Search results for: 10]phenanthroline

Authors: Zahra Sadeghian

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This paper reports on the geometrical parameters optimized of the stationary point for the 2,3-Bis(furan-2-yl)pyrazino[2,3-f][1,10]phenanthroline. The calculations are performed using density functional theory (DFT) method at the B3LYP/LanL2DZ level. We determined bond lengths and bond angles values for the compound and calculate the amount of bond hybridization according to the natural bond orbital theory (NBO) too. The energy of frontier orbital (HOMO and LUMO) are computed. In addition, calculated data are accurately compared with the experimental result. This comparison show that the our theoretical data are in reasonable agreement with the experimental values.

Keywords: 2, 3-Bis(furan-2-yl)pyrazino[2, 3-f][1, 10]phenanthroline, density functional theory, theorical calculations, LanL2DZ level, B3LYP level

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Authors: S. N. Harun, H. Ahmad

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A series of ruthenium(II) complexes, including two novel compounds [Ru(dppz)2(L)]2+ where dppz = dipyrido-[3,2-a:2’,3’-c]phenazine, and L = 2-phenylimidazo[4,5-f][1,10]phenanthroline (PIP) or 2-(4-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline (p-HPIP) have been synthesized and characterized. The previously reported complexes [Ru(bpy)2L]2+ and [Ru(phen)2L]2+ were also prepared. All complexes were characterized by elemental analysis, 1H-NMR spectroscopy, ESI-Mass spectroscopy and FT-IR spectroscopy. The photophysical properties were analyzed by UV-Visible spectroscopy and fluorescence spectroscopy. [Ru(dppz)2(PIP)]2+ and [Ru(dppz)2(p-HPIP)]2+ displayed ‘molecular light-switch’ effect as they have high emission in acetonitrile but no emission in water. The cytotoxicity of all complexes against cancer cell lines Hela and MCF-7 were investigated through standard MTT assay. [Ru(dppz)2(PIP)]2+ showed moderate toxicity on both MCF-7 and Hela with IC50 of 37.64 µM and 28.02 µM, respectively. Interestingly, [Ru(dppz)2(p-HPIP)]2+ exhibited remarkable cytotoxicity results with IC50 of 13.52 µM on Hela and 11.63 µM on MCF-7 cell lines which are comparable to the infamous anti-cancer drug, cisplatin. The cytotoxicity of this complex series increased as the ligands size extended in order of [Ru(bpy)2(L)]2+ < [Ru(phen)2(L)]2+ < [Ru(dppz)2(L)]2+.

Keywords: ruthenium, cytotoxicity, molecular light-switch, anticancer

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Authors: Salem El Ashoor, Fathia M. El-Meheishi, Ibtisam M. Diab

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Zirconium diammin and triammin complexes can be possess biological activities, these complexes were synthesized via the reaction equimolar quantity of (1:10-phenanthroline){NC3H3(C6H2)NC3H3} (L1) or 4-4-amino phenazone {ONC6H5(NH)CH(NH2} (L2) or diphenyl carbizon {HNNCO(NH)2(C6H5)} (L3) with Zirconium Salt {ZrOCl2} in ratio (1:1) to form complexes [{NC3H3(C6H2)NC3H3}ZrOCl2}] [ZrOCl2L1], [{(O2NC6H4(NH)(NH2)}ZrOCl2] [ZrOCl2L2] and [{HNNCO(NH)2(C6H5)ZrOCl2}] [ZrOCl2L3] respectively. The characterization of these complexes were follow by using Fourier Transform Infrared (FT-IR) and UV-Visible spectroscopy. Also a variable temperature study of these complexes has been followed by using UV-Visible spectroscopy to follow electronic transform behaviors under temperature control also DFT study calculation was follow these complexes via the information from FT-IR and UV-Visible spectroscopy. A coordination number of these complexes of types five and six of the geometry can be suggested. These complexes were found to shown deferent inhibition to the growth of bacterial strains of Bacillus spp & Klebsiella spp & E.coli & proteus spp & pseudomona spp) while all complexes were in deferent's concentration (0.001, 0.2 and 1M) and the result as evidenced from the presence. For better understanding these complexes were examined by using Density functional theory (DFT) calculation.

