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Recently, progress has been made in fabricating diamond-based scintillators with integrated rare-earth luminescent particles. These luminescent particles are integrated into the bulk of diamond during their synthesis by chemical vapor deposition (CVD). However, the growth conditions include a chemically aggressive plasma environment and elevated temperatures, which results in the partial degradation of particles and a decrease in the intensity of their luminescence. Here, we investigate the effect of thermal annealing of luminescent EuF3 and SrF2:Eu powders in microwave plasma that simulates the growth conditions of polycrystalline diamond. It was found that silicon substrates act as efficient reducing agents that lead to the partial reduction of trivalent europium to divalent europium. When annealing occurs on a diamond substrate, the reduction processes proceed at a significantly slower rate. The observed luminescence spectra showed both Eu2+ and Eu3+ luminescence bands, which allows for a targeted tuning of the luminescence spectrum of europium in composites and can be used to fabricate detectors and visualizers of X-ray radiation using a visible signal from the desired combination of Eu2±/Eu3± ions. During plasma annealing in pure hydrogen at moderate temperatures (600 °C), an intensive hydrogenation of particles is observed. Such hydrogen plasma treatment of fluorides may be considered a promising route to fabricate hydrides of various metals. [ABSTRACT FROM AUTHOR]

We report a synthesis of a series of molecular compounds and coordination polymers of Zn2+, Mn2+ Cd2+, Eu3+, and Tb3+ with 4-allyl-2,3,5,6-tetrafluorobenzoic acid (4-Afb) anions and 1,10-phenanthroline with compositions [Zn(H2O)(phen)(4-Afb)2] (1), [Mn(H2O)(phen)(4-Afb)2]n·nH2O (2), [Cd(H2O)(phen)(4-Afb)2]n (3), [Cd(phen)(4-Afb)2]n (4), [Ln2(phen)2(4-Afb)6] (Ln = Eu 5Eu; Tb 5Tb). It is shown that the obtained cadmium coordination polymers have various compositions and structures, depending on crystallization conditions. The prepared compounds are characterized by single-crystal XRD, powder XRD, IR spectroscopy, and CHN analysis. Noncovalent interactions are analyzed using the Hirshfeld surface analysis. It is determined that the crystal packings is mainly stabilized by π⋯π, C–H⋯F, and C–F⋯π interactions. The photoluminescent properties of the 5Eu and 5Tb complexes are studied. It is shown that the structure-forming effects of non-covalent "arene–perfluoroarene" interactions can be possibly used for preorganizing reactive functional groups in the crystal. [ABSTRACT FROM AUTHOR]

A study was carried out on the effect of a heavy chlorine atom introduced into the aromatic fragment of a 1,3-diketone ligand in Eu3+ coordination compounds on the spectral and luminescent properties of complex compounds. The data obtained from the absorption, optical excitation, fluorescence, and phosphorescence spectra as well as from the kinetics of the luminescence intensity permit estimation of the efficiency of energy transfer processes within the compounds studied. Introduction of a heavy chlorine atom was found to raise the energy of the first excited singlet state from 24,500 to 26,000 cm–1 but not affect the energy of the triplet level of the ligand. Furthermore, introduction of a chlorine atom leads to a decrease in the nonradiative relaxation constant (from 1290 to 840 s–1) and thereby triples the luminescence quantum yield from 23 to 64%. Hence, a new approach for the rational construction of useful coordination compounds of Eu3+ ions with 1,3-diketone ligands has been developed consisting of the substitution of a hydrogen atom by a heavy chlorine atom in the aromatic fragment of the ligand. [ABSTRACT FROM AUTHOR]

