Synthesis of New LnxBi2–xSe3 (Ln: Sm3+, Eu3+, Gd3+, Tb3+) Nanomaterials and Investigation of Their Optical Properties

New Ln_xBi_2–xSe₃ (Ln: Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺) based nanomaterials were synthesized by a co‐reduction method. Powder XRD patterns indicate that the Ln_xBi_2–xSe₃ crystals (Ln = Sm³⁺, Eu³⁺, x = 0.00–0.44 and Ln = Gd³⁺, Tb³⁺, x = 0.00–0.50) are isostructural with Bi₂Se₃. The cell parameter c decreases for Ln = Eu³⁺, Gd³⁺, Tb³⁺ upon increasing the dopant content (x), while a slightly increases. Changes in lattice parameters could be related to the radii of cations. SEM images show that doping of the lanthanide ions in the lattice of Bi₂Se₃ generally results in nanoflowers. For the terbium compound two kinds of morphologies (nanoflowers and nanobelts) were observed. UV/Vis absorption and emission spectroscopy reveals mainly electronic transitions of the Ln³⁺ ions. Emission spectra show intense transitions from the excited to the ground state of Ln³⁺ and energy transfer from the Bi₂Se₃ lattice. Emission spectra of europium‐doped materials, in addition to the characteristic red emission peaks of Eu³⁺, show an intense blue emission band centered at 432 nm, originating from the 4f⁶5d¹ to 4f⁷ configuration in Eu²⁺. EPR measurements confirm the existence of Eu²⁺ in the materials. Interestingly, for all samples starting at low Ln³⁺ concentration, the emission intensity rises to a maximum at a Ln³⁺ concentration of x = 0.2 and falls again steadily to a minimum at x = 0.45.     

Potentiometric Study of Lanthanide Salicylaldimine Schiff Base Complexes

Formation of complexes between the lanthanide ions and N,N′-bis(salicylidene)-4-methyl-1,3-phenylenediamine ligand was studied in solution by pH potentiometry. The potentiometric titration was performed at 25.00 °C in 0.1 mol·dm^?3 NaClO₄ ionic strength and in DMSO:water (30:70 v:v) solvent mixture. N,N′-bis(salicylidene)-4-methyl-1,3-phenylenediamine ligand (H₂L) occurs in three forms: fully or partially deprotonated and unionized. Computer analysis of potentiometric data indicated that in solution the lanthanide (Ln) complexes exist as LnL₂, Ln(HL)₂ and Ln(H₂L)₂ species. This observation appears to be in contrast to the solid-state behavior of these complexes prepared in a self-assembly process and structurally defined. Stability constants for La³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Ho³⁺ and Lu³⁺ (Ln³⁺) complexes were determined. The order of stabilities of LnL₂ species in terms of metal ions is La³⁺ > Eu³⁺ ≈ Gd³⁺ = Tb³⁺ < Ho³⁺ < Lu³⁺ with a prominent “gadolinium break”.     

Potentiometric study of reactions of rare-earth elements with 3-allylpentanedione in a water-dioxane medium

Reactions of the ions of La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, and Lu with 3-allylpentanedione (HL) in a water-dioxane (50 vol%) medium were studied by pH-metric titration. Stability constants of LnL²⁺ and LnL ₂ ⁺ complexes and pH range where these compounds are mainly formed were determined. The dependence of the stability constants on the atomic number of an element has a characteristic break on the gadolinium ion and shows that the stability of the complexes increases as the size of Ln³⁺ ions decreases.     

Coordination and recognition of lanthanide cations by a methyl-substituted cucurbit[6]uril derived from 3α-methyl-glycoluril

The interactions between a series of lanthanide cations (Ln³⁺) and a methyl-substituted cucurbit[6]uril derived from 3α-methyl-glycoluril (SHMeQ[6]) in the presence of [CdCl₄]^2 ? as a structure-directing agent in aqueous HCl solutions (6.0 mol·L ^? 1) have been investigated. The formation of ionic radius-dependent complexes, the crystal structures of six of which have been obtained, shows the recognition ability of SHMeQ[6] towards lanthanide cations. For example, SHMeQ[6] forms molecular capsule-like complexes with the two lightest lanthanide cations, La³⁺ and Ce³⁺; molecular pairs with Nd³⁺, Sm³⁺, Eu³⁺ and Gd³⁺, and no solid crystals are formed with the heavier lanthanides.     