Keywords: (1:10-phenanthroline) (L1), 4-4-amino phenazone (L2), diphenyl carbizon (L3), DFT study, antibacterial

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Authors: H. Yousefnia, S. Zolghadri, A. Golabi Dezfuli

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Tris (1,10-phenanthroline) lanthanum(III)] trithiocyanate is a new compound that has shown to stop DNA synthesis in CCRF-CEM and Ehrlich ascites cells leading to a cell cycle arrest in G0/G1. One other important property of the phenanthroline nucleus is its ability to act as a triplet-state photosensitizer especially in complexes with lanthanides. In Nowadays, the radiation dose assessment resource (RADAR) method is known as the most common method for absorbed dose calculation. 177Lu was produced by irradiation of a natural Lu2O3 target at a thermal neutron flux of approximately 4 × 1013 n/cm2•s. 177Lu-PL3 was prepared in the optimized condition. The radiochemical yield was checked by ITLC method. The biodistribution of the complex was investigated by intravenously injection to wild-type rats via their tail veins. In this study, the absorbed dose of 177Lu-PL3 to human organs was estimated by RADAR method. 177Lu was prepared with a specific activity of 2.6-3 GBq.mg-1 and radionuclide purity of 99.98 %. The 177Lu-PL3 complex can prepare with high radiochemical yield (> 99 %) at optimized conditions. The results show that liver and spleen have received the highest absorbed dose of 1.051 and 0.441 mSv/MBq, respectivley. The absorbed dose values for these two dose-limiting tissues suggest more biological studies special in tumor-bearing animals.

Keywords: internal dosimetry, Lutetium-177, radar, animals

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Authors: Hossein Tavallali, Mohammad Ali Karimi, Gohar Deilamy-Rad

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The proposed method for speciation, preconcentration and determination of Fe(II) and Fe(III) in pharmaceutical products was developed using of alumina-coated magnetite nanoparticles (Fe₃O₄/Al₂O₃ NPs) as solid phase extraction (SPE) sorbent in magnetic mixed hemimicell solid phase extraction (MMHSPE) technique followed by flame atomic absorption spectrometry analysis. The procedure is based on complexation of Fe(II) with 1, 10-phenanthroline (OP) as complexing reagent for Fe(II) that immobilized on the modified Fe₃O₄/Al₂O₃ NPs. The extraction and concentration process for pharmaceutical sample was carried out in a single step by mixing the extraction solvent, magnetic adsorbents under ultrasonic action. Then, the adsorbents were isolated from the complicated matrix easily with an external magnetic field. Fe(III) ions determined after facility reduced to Fe(II) by added a proper reduction agent to sample solutions. Compared with traditional methods, the MMHSPE method simplified the operation procedure and reduced the analysis time. Various influencing parameters on the speciation and preconcentration of trace iron, such as pH, sample volume, amount of sorbent, type and concentration of eluent, were studied. Under the optimized operating conditions, the preconcentration factor of the modified nano magnetite for Fe(II) 167 sample was obtained. The detection limits and linear range of this method for iron were 1.0 and 9.0 - 175 ng.mL⁻¹, respectively. Also the relative standard deviation for five replicate determinations of 30.00 ng.mL^-1 Fe²⁺ was 2.3%.