The reaction of 4,4,5,5,6,6,6-heptafluoro-1-(1-methyl-1H-pyrazol-4-yl)hexane-1,3-dione (HPyrC3F7) with freshly precipitated hydrated europium(ɪɪɪ) and samarium(ɪɪɪ) hydroxides in EtOH afforded crystalline complexes of the composition [Ln(PyrC3F7)3(EtOH)2], the features of their formation depending on the stoichiometric ligand/metal ratios were studied. The structure and composition of the complexes were characterized by physicochemical methods, including single-crystal X-ray diffraction. The luminescent properties of these compounds in the crystalline state and in solutions were studied in detail. Possible ways of transferring electronic excitation in the complex [Eu(PyrC3F7)3(EtOH)2] were considered. [ABSTRACT FROM AUTHOR]

Four new complexes [Ln(pfaa)3(H2O)2] n (Ln = Eu (1), Tb (2)) and [Ln2Cd2(pfaa)10 (phen)2(EtOH)2]·2MeCN (Ln = Eu (3), Tb (4), phen = 1,10-phenanthroline) based on pentaphorphenylacetic acid (Hpfaa) have been prepared and completely investigated. The structures of compounds 1 and 3 were studied by single crystal X-ray diffraction analysis: the isostructural complexes 1 and 2 represent 1D coordination polymer, while the isostructural complexes 3 and 4 are molecular compounds. Complexes 1–4 show strong lanthanide-centred luminescence, since the introduction of phenanthroline leads to a significant increase in the observed lifetime (τ obs) and photoluminescent quantum yield. New complexes of Eu3+ and Tb3+ with pentafluorophenylacetic acid have been studied. During synthesis under hydrothermal conditions, polymer structures are formed, while the introduction of phenanthroline and Cd2+ makes it possible to obtain molecular complexes. A change in the structure leads to significant changes in the luminescent properties. [ABSTRACT FROM AUTHOR]

The reaction of Cd(NO3)2 · 4H2O and Eu(NO3)3 · 6H2O or Tb(NO3)3 · 6H2O with potassium 3,5-di-tert-butylbenzoate (Kbzo) and N-donor ligands (1,10-phenanthroline (phen), 2,4-lutidine (2,4-lut), 3,4-lutidine (3,4-lut), phenanthridine (phtd), 2,3-cyclododecenopyridine (cdpy), acridine (acr)) afforded heterometallic LnCd2 complexes: [EuCd2(bzo)7(EtOH)2(phen)] (2), [LnCd2(bzo)7(2,4-lut)4] (Ln = Eu (3), Tb (4)), [EuCd2(bzo)7(H2O)2(2,4-lut)2] · MeCN (5), [EuCd2(NO3)(bzo)6(EtOH)2(2,4-lut)2] (6), [EuCd2(bzo)7(H2O)(EtOH)(3,4-lut)2] · 5EtOH (7), 3[EuCd2(bzo)7(H2O)2(phtd)2] · 4phtd (8), [EuCd2(bzo)7(EtOH)3(cdpy)] (9), 2[EuCd2-(bzo)2(EtOH)4] · acr (10). The structures of complexes 2, 3, and 5–10 were determined by single-crystal X-ray diffraction. The isostructurality of complexes 3 and 4 was confirmed by powder X-ray diffraction. The structure of the trinuclear {Ln2Cd} metal core is stable and independent of the type of peripheral ligands coordinated to cadmium atoms. Photoluminescent properties of compounds 3 and 4 were studied. [ABSTRACT FROM AUTHOR]

Features of nonlinear refraction formation in colloidal solutions containing Ag2S quantum dots passivated with thioglycolic acid (Ag2S/TGA QDs) with a concentration of 0.1% and an average size of 2.0 nm are considered. Nonthermal self-focusing caused by the "band filling" effect under exciton excitation was detected by the Z-scanning method for 10-ns pulses of a YAG:Nd laser at a wavelength of 532 nm for Ag2S/TGA QDs having an exciton absorption maximum at 590 nm. [ABSTRACT FROM AUTHOR]