Luminescence in NaLn(SO4)2H2O: A host lattice with high-energy vibrations

The luminescence of Ce³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, and Dy³⁺ in NaLn(SO₄)₂H₂O (Ln = lanthanide) is reported. Only Ce³⁺, Gd³⁺, and Tb³⁺ show efficient emission. This is explained in terms of an energy-gap law. Energy transfer is studied in several codoped compositions. The mutual transfer between Gd³⁺ ions is the only one encountered with high probability. The several transfers are discussed and where possible their rates are calculated.     

Complex formation of certain rare earth metals with 1-(2-pyridylazo)-2-naphthol (PAN) in alcohol-water solutions

The formation ofPAN complexes in the systems:Ln(III)—PAN—alcohol—water [whereLn(III) = Pr, Nd, Sm, Eu, Gd, Tb, alcohol - ethanol andLn(III) = Eu, alcohol =n-propanol, isopropanol] was investigated by a spectrophotometric method. Equilibrium constants for the reactionLn ³⁺+HLLnL ²⁺+H⁺ (HL =PAN) and stability constants of complexesLnL ²⁺ are reported.

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Komplexbildung einiger Seltenerdmetalle mit 1-(2-Pyridylazo)-2-naphthol (PAN) in alkoholisch-wäßrigen Lösungen

Zusammenfassung Die Bildung der Komplexe vonPAN in den SystemenLn(III)—PAN—Alkohol—Wasser [Ln(III) = Pr, Nd, Sm, Eu, Gd, Tb, Alkohol = Ethanol undLn(III) = Eu, Alkohol =n-Propanol, Isopropanol] wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstanten der ReaktionenLn ³⁺+HLLnL ²⁺+H⁺ (HL =PAN) und die Stabilitätskonstanten der KomplexeLnL ²⁺ wurden berechnet.

     

Synthesis and characterization of monodisperse spherical SiO2@RE2O3 (RE=rare earth elements) and SiO2@Gd2O3:Ln (Ln=Eu, Tb, Dy, Sm, Er, Ho) particles with core-shell structure

Spherical SiO₂ particles have been coated with rare earth oxide layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO₂@RE₂O₃ (RE=rare earth elements) and SiO₂@Gd₂O₃:Ln³⁺ (Ln=Eu, Tb, Dy, Sm, Er, Ho) particles. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL), and cathodoluminescence spectra as well as lifetimes were used to characterize the resulting SiO₂@RE₂O₃ (RE=rare earth elements) and SiO₂@Gd₂O₃:Ln³⁺ (Eu³⁺, Tb³⁺, Dy³⁺, Sm³⁺, Er³⁺, Ho³⁺) samples. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 380 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (40 nm for two deposition cycles). Under the excitation of ultraviolet, the Ln³⁺ ion mainly shows its characteristic emissions in the core-shell particles from Gd₂O₃:Ln³⁺ (Eu³⁺, Tb³⁺, Sm³⁺, Dy³⁺, Er³⁺, Ho³⁺) shells.     

Sorption of microamounts of Ce3+, Pm3+, Eu3+, Gd3+ and Yb3+ on aluminium hydroxide

The sorption of microamounts of trivalent lanthanides (Ln³⁺) on freshly precipitated Al(OH)₃ has been measured in dependence on pH and the time of sorption. Also, the influence of organic complexing ligands and inorganic electrolytes on the sorption process has been investigated. The mechanism of sorption is discussed. Freshly precipitated Al(OH)₃ can be used for the preconcentration of microamounts of trivalent lanthanides. However, the preconcentration is not quantitative in the presence of high concentrations of complexing ligands (citrate and similar) which form strong complexes with Ln³⁺ ions.     