Keywords: Alumina-Coated magnetite nanoparticles, Magnetic Mixed Hemimicell Solid-Phase Extraction, Fe(ΙΙ) and Fe(ΙΙΙ), pharmaceutical sample

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Authors: Othmane Essahili, Mohamed Ilsouk, Carine Duhayon, Omar Moudam

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Due to their excellent and promising properties, a great deal of attention has recently been devoted to luminescent materials, particularly those utilizing rare earth elements. These materials play an essential role in low-cost energy conversion technology applications, such as luminescent solar concentrators (LSCs). They also have potential applications in Agri-PV systems and smart building windows. Luminescent materials based on europium (III) complexes are known for their high luminescence efficiency, long fluorescence lifetimes, and sharp emission bands. However, they present certain drawbacks related to their limited absorption capacity due to the forbidden 4f-4f electronic transitions. To address these drawbacks, using β-diketonate ligands as sensitizers appears as a promising solution to enhance luminescence intensity through the antenna effect, where the ligand's excited energy is transferred to the europium ions. In this study, we synthesized β-diketonate-based europium complexes with phenanthroline derivatives, modified with various methyl groups, to examine their effects on the complexes' stability in poly(methyl methacrylate) (PMMA) films. Our findings reveal that these complexes exhibit remarkable red emission and high photoluminescence quantum yield. Stability tests under different conditions for 1200 hours showed that complexes with a higher number of methyl substitutions offer improved photoluminescent stability and resistance to degradation, particularly in outdoor settings. This research underscores the potential of chemically tuned phenanthroline ligands in developing stable, efficient luminescent materials for future optoelectronic devices, including efficient and durable LSCs.

Keywords: luminescent materials, photochemistry, luminescent solar concentrators, β-diketonate-based europium complexes

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Authors: Anna Kolanowska, Anna Kuziel, Sławomir Boncel

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Carbon nanotubes (CNTs) represent a combination of lightness and nanoscopic size with high tensile strength, excellent thermal and electrical conductivity. By now, CNTs have been used as a support in heterogeneous catalysis (CuCl anchored to pre-functionalized CNTs) in the Ullmann-type coupling with aryl halides toward formation of C-N and C-O bonds. The results indicated that the stability of the catalyst was much improved and the elaborated catalytic system was efficient and recyclable. However, CNTs have not been considered as the substrate itself in the Ullmann-type reactions. But if successful, this functionalization would open new areas of CNT chemistry leading to enhanced in-solvent/matrix nanotube individualization. The copper-catalyzed Ullmann-type reaction is an attractive method for the formation of carbon-heteroatom and carbon-carbon bonds in organic synthesis. This condensation reaction is usually conducted at temperature as high as 200 oC, often in the presence of stoichiometric amounts of copper reagent and with activated aryl halides. However, a small amount of organic additive (e.g. diamines, amino acids, diols, 1,10-phenanthroline) can be applied in order to increase the solubility and stability of copper catalyst, and at the same time to allow performing the reaction under mild conditions. The copper (pre-)catalyst is prepared by in situ mixing of copper salt and the appropriate chelator. Our research is focused on the application of Ullmann-type reaction for the covalent functionalization of CNTs. Firstly, CNTs were chlorinated by using iodine trichloride (ICl3) in carbon tetrachloride (CCl4). This method involves formation of several chemical species (ICl, Cl2 and I2Cl6), but the most reactive is the dimer. The fact (that the dimer is the main individual in CCl4) is the reason for high reactivity and possibly high functionalization levels of CNTs. This method, indeed, yielded a notable amount of chlorine onto the MWCNT surface. The next step was the reaction of CNT-Cl with three substrates: aniline, iodobenzene and phenol for the formation C-N, C-C and C-O bonds, respectively, in the presence of 1,10-phenanthroline and cesium carbonate (Cs2CO3) as a base. As the CNT substrates, two multi-wall CNT (MWCNT) types were used: commercially available Nanocyl NC7000™ (9.6 nm diameter, 1.5 µm length, 90% purity) and thicker MWCNTs (in-house) synthesized in our laboratory using catalytic chemical vapour deposition (c-CVD). In-house CNTs had diameter ranging between 60-70 nm and length up to 300 µm. Since classical Ullmann reaction was found as suffering from poor yields, we have investigated the effect of various solvents (toluene, acetonitrile, dimethyl sulfoxide and N,N-dimethylformamide) on the coupling of substrates. Owing to the fact that the aryl halides show the reactivity order of I>Br>Cl>F, we have also investigated the effect of iodine presence on CNT surface on reaction yield. In this case, in first step we have used iodine monochloride instead of iodine trichloride. Finally, we have used the optimized reaction conditions with p-bromophenol and 1,2,4-trihydroxybenzene for the control of CNT dispersion.

