Europium-based ß-hydroxyketone complexes: synthesis, optoelectronic, thermal and computational analyses.

Six red-light-emitting Eu(III) complexes having a ß-hydroxyketone as ligand and heterocyclic ring containing compounds as ancillary ligands were synthesized to explore their use in displays and optoelectronics. The coordinating behavior of complexes was determined by various techniques such as FTIR (Fourier transform infrared), 1H-NMR (Nuclear magnetic resonance), and 13C-NMR that establishes a bonding of ligand and ancillary ligand with the Eu(III) ion. Morphology and purity were investigated through XRD (X-ray diffraction), SEM (scanning electron microscopy) and EDS (energy-dispersive X-ray spectroscopy) analyses that suggest semicrystalline and pure complex formation. Thermal analysis of complexes by TGA/DTG (thermogravimetric/derivative thermogravimetric) indicates that complexes are stable upto 200 ºC temperature making them suitable for use in display devices. Analysis of the photophysical properties was carried out in both solid and solution states using PL (photoluminescence) studies, color parameters, J-O (Judd-Ofelt) analysis and bandgap. Most emissive transition (5D0 → 7F2) is responsible for the red emission in the complexes. The CIE (Commission International de I'Eclairage) coordinates of complexes also indicate the red emission on UV excitation. The bandgap which was obtained in the range of 2.54-3.02 eV reveals the semiconducting behavior of complexes. Values of J-O parameters and Ω2 in the complexes reflect asymmetric chemical environment around Eu (III) and less covalence and the Ω4 indicates that complexes are less rigid. Bandgap calculated through DFT (density function theory) for complexes is in range of 2.37-2.77 eV, and intensity parameters (J-O), energy transfer rates, and spherical coordinates were determined by LUMPAC software. The computational data are in good harmony with the experimental data. Further biological aspects of complexes were studied using antioxidant and antimicrobial studies.

New Highly Luminescent Red Emitting Complexes: Synthesis, Characterization, Judd-Ofelt Intensity Parameters and Pharmacological Investigations.

A series of new red luminescent Eu(III) complexes were integrated by ß-hydroxyketone ligand 2-(4-chlorophenyl)-1-(2-hydroxy-4,6-dimethoxyphenyl)ethan-1-one (CHDME) as main ligand and 1,10-phenanthroline (phen) or 5,6-dimethyl-1,10-phenanthroline (dmphen) or bathophenanthroline (bathophen) as ancillary ligand. The complexes were synthesised by solution precipitation method. The CHDME is taken as ligand and its analogous Eu(III) complexes were characterized by elemental analysis, FT-IR and 1H-NMR. The photoluminescent properties were also examined in solid state. The Judd-Ofelt intensity parameters (Ω2 and Ω4) and luminescence quantum efficiency (η) of Eu(III) complexes were additionally figured out as per luminescence spectra and decay cure. UV analysis and optical band was also calculated. Computational analysis were carried out and optical band and Judd-Ofelt intensity parameters were determined. Furthermore, the pharmacological activities such as antimicrobial and antioxidant activity of ligand CHDME and its analogous Europium complexes were also examined. The methods used were tube dilution method for calculating antimicrobial activity and DPPH free radical method for antioxidant activity.

Exploration of Optical and Radiative Properties of Fluorinated ß-keto Carboxylate Tb3+ Complexes Emanating Cool Green Light.

Tb3+ complexes with ß-ketocarboxylic acid as main ligand and heterocyclic systems as auxiliary ligand were synthesized and analyzed to assess their prospective relevance as green light emitting material. The complexes were characterized via various spectroscopic techniques and were found to be stable up to ≈ 200 ℃. Photoluminescent (PL) investigation was performed to assess the emissive nature of complexes. Longest luminescence time of decay (1.34 ms) and highest intrinsic quantum efficiency (63.05%) were fetched for complex T5. Color purity of complexes was found to be in range 97.1 - 99.8% which demonstrated the aptness of these complexes in green color display devices. NIR Absorption spectra were employed to evaluate Judd-Ofelt parameters to appraise the luminous performance and environment encircling Tb3+ ions. The JO parameters were found to follow the order: Ω2 > Ω4 > Ω6 and suggested the higher covalence character in complexes. Theoretical branching ratio in the range 65.32 - 72.68%, large stimulated emission cross section and narrow FWHM for 5D4 → 7F5 transition unlocked the relevance of these complexes as a green color laser media. Band gap and Urbach analysis were consummated via enforcing nonlinear curve fit function on absorption data. Two band gaps with values in between 2.02 - 2.93 eV established the prospective use of complexes in photovoltaic devices. Energies of HOMO and LUMO were estimated employing geometrically optimized structures of complexes. Investigation of biological properties accomplished via antioxidant and antimicrobial assays which communicated their applicability in biomedical domain.

Computational and optoelectronic quantification of semi-conducting, warm ruby red color emanating Eu3+ complexes with hetro-cyclic ligands.

Six Eu3+ complexes were synthesised with ß-keto acid as main ligand and secondary ligands through liquid assisted grinding method. These complexes were characterised by various techniques such as spectroscopic technique, XRD, EDAX, SEM analysis, thermal technique, Urbach energy and optical band gap investigation. The luminous photophysical properties were studied by PL spectroscopy in solid as well as solution phase and some theoretical calculation was done to investigate the radiative (Arad) & non-radiative (Anrad) transition rate, quantum efficiency (ɸ), Judd Ofelt parameters for 5D0 → 7F2,4 transitions in both states. Judd Ofelt parameters were also calculated by the JOES software and the outcomes are well harmonised with theoretical values. The complexes have CIE color coordinate value in ruby red region and above 88.65% color purity in both phases, which made them attractive candidates for red light-emitting displays. 5D0 → 7F2 transition was proposed as a laser emission transition owing to their high branching ratio (67.18-74.24%) in solid and (60.09-74.40%) in solution phase. Computational methods were employed to determine the structure and energy of various molecular orbitals. Antimicrobial assay of complexes was also rationalised and found that the complexes are pertinent as good bactericidal and fungicidal agents in pharmaceutical industry.

Study of Judd-Ofelt, Urbach energy and photosensitization process in luminescent Sm(III) complexes with heterocyclic ligands.

Six samarium (III) complexes were synthesised by employing the ß-ketocarboxylic acid as main ligand and five N-donor systems as ancillary ligands through the environmentally safe liquid-assisted grinding method. Various characterisation techniques were employed to determine the structure of the complexes i.e. NMR, IR, XRD and SEM. Photoluminescent studies were carried out in solid as well as in solution form. In solid and solution form emission spectra show maximum intensity peak at 604 and 602 nm, respectively, assigned to 4G5/2 → 6H7/2 transition which explains orange emission on UV excitation in complexes. CCT, CP, colorimetric parameters and quantum yield (relative and intrinsic) of the synthesized complexes were calculated. With the help of reflectance spectra, band gap and Urbach energy were determined. Lasing parameters were also calculated by employing FWHM values obtained from Gaussian fitting. Energy transfer study revealed the efficacious energy transfer from ligand to metal's emissive level. Further antimicrobial studies revealed higher activity in case of complexes in comparison to ligand.

Computational analysis, Urbach energy and Judd-Ofelt parameter of warm Sm3