Synthesis, Crystal Structure, Magnetism, and Optical Properties of Gd3[SiON3]O—An Oxonitridosilicate Oxide with Noncondensed SiON3 Tetrahedra

The novel oxonitridosilicate oxide (sion oxide) Gd₃[SiON₃]O was obtained by the reaction of gadolinium metal with its carbonate oxide and silicon diimide in a radiofrequency (r.f.) furnace at a temperature of 1400°C. The crystal structure of Gd₃[SiON₃]O (I4/mcm, a=649.1(2) pm, c=1078.8(6) pm, Z=4, R₁=0.0411, wR₂=0.0769, 405 F² values, 19 parameters, 123 K) is isotypic with that of Ba₃[SiO₄]O and Cs₃[CoCl₄]Cl. It can be derived from the perovskite structure type by a hierarchical substitution: Ti⁴⁺→O^2-, O^2-→Gd³⁺, Ca²⁺→[SiON₃]^7- resulting in the formation of large [OGd₆]¹⁶⁺ octahedra, which are twisted by ξ=16.47(1)° around [001]. The low-temperature single-crystal data investigation led to a crystallographic splitting of the central O atom which could not be resolved at room temperature. The UV-Vis absorption spectra in reflection geometry of the yellow title compound revealed two overlaying broad bands, one peaking at almost the same wavelength as observed in gadolinium oxide (340 nm) and a second red-shifted band at approximately 400 nm indicating a strong influence of nitrogen on the ligand field splitting of the 5d states of Gd³⁺. Temperature-dependent magnetic susceptibility measurements of Gd₃[SiON₃]O show Curie-Weiss behavior from 2 to 300 K with an experimental magnetic moment of 7.68(5) μ_B/Gd, indicating trivalent gadolinium. There is no evidence for magnetic ordering down to 2 K. According to the paramagnetic Curie temperature of −7(1) K, the exchange between the gadolinium magnetic moments is supposed to be only weak. The vibrational spectroscopic data (IR and Raman) are reported.     

Luminescent-technique study on the structure of cation subsystem in the ionic conductor Na5RESi4O12 (RE is a rare-earth cation Tb3+, Ho3+, Er3+, Gd3+, Eu3+)

Results of experimental studies of luminescence in a group of materials with common formula Na₅RESi₄O₁₂ (RE is a rare-earth cation Tb³⁺, Ho³⁺, Er³⁺, Gd³⁺, Eu³⁺ entering the stoichiometric formula of the substance) are summarized. The luminescence spectra give information on the mobile-cation sublattice structure and dynamics. It follows from experimental results that the current opinion on the disordering of mobile sublattice is not quite correct. At relatively low temperatures (T < 100 K), a small number of typical local configurations of cations can be elucidated, which in aggregate can describe the Na⁺ cation sublattice to rather high degree of accuracy. At higher temperatures, the number of spectral lines and their positions change, which formally corresponds to changes in the symmetry of sites of the lattice, hence, is the sign of a second order phase transition. This phenomenon is given an explanation based on a suggestion on the local dynamic averaging of the mobile cation electrical fields.     

Attaining record-high magnetic exchange,magnetic anisotropy and blocking barriers in dilanthanofullerenes

While the blocking barrier (U_eff) and blocking temperature (T_B) for “Dysprocenium” SIMs have been increased beyond liquid N₂ temperature, device fabrication of these molecules remains a challenge as low-coordinate Ln³⁺ complexes are very unstable. Encapsulating the lanthanide ion inside a cage such as a fullerene (called endohedral metallofullerene or EMF) opens up a new avenue leading to several Ln@EMF SMMs. The ab initio CASSCF calculations play a pivotal role in identifying target metal ions and suitable cages in this area. Encouraged by our earlier prediction on Ln₂@C₇₉N, which was verified by experiments, here we have undertaken a search to enhance the exchange coupling in this class of molecules beyond the highest reported value. Using DFT and ab initio calculations, we have studied a series of Gd₂@C_2n (30 ≤ 2n ≤ 80), where an antiferromagnetic J_Gd⋯Gd of −43 cm⁻¹ was found for a stable Gd₂@C₃₈-D_3h cage. This extremely large and exceptionally rare 4f⋯4f interaction results from a direct overlap of 4f orbitals due to the confinement effect. In larger cages such as Gd₂@C₆₀ and Gd₂@C₈₀, the formation of two centre-one-electron (2c-1e⁻) Gd–Gd bonds is perceived. This results in a radical formation in the fullerene cage leading to its instability. To avoid this, we have studied heterofullerenes where one of the carbon atoms is replaced by a nitrogen atom. Specifically, we have studied Ln₂@C₅₉N and Ln₂@C₇₉N, where strong delocalisation of the electron yields a mixed valence-like behaviour. This suggests a double-exchange (B) is operational, and CASSCF calculations yield a B value of 434.8 cm⁻¹ and resultant J_Gd–rad of 869.5 cm⁻¹ for the Gd₂@C₅₉N complex. These parameters are found to be two times larger than the world-record J reported for Gd₂@C₇₉N. Further ab initio calculations reveal an unprecedented U_cal of 1183 and 1501 cm⁻¹ for Dy₂@C₅₉N and Tb₂@C₅₉N, respectively. Thus, this study offers strong exchange coupling as criteria for new generation SMMs as the existing idea of enhancing the blocking barrier via crystal field modulation has reached its saturation point.