Keywords: carbon nanotubes, coupling reaction, functionalization, Ullmann reaction

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Authors: Raafat A. Mandour

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Background; Water may be regarded as polluted if it contains substances that render it unsafe for public use. The surface, subsoil waters and the shallow water-bearing geologic formation are more subjected to pollution due to its closeness to the human daily work. Aim of the work; determine the distribution of iron level in drinking water and its relation to iron level in blood patients suffering from liver diseases. Materials and Methods; For the present study, a total number of (71) drinking water samples (surface, wells and tap) have been collected and Blood samples were carried out on (71) selected inhabitants who attended in different hospitals, from different localities and suffering from liver diseases. Serum iron level in these patients was estimated by using IRON-B kit, Biocon company (Germany) and the 1, 10-phenanthroline method. Results; The water samples analyzed for iron are found suitable for drinking except two samples at Mit-Ghamr district showing values higher than the permissible limit of Egyptian Ministry of Health (EMH) and World Health Organization (WHO).The comparison between iron concentrations in drinking water and human blood samples shows a positive relationship. Conclusion; groundwater samples from the polluted areas should have special attention for treatment.

Keywords: water samples, blood samples, EMH, WHO

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Authors: Md. Maksudur Rahman Khan, Chee Wai Woon, Huei Ruey Ong, Vignes Rasiah, Chin Kui Cheng, Kar Min Chan, E. Baranitharan

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The present work represents a preparation of non-precious iron-based electrocatalyst (FeN) for ORR in air-cathode microbial fuel cell by pyrolysis treatment. Iron oxalate which recovered from the industrial wastewater and Phenanthroline (Phen) were used as the iron and nitrogen precursors, respectively in preparing FeN catalyst. The performance of as prepared catalyst (FeN) was investigated in a single chambered air cathode MFC in which anaerobic sludge was used as inoculum and palm oil mill effluent as substrate. The maximum open circuit potential (OCV) and the highest power density recorded were 0.543 V and 4.9 mW/m2, respectively. Physical characterization of FeN was elucidated by using Brunauner Emmett Teller (BET), X-Ray Diffraction (XRD) analysis and Field Emission Scanning Electron Microscopy (FESEM) while the electrochemical properties were characterized by cyclic voltammetry (CV) analysis. The presence of biofilm on anode surface was examined using FESEM and confirmed using Infrared Spectroscopy and Thermogravimetric Analysis. The findings of this study demonstrated that FeN is electrochemically active and further modification is needed to increase the ORR catalytic activity.

Keywords: iron based catalyst, microbial fuel cells, oxygen reduction reaction, palm oil mill effluent

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Authors: Morlu Stevens, Bareki Batlokwa