Four new complexes [Ln(pfaa)3(H2O)2] n (Ln = Eu (1), Tb (2)) and [Ln2Cd2(pfaa)10 (phen)2(EtOH)2]·2MeCN (Ln = Eu (3), Tb (4), phen = 1,10-phenanthroline) based on pentaphorphenylacetic acid (Hpfaa) have been prepared and completely investigated. The structures of compounds 1 and 3 were studied by single crystal X-ray diffraction analysis: the isostructural complexes 1 and 2 represent 1D coordination polymer, while the isostructural complexes 3 and 4 are molecular compounds. Complexes 1–4 show strong lanthanide-centred luminescence, since the introduction of phenanthroline leads to a significant increase in the observed lifetime (τ obs) and photoluminescent quantum yield. New complexes of Eu3+ and Tb3+ with pentafluorophenylacetic acid have been studied. During synthesis under hydrothermal conditions, polymer structures are formed, while the introduction of phenanthroline and Cd2+ makes it possible to obtain molecular complexes. A change in the structure leads to significant changes in the luminescent properties. [ABSTRACT FROM AUTHOR]

In this study, two novel Pr 3+ complexes with different 1,3-diketonate ligands were synthesized and investigated. To study the effect of the ancillary ligand on the energy transfer mechanisms in the complexes, a phenanthroline ligand was introduced. To take into account the influence of the ligand environment composed of different ligands on the energy transfer and relaxation processes, we compared the synthesized compounds with a similar complex containing the phenanthroline ligand. The spectroscopic studies in the visible and near-infrared spectral regions were supplemented with DFT and TD-DFT calculations. We found two ligand-to-ligand charge transfer (LLCT) states, with one state corresponding to energy transfer between 1,3-diketones and the other - to energy transfer from the 1,3-diketone to the phenanthroline motif. It was demonstrated that optical excitation via the latter channel leads to a fourfold increase in the luminescence quantum yield as compared with excitation via the π-π ∗ transitions in 1,3-diketones. Moreover, both LLCT states provide sensitization of the Pr 3+ luminescence involving the 3 P 0 and 3 P 1 levels., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Two new Sm 3+ complexes with pyrazolic β-diketones bearing a CF 3 group acting as main ligands and with 2,2'-bipyridine or 1,10-phenanthroline being the ancillary ligand were studied, and their energy level structure was established. Stark splitting observed in the photoluminescence spectra of the complexes points to their non-cubic symmetry, confirmed by the calculated Judd-Ofelt intensity parameters. Internal quantum yields obtained for the compounds by the Judd-Ofelt calculations were of the order of 5.5%, whereas the measured external quantum yields were 0.75% and 1.5% for Sm 3+ complexes involving 2,2'-bipyridine and 1,10-phenanthroline ancillary ligands, respectively, with the corresponding sensitization efficiencies calculated as 0.16 and 0.26. It was demonstrated that replacing the 1,10-phenanthroline ancillary ligand with 2,2'-bipyridine provides an increase in the intensity of 650 nm emission of the Sm 3+ complexes, with the branching ratio reaching 55%. Intensive emission of the studied complexes at 650 nm offers hope for their use as spectrally pure red emitters., (Copyright © 2019 Elsevier B.V. All rights reserved.)

We performed spectroscopic investigations of a novel tris(1,3-bis(1,3-dimethyl-1H-pyrazol-4-yl)propane-1,3-dionato)(1,10-phenanthroline) holmium (III) complex. It was demonstrated that bonding the corresponding ligand environment to Ho 3+ results in sensitization of the luminescence of the complex. The luminescence decay of the complex exhibits a biexponential behaviour. The short-lived component is attributed to the fluorescence of the ligand, whereas the long-lived component is connected with the Ho 3+ emission. Using fluorescence lifetime imaging, it was shown that there is a single type of emission sites in the studied complex. Based on the results of the optical measurements, the energy diagram for the investigated Ho 3+ complex was developed. It was shown that the energy transfer from the excited triplet level of the ligand environment to the 5 F 5 level of Ho 3+ is responsible for the emission of the ion in the complex., (Copyright © 2019 Elsevier B.V. All rights reserved.)