Using ab initio calculations, we have made some robust predictions towards lanthanofullerene SMMs exhibiting remarkable characteristics.     

Complex formation studies on Ho(III) and Lu(III) with 1-(2-pyridylazo)-2-naphthol (PAN) in alcohol-water solutions

The formation ofPAN complexes in the systemsLn(III)—PAN—alcohol-water (where:Ln(III)=Ho, Lu and alcohol=ethanol,n-propanol,iso-propanol) was investigated by a spectrophotometric method. Equilibrium constants for the reactionLn ³⁺ + HLLnL ²⁺ + H⁺ (HL=PAN) and stability constants of complexesLnL ²⁺ were calculated.

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Untersuchungen zur Komplexbildung von Ho(III) und Lu(III) mit 1-(2-Pyridylazo)-2-naphthol (PAN) in alkoholisch-;wä\rigen Lösungen

Zusammenfassung Die Bildung der Komplexe vonPAN in den SystemenLn(III)—PAN—Alkohol-Wasser (Ln(III)=Ho, Lu; Alkohol=Ethanol,n-Propanol,iso-Propanol) wurde mit einer spektrophotometrischen Methode untersucht. Die Gleichgewichtskonstanten der ReaktionenLn ³⁺ + HLLnL ²⁺ + H⁺ (HL==PAN) und die Stabilitätskonstanten der KomplexeLnL ²⁺ wurden berechnet.

     

Complexation and Self-Assembling of Sulfonatomethylated Calix[4]resorcinarene with Both Organic and Lanthanide Ions in Aqueous Media

The stoichiometry and binding constant of the paramagnetic lanthanide ion(Gd³⁺) with sulfonatomethylated calix[4]resorcinarene (H₈Xna₄) were evaluated from the NMR relaxation data. Both ¹H NMR spectroscopy and NMR relaxation data indicate that interaction of tetramethylammonium (TEMA) and N-methylpyridinium (MePy) cations with H₈Xna₄ in the presence of Ln³⁺ (Lu³⁺ or Gd³⁺) results in theformation of ternary complexes [Ln(G)H₈X] with lanthanide ions,coordinated via sulfonate groups and organic cation included intothe cavity of H₈Xna₄. The inclusion of long-chainedN-decyl-(DePy) and N-cetylpyridinium (CPy) ions into H₈Xna₄ cavity leads to self-assembling which can be revealed by NMR relaxation method with Gd³⁺ probe ions. The excess of alkylpyridinium or TEMA cations leads to disassembling of (Gd)_n(H₈X)_m(RPy)_maggregates.     

A template-free solvothermal synthesis and photoluminescence properties of multicolor Gd2O2S:xTb3+, yEu3+ hollow spheres

