl) substituents at the nitrogen atoms, were synthesized. The obtained complexes were isolated as white crystalline powders. The single crystal XRD of the obtained complexes revealed the strong aurophilic interactions between two gold(I) atoms with the Au…Au distance values of 2.9977(6) and 3.1680(5) Å. The comparison of the gold complexes, based on the N,N-diaryl- and N,N-dibenzhydryl substituted 1,5-diaza-3,7-diphosphacyclooctanes, allowed to reveal the strong impact of the initial heterocycle conformation on the realization of the aurophilic interactions, where the geometry of N,N-dibenzhydryl substituted 1,5-diaza-3,7-diphosphacyclooctane, is pre-organized for the intramolecular aurophilic interactions of the complexes. The obtained complexes exhibit a bluish-green phosphorescence (λem 505 (-Cl) and 530(-I)) in the solid state at room temperature, originated by the metal-halide centered transitions, which was confirmed by the TDDFT calculations. It was found that the aurophilic interactions are realized in the ground and in the triplet excited states of the complexes. The slighter change of the geometry of the N,N-dibenzhydryl substituted gold(I) iodide complexes, under the transition from the ground state to the excited state, in comparison with their N,N-diaryl substituted analogues, results in the reduced values of the Stokes shift of luminescence (ca. 150 nm vs. 175 nm).

Doping the semiconductor nanocrystals is one of the most effective ways to obtain unique materials suitable for high-performance next-generation optoelectronic devices. In this study, we demonstrate a novel nanomaterial for the near-infrared spectral region. To do this, we developed a partial cation exchange reaction on the HgTe nanoplatelets, substituting Hg cations with Pb cations. Under the optimized reaction conditions and Pb precursor ratio, a photoluminescence band shifts to ~1100 nm with a quantum yield of 22%. Based on steady-state and transient optical spectroscopies, we suggest a model of photoexcitation relaxation in the HgTe:Pb nanoplatelets. We also demonstrate that the thin films of doped nanoplatelets possess superior electric properties compared to their pristine counterparts. These findings show that Pb-doped HgTe nanoplatelets are new perspective material for application in both light-emitting and light-detection devices operating in the near-infrared spectral region.

A new series of luminescent heterometallic europium(III)–lutetium(III) terephthalate metal–organic frameworks, namely (EuxLu1−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 (EuxLu1−x)2bdc3 and (EuxLu1−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: (EuxLu1−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 Eu3+ 5D0-7FJ (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.

Anti-cancer treatment efficiency can be significantly enhanced by the synergistic effect of the combined phototherapy that nowadays is under intensive preclinical and clinical studies. To minimize collateral damage, the combined phototherapy should be accompanied by a real-time thermal sensing. However, it is still challenging to develop multifunctional agent which combines therapy and temperature control. In the present study, contactless fluorescent thermometry based on ratiometric and lifetime approaches was realized using water-soluble anionic meso-tetrasulfonatophenylporphyrinate (tetra sodium salt) TSPH2 and cationic meso-mono(4-pyridyl)-triphenylporphyrinato)phosphorus(V) bromide MPyPP(OH)2 porphyrins photosensitizers. Both sensing techniques provide simple linear calibration curves in the biological temperature range. Thermometric performance of the suggested porphyrins was evaluated in terms of relative sensitivity, temperature resolution and repeatability and was found to be in upper range among porphyrin-based thermometers reaching 1% K−1 and 0.1 °C. The relative sensitivity was enhanced from 2 to 7 times by using peak-to-valley ratio compared to usual peak-to-peak ratio. Porphyrins' cytotoxicity was studied in vitro both in dark and blue-light activated conditions. Exposure-dependent cell viability showed that porphyrins could be used as molecular thermometers for phototherapy to avoid heat-induced adverse effects or as promising photosensitizers depending on chosen laser power.

Optical materials doped with several lanthanides are unique in their properties and are widely used in various fields of science and technology. The study of these systems provides solutions for noncontact thermometry, bioimaging, sensing technology, and others. In this paper, we report on the demonstration of YVO4 nanoparticles doped with one, two, and three different rare earth ions (Tm3+, Er3+, and Nd3+). We discuss the morphology, structural properties, and luminescence behavior of particles. Luminescence decay kinetics reveal the energy transfer efficiency (up to 78%) for different ions under the selective excitation of individual ions. Thus, we found that the energy transition from Tm3+ is more favorable than from Er3+ while we did not observe any significant energy rearrangement in the samples under the excitation of Nd3+. The observed strong variation of REI lifetimes makes the suggested nanoparticles promising for luminescent labeling, anticounterfeiting, development of data storage systems, etc.