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The use of treated wastewater is widely employed to compensate for the scarcity of safe and uncontaminated freshwater. However, the existence of toxic heavy metal ions in the wastewater pose a health hazard to animals and the environment, hence, the importance for an effective technique to tackle the challenge. A multi-templated ion imprinted sorbent (Fe,Ni,Cu-IIP) for the simultaneous removal of heavy metal ions from waste water was synthesised employing molecular imprinting technology (MIT) via thermal free radical bulk polymerization technique. Methacrylic acid (MAA) was employed as the functional monomer, and ethylene glycol dimethylacrylate (EGDMA) as cross-linking agent, azobisisobutyronitrile (AIBN) as the initiator, Fe, Ni, Cu ions as template ions, and 1,10-phenanthroline as the complexing agent. The template ions were exhaustively washed off the synthesized polymer by solvent extraction in several washing steps, while periodically increasing solvent (HCl) concentration from 1.0 M to 10.0 M. The physical and chemical properties of the sorbents were investigated using Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD) and Atomic Force Microscopy (AFM) were employed. Optimization of operational parameters such as time, pH and sorbent dosage to evaluate the effectiveness of sorbents were investigated and found to be 15 min, 7.5 and 666.7 mg/L respectively. Selectivity of ion-imprinted polymers and competitive sorption studies between the template and similar ions were carried out and showed good selectivity towards the targeted metal ion by removing 90% - 98% of the templated ions as compared to 58% - 62% of similar ions. The sorbents were further applied for the selective removal of Fe, Ni and Cu from real wastewater samples and recoveries of 92.14 ± 0.16% - 106.09 ± 0.17% and linearities of R2 = 0.9993 - R2 = 0.9997 were achieved.

Keywords: ion imprinting, ion imprinted polymers, heavy metals, wastewater

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Authors: Anurak Khrueakham, Tassanee Chanphuthin

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Indigo is a well-known natural blue dye that is used hither to even though synthetic ones are commercially available. The removal of indigo from effluents is difficult due to its resistance towards biodegradation which causes an aquatic environment effect. Fenton process is a reaction between hydrogen peroxide H2O2 and Fe2+ to generate •OH (highly reactive oxidant (E◦= 2.8 V)). Additionally, •OH is non-selective oxidant which is capable of destroying wide range of organic pollutants in water and wastewater. The aims of this research were to investigate the effect of H2O2, Fe2+ and pH on indigo wastewater oxidation by Fenton process. A liter reactor was operated in all experiments. The batch reactor was prepared by filling 1 liter of indigo wastewater. The pH was adjusted to the desired value; then, FeSO4 at predetermined amount was added. Finally, H2O2 was immediately added to start the Fenton’s reaction. The Fenton oxidation of indigo wastewater was operated for 60 minutes. Residual H2O2 was analyzed using titanium oxalate method. The Fe2+ concentration was determined by phenanthroline method. COD was determined using closed-reflux titrimetric method to indicate the removal efficiency. The results showed that at pH 2 increasing the initial ferrous concentration from 0.1 mM to 1 mM enhanced the indigo removal from 36% to 59%. Fenton reaction was rapidly due to the high generation rate of •OH. The degradation of indigo increased with increasing pH up to pH 3. This can be explained that the scavenging effect of the •OH by H+ in the condition of low pH is severe to form an oxonium ion, resulting in decrease the production of •OH and lower the decolorization efficiency of indigo. Increasing the initial H2O2 concentration from 5 mM to 20 mM could enhance the decolorization. The COD removal was increased from 35% to 65% with increasing H2O2 concentration from 5 mM to 20 mM. The generations of •OH were promoted by the increase of initial H2O2 concentration. However, the higher concentration of H2O2 resulted in the reduction of COD removal efficiency. The initial ferrous concentrations were studied in the range of 0.05-15.0 mM. The results found that the COD removals increased with increasing ferrous concentrations. The COD removals were increased from 32% to 65% when increase the ferrous concentration from 0.5 mM to 10.0 mM. However, the COD removal did not significantly change at higher 10.0 mM. This is because •OH yielding was lower level of oxidation, therefore, the COD removals were not improved. According to the studies, the Fenton’s reagents were important factors for COD removal by Fenton process. The optimum condition for COD removal of indigo dye wastewater was 10.0 mM of ferrous, 20 mM of H2O2 and at pH 3.