The multicolor Gd₂O₂S:xTb³⁺, yEu³⁺ hollow spheres were successfully synthesized via a template-free solvothermal route without the use of surfactant from commercially available Ln (NO₃)₃·6H₂O (Ln = Gd, Tb and Eu), absolute ethanol, ethanediamine and sublimed sulfur as the starting materials. The phase, structure, particle morphology and photoluminescence (PL) properties of the as-obtained products were investigated by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM) and photoluminescence spectra. The influence of synthetic time on phase, structure and morphology was systematically investigated and discussed. The possible formation mechanism depending on synthetic time t for the Gd₂O₂S phase has been presented. These results demonstrate that the Gd₂O₂S hollow spheres could be obtained under optimal condition, namely solvothermal temperature T = 220 °C and synthetic time t = 16 h. The as-obtained Gd₂O₂S sample possesses hollow sphere structure, which has a typical size of about 2.5 μm in diameter and about 0.5 μm in shell thickness. PL spectroscopy reveals that the strongest emission peak for the Gd₂O₂S:xTb³⁺ and the Gd₂O₂S:yEu³⁺ samples is located at 545 nm and 628 nm, corresponding to ⁵D₄→⁷F₅ transitions of Tb³⁺ ions and ⁵D₀→⁷F₂ transitions of Eu³⁺ ions, respectively. The quenching concentration of Tb³⁺ ions and Eu³⁺ ions is 7%. In the case of Tb³⁺ and Eu³⁺ co-doped samples, when the concentration of Tb³⁺ or Eu³⁺ ions is 7%, the optimum concentration of Eu³⁺ or Tb³⁺ ions is determined to be 1%. Under 254 nm ultraviolet (UV) light excitation, the Gd₂O₂S:7%Tb³⁺, the Gd₂O₂S:7%Tb³⁺,1%Eu³⁺ and the Gd₂O₂S:7%Eu³⁺ samples give green, yellow and red light emissions, respectively. And the corresponding CIE coordinates vary from (0.3513, 0.5615), (0.4120, 0.4588) to (0.5868, 0.3023), which is also well consistent with their luminous photographs.     

Nitrate ion association with La3+, Gd3+, and Dy3+

Using the solvent extraction method it was found that the stability constantsK ₁ ⁰ of the La, Gd, DyNO₃ ²⁺ complexes are 41, 39, 21, respectively. The change of stability constants ofLnNO₃ ²⁺ complexes in the lanthanide series was related to the change of the amount of inner sphere complexation.

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Zur Assoziation von Nitrationen mit La³⁺, Gd³⁺ und Dy³⁺

Zusammenfassung Mittels der Lösungsmittelextraktionsmethode wurden die Stabilitäts-konstantenK ₁ ⁰ von La, Gd und DyNO ₃ ²⁺ zu 41, 39 und 21 bestimmt. Der Unterschied der Stabilitätskonstanten derLnNO ₃ ²⁺ -Komplexe innerhalb der Lanthanidenserie wurde mit dem Wechsel der Inneren-Sphären-Komplexierung verknüpft.

     

Effects of Cations on HPTS Fluorescence and Quantification of Free Gadolinium Ions in Solution; Assessment of Intracellular Release of Gd3+ from Gd-Based MRI Contrast Agents

8-Hydroxypyrene-1,3,6-trisulfonate (HPTS) is a small, hydrophilic fluorescent molecule. Since the pKa of the hydroxyl group is close to neutrality and quickly responds to pH changes, it is widely used as a pH-reporter in cell biology for measurements of intracellular pH. HPTS fluorescence (both excitation and emission spectra) at variable pH was measured in pure water in the presence of NaCl solution or in the presence of different buffers (PBS or hepes in the presence or not of NaCl) and in a solution containing BSA. pKa values have been obtained from the sigmoidal curves. Herein, we investigated the effect of mono-, di-, and trivalent cations (Na⁺, Ca²⁺, La³⁺, Gd³⁺) on fluorescence changes and proposed its use for the quantification of trivalent cations (e.g., gadolinium ions) present in solution as acqua-ions. Starting from the linear regression, the LoD value of 6.32 µM for the Gd³⁺ detection was calculated. The effects on the emission were also analyzed in the presence of a combination of Gd³⁺ at two different concentrations and the previously indicated mono and di-valent ions. The study demonstrated the feasibility of a qualitative method to investigate the intracellular Gd³⁺ release upon the administration of Gd-based contrast agents in murine macrophages.     

Nd3+, Eu3+, and Gd3+ ions as local probes in the NaxSr3−2xLnx(PO4)2 and KCaLn(PO4)2 rare earth phosphates

Use of Nd³⁺, Eu³⁺, and Gd³⁺ as local structural probes allows the determination of the rare earth positions in the Na_xSr_3?2xLn_x(PO₄)₂ (Ln = La to Tb) and KCaLn(PO₄)₂ phases (Ln = rare earth). Moreover, a common feature of both series is a particularly high splitting of the excitation ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ and ${}^6\text{P}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ levels of the Gd³⁺ ions.     