In this data article, we present the single-crystal XRD data of phenanthrene-9,10-dicarbonitriles. Detailed structure analysis and photophysical properties were discussed in our previous study, “Intermolecular interactions-photophysical properties relationships in phenanthrene-9,10-dicarbonitrile assemblies” (Afanasenko et al., 2020). The data include the intra- and intermolecular bond lengths and angles. Keywords: Aromatic stacking interactions, Non-covalent interactions, Phenanthrene-9,10-dicarbonitriles, Single-crystal X-ray diffraction

Multimetallic plasmonic systems usually have distinct advantages over monometallic nanoparticles due to the peculiarity of the electronic structure appearing in advanced functionality systems, which is of great importance in a variety of applications including catalysis and sensing. Despite several reported techniques, the controllable synthesis of multimetallic plasmonic nanoparticles in soft conditions is still a challenge. Here, mono-, bi- and tri-metallic nanoparticles were successfully obtained as a result of a single step laser-induced deposition approach from monometallic commercially available precursors. The process of nanoparticles formation is starting with photodecomposition of the metal precursor resulting in nucleation and the following growth of the metal phase. The deposited nanoparticles were studied comprehensively with various experimental techniques such as SEM, TEM, EDX, XPS, and UV-VIS absorption spectroscopy. The size of monometallic nanoparticles is strongly dependent on the type of metal: 140–200 nm for Au, 40–60 nm for Ag, 2–3 nm for Pt. Bi- and trimetallic nanoparticles were core-shell structures representing monometallic crystallites surrounded by an alloy of respective metals. The formation of an alloy phase took place between monometallic nanocrystallites of different metals in course of their growth and agglomeration stage.

This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane-co-dimethylsiloxane) (N3-PDMS) was synthesized for incorporation of azide function in polysiloxane chain. [Re(CO)3(MeCN)(5-(4-ethynylphenyl)-2,2′-bipyridine)]OTf (Re1) luminescent complex was used to prepare a luminescent copolymer with N3-PDMS (Re1-PDMS), while [Re(CO)3Cl(5,5′-diethynyl-2,2′-bipyridine)] (Re2) was used as a luminescent cross-linking agent of N3-PDMS to obtain luminescent silicone rubber (Re2-PDMS). The examination of photophysical properties of the hybrid polymer materials obtained show that emission profile of Re(I) moiety remains unchanged and metallocenter allows to control the creation of polysiloxane-based materials with specified properties.

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 5D0–7FJ 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.

Reaction of linear conjugated enynones, 1,5-diarylpent-2-en-4-yn-1-ones, with malononitrile in the presence of lithium diisopropylamide LDA, as a base, in THF at room temperature for 3–7 h resulted in the formation of the product of dimerization, multisubstituted polyfunctional cyclohexanes, 4-aryl-2,6-bis(arylethynyl)-3-(aryloxomethyl)-4-hydroxycyclohexane-1,1-dicarbonitriles, in yields up to 60%. Varying the reaction conditions by decreasing time and temperature and changing the ratio of starting compounds (enynone and malononitrile) allowed isolating some intermediate compounds, which confirmed a plausible reaction mechanism. The relative stability of possible stereoisomers of such cyclohexanes was estimated by quantum chemical calculations (DFT method). The obtained cyclohexanes were found to possess photoluminescent properties.

Surfaces functionalized with metal nanoparticles (NPs) are of great interest due to their wide potential applications in sensing, biomedicine, nanophotonics, etc. However, the precisely controllable decoration with plasmonic nanoparticles requires sophisticated techniques that are often multistep and complex. Here, we present a laser-induced deposition (LID) approach allowing for single-step surface decoration with NPs of controllable composition, morphology, and spatial distribution. The formation of Ag, Pt, and mixed Ag-Pt nanoparticles on a substrate surface was successfully demonstrated as a result of the LID process from commercially available precursors. The deposited nanoparticles were characterized with SEM, TEM, EDX, X-ray diffraction, and UV-VIS absorption spectroscopy, which confirmed the formation of crystalline nanoparticles of Pt (3–5 nm) and Ag (ca. 100 nm) with plasmonic properties. The advantageous features of the LID process allow us to demonstrate the spatially selective deposition of plasmonic NPs in a laser interference pattern, and thereby, the formation of periodic arrays of Ag NPs forming diffraction grating

Quasi-spherical nanoparticles of ZrO2 containing EuO1.5 from 2 to 15 mol.% were synthesized from the chlorides of the corresponding metals under hydrothermal conditions. The structural changes of Zr1–xEuxO2–0.5x (x = 0.02 ÷ 0.15) nanoparticles depending on the content of europium (III) ions were studied using the complementary methods (X-ray diffraction, electron microdiffraction, Raman and photoluminescence spectroscopy). It was shown that increasing the Eu3+ concentration in the Zr1–xEuxO2–0.5x nanoparticles leads to a transition from the equilibrium monoclinic zirconia phase to metastable tetragonal and cubic polymorphic modifications. In this case, the size of the nanoparticles decreases from 11.5 nm to 9 nm; the specific surface area grows from 80.2 to 111.3 m2/g, and the electrokinetic potential increases monotonously from −8.7 to 16.3 mV. The evolution of the phase composition of Zr1–xEuxO2-0.5x nanoparticles from monoclinic to tetragonal/cubic allomorphs with an increase in the molar fraction of stabilizer ions was correlated with changes in the sublevel structure of 5D0 → 7F2 and 5D0 → 7F4 optical transitions for Eu3+ in the luminescence spectra. Besides, for the nanoparticles obtained by hydrothermal synthesis from chlorides, the quantum efficiency does not exceed 3%. According to the M.T.T. assay, as a result of three-day human fibroblast cultivation in the aqueous dispersion of Zr1–xEuxO2–0.5x (x = 0.02 ÷ 0.15) nanoparticles, the proliferation activity of the cells is maintained, indicating that they do not have cytotoxic properties. Such nanoparticles can be used in organic–inorganic composites for medical applications in order to strengthen the polymer scaffolds and visualize changes in their structure within time.

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.