Keywords: indigo dye, fenton oxidation, wastewater treatment, advanced oxidation processes

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Authors: Marinela Miclau, Melinda Vajda, Nicolae Miclau, Daniel Ursu

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Characterized by a simple structure, easy and low cost fabrication, the dye-sensitized solar cell (DSSC) attracted the interest of the scientific community as an attractive alternative of conventional Si-based solar cells and thin-film solar cells. Over the past 20 years, the main efforts have attempted to enhance the efficiency of n-type DSSCs, the highest efficiency record of 14.30% was achieved using the co-sensitization of two metal-free organic dyes and Co (II/III) tris(phenanthroline)-based redox electrolyte. In the last years, the development of the efficient p-type DSSC has become a research focus owing to the fact that the concept of tandem solar cell was proposed as the solution to increase the power conversion efficiency. A promising alternative for the photocathodes of p-type DSSC, cuprous (Cu2O) and cupric (CuO) oxides have been investigated because of its nontoxic nature, low cost, high natural abundance, a good absorption coefficient for visible light and a higher dielectric constant than NiO. In case of p-type DSSC based on copper oxides with I3-/I- as redox mediator, the highest conversion efficiency of 0.42% (Cu2O) and 0.03% (CuO) has achieved. Towards the increase in the performance, we have fabricated and analyzed the performance of p-type DSSC prepared with the binder-free porous Cu2O photocathodes. Porous thin film could be an attractive alternative for DSSC because of their large surface areas which enable the efficient absorption of the dyes and light. We propose a simple and one-step hydrothermal method for the preparation of porous Cu2O thin film using copper substrate, cupric acetate and ethyl cellulose. The cubic structure of Cu2O has been determined by X-ray diffraction (XRD) and porous morphology of thin film was emphasized by Scanning Electron Microscope Inspect S (SEM). Optical and Mott-Schottky measurements attest of the high quality of the Cu2O thin film. The binder-free porous Cu2O photocathode has confirmed the excellent photovoltaic properties, the best value reported for p-type DSSC (1%) in similar conditions being reached.

Keywords: cuprous oxide, dye-sensitized solar cell, hydrothermal method, porous photocathode

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Authors: Zubair Ahmed, Andrea Barbieri

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The need to reduce energy consumption has prompted a considerable research effort for developing alternative energy-efficient lighting systems to replace conventional light sources (i.e., incandescent and fluorescent lamps). Organic light emitting device (OLED) technology offers the distinctive possibility to fabricate large area flat devices by vacuum or solution processing. Lanthanide β-diketonates complexes, due to unique photophysical properties of Ln(III) ions, have been explored as emitting layers in OLED displays and in solid-state lighting (SSL) in order to achieve high efficiency and color purity. For such applications, the excellent photoluminescence quantum yield (PLQY) and stability are the two key points that can be achieved simply by selecting the proper organic ligands around the Ln ion in a coordination sphere. Regarding the strategies to enhance the PLQY, the most common is the suppression of the radiationless deactivation pathways due to the presence of high-frequency oscillators (e.g., OH, –CH groups) around the Ln centre. Recently, a different approach to maximize the PLQY of Ln(β-DKs) has been proposed (named 'Escalate Coordination Anisotropy', ECA). It is based on the assumption that coordinating the Ln ion with different ligands will break the centrosymmetry of the molecule leading to less forbidden transitions (loosening the constraints of the Laporte rule). The OLEDs based on such complexes are available, but with low efficiency and stability. In order to get efficient devices, there is a need to develop some new Ln complexes with enhanced PLQYs and stabilities. For this purpose, the Ln complexes, both visible and (NIR) emitting, of variant coordination structures based on the various fluorinated/non-fluorinated β-diketones and O/N-donor neutral ligands were synthesized using a one step in situ method. In this method, the β-diketones, base, LnCl₃.nH₂O and neutral ligands were mixed in a 3:3:1:1 M ratio in ethanol that gave air and moisture stable complexes. Further, they were characterized by means of elemental analysis, NMR spectroscopy and single crystal X-ray diffraction. Thereafter, their photophysical properties were studied to select the best complexes for the fabrication of stable and efficient OLEDs. Finally, the OLEDs were fabricated and investigated using these complexes as emitting layers along with other organic layers like NPB,N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (hole-transporting layer), BCP, 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (hole-blocker) and Alq3 (electron-transporting layer). The layers were sequentially deposited under high vacuum environment by thermal evaporation onto ITO glass substrates. Moreover, co-deposition techniques were used to improve charge transport in the devices and to avoid quenching phenomena. The devices show strong electroluminescence at 612, 998, 1064 and 1534 nm corresponding to ⁵D₀ →⁷F₂(Eu), ²F₅/₂ → ²F₇/₂ (Yb), ⁴F₃/₂→ ⁴I₉/₂ (Nd) and ⁴I1₃/₂→ ⁴I1₅/₂ (Er). All the devices fabricated show good efficiency as well as stability.

Keywords: electroluminescence, lanthanides, paramagnetic NMR, photoluminescence

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Authors: Juliana A. B. Silva, Caio H. T. L. Albuquerque, Leonardo L. dos Santos, Cristiane K. Oliveira, Ivani Malvestiti, Fernando Hallwass, Ricardo L. Longo

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Complexes with lanthanide ions have been extensively studied due to their applications as luminescent, magnetic and catalytic materials as molecular or extended crystals, thin films, glasses, polymeric matrices, ionic liquids, and in solution. NMR chemical shift data in solution have been reported and suggest fluxional structures in a wide range of coordination compounds with rare earth ions. However, the fluxional mechanisms for these compounds are still not established. This structural fluxionality may affect the photophysical, catalytic and magnetic properties in solution. Thus, understanding the structural interconversion mechanisms may aid the design of coordination compounds with, for instance, improved (electro)luminescence, catalytic and magnetic behaviors. The [Eu(btfa)₃bipy] complex, where btfa= 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and bipy= 2,2’-bipiridyl, has a well-defined X-ray crystallographic structure and preliminary 1H NMR data suggested a structural fluxionality. Thus, we have investigated a series of coordination compounds with lanthanide ions [Ln(btfa)₃L], where Ln = La, Eu, Gd or Yb and L= bipy or phen (phen=1,10-phenanthroline) using a combined theoretical-experimental approach. These complexes were synthesized and fully characterized, and detailed NMR measurements were obtained. They were also studied by quantum chemical computational methods (DFT-PBE0). The aim was to determine the relevant factors in the structure of these compounds that favor or not the fluxional behavior. Measurements of the 1H NMR signals at variable temperature in CD₂Cl₂ of the [Eu(btfa)₃L] complexes suggest that these compounds have a fluxional structure, because the crystal structure has non-equivalent btfa ligands that should lead to non-equivalent hydrogen atoms and thus to more signals in the NMR spectra than those obtained at room temperature, where all hydrogen atoms of the btfa ligands are equivalent, and phen ligand has an effective vertical symmetry plane. For the [Eu(btfa)₃bipy] complex, the broadening of the signals at –70°C provides a lower bound for the coalescence temperature, which indicates the energy barriers involved in the structural interconversion mechanisms are quite small. These barriers and, consequently, the coalescence temperature are dependent upon the radii of the lanthanide ion as well as to their paramagnetic effects. The PBE0 calculated structures are in very good agreement with the crystallographic data and, for the [Eu(btfa)₃bipy] complex, this method provided several distinct structures with almost the same energy. However, the energy barrier for structural interconversion via dissociative pathways were found to be quite high and could not explain the experimental observations. Whereas the pseudo-rotation pathways, involving the btfa and bipy ligands, have very small activation barriers, in excellent agreement with the NMR data. The results also showed an increase in the activation barrier along the lanthanide series due to the decrease of the ionic radii and consequent increase of the steric effects. TD-DFT calculations showed a dependence of the ligand donor state energy with different structures of the complex [Eu(btfa)₃phen], which can affect the energy transfer rates and the luminescence. The energy required to promote the structural fluxionality may also enhance the luminescence quenching in solution. These results can aid in the design of more luminescent compounds and more efficient devices.

Keywords: computational chemistry, lanthanide-based compounds, NMR, structural fluxionality

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