Double titanium and rare-earth phosphates

Phosphates Ln_1/3Ti₂(PO₄)₃ (Ln = Y, La, Ce, Pr, Eu, Gd, Ho) were synthesized by the citrate solgel (Pechini) method. Solid-phase reactions were activated using dispersion, pressing, and sintering microadditives. Synthesized samples were characterized by X-ray diffraction (Rietveld method), IR spectroscopy, electron microscopy, and microprobe analysis. The specific features of their structure formation were studied. The studied phosphates were shown to crystallize in the NaZr₂(PO₄)₃ (NZP/NASICON) structural type with space group R3. The framework of their structure is built of columns of TiO₆ and РО₄ polyhedra, and one of the two types of extraframework positions inside columns of polyhedra was occupied by Ln³⁺ cations at 2/3. The dependences of the unit cell parameters of Ln_1/3Ti₂(PO₄)₃ on the Ln³⁺ radius was observed to have a gadolinium kink.     

Zwei Fluoridborate des Gadoliniums: Gd2F3[BO3] und Gd3F3[BO3]2

Two Fluoride Borates of Gadolinium: Gd₂F₃[BO₃] and Gd₃F₃[BO₃]₂ By flux‐supported solid‐state reaction of Gd₂O₃ and GdF₃ with B₂O₃ (flux: CsCl, molar ratio: 1 : 1 : 1 : 6, sealed tantalum capsule, 700 °C, 7 d) the new gadolinium fluoride borate Gd₂F₃[BO₃] (monoclinic, P2₁/c; a = 1637.2(1), b = 624.78(4), c = 838.04(6) pm, β = 93.341(8)°; V_m = 64.418(6) cm³/mol, Z = 8) was obtained as colourless, prismatic, face‐rich single crystals. The four crystallographically different Gd³⁺ cations (CN = 9) are all capped square‐antiprismatically surrounded by fluoride and oxide anions, in which the latter represent always components of isolated trigonal planar [BO₃]^3— anions. The six crystallographically independent F^— anions all reside in more or less planar coordination of three Gd³⁺ cations. Thus the constitution of Gd₂F₃[BO₃] can be described as a sequence of alternating layers each of the composition Gd[BO₃] and GdF₃ parallel (100), respectively. The crystal structures of Gd₂F₃[BO₃] and the shortly published Gd₃F₃[BO₃]₂ (monoclinic, C2/c; a = 1253.4(1), b = 623.7(1), c = 836.0(1) pm, β = 97.404(6)°; V_m = 97.571(9) cm³/mol, Z = 4) are compared with each other. Due to the structural analogies between these two gadolinium fluoride borates, a disorder model of the boron atoms frequently found for Gd₂F₃[BO₃] is able to be transferred to Gd₃F₃[BO₃]₂ as well.     

The Photophysical Properties of Quaternary Lanthanide (Eu3+, Tb3+, Sm3+, Dy3+) Functional Molecular Complexes

Summary. In this paper, according to the molecular fragment principle, a series of twelve quaternary luminescent lanthanide complex molecular systems were assembled. Both elemental analysis and infrared spectroscopy allowed to determine the complexes formula: Ln(Nic)₃(L)·H₂O, where Ln=Sm, Eu, Tb, Dy; HNic=pyridine-3-carboxylic acid; L=N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), pyrrolidone (pyro). The photophysical properties of these functional molecular systems were studied by recording both ultraviolet-visible absorption, phosphorescence, fluorescence excitation, and emission spectra. It was found that the conjugated pyridine-3-carboxylic acid acts as the main energy donor and luminescence sensitizer due to the suitable energy match and effective energy transfer to the luminescent Ln ³⁺ ions. Amide molecules (DMF, DMA, pyro) were only used as assistant structural ligands to enhance the luminescence. Especially the europium complexes show the strongest luminescence due to the optimum energy transfer between the HNic triplet state energy level and Eu³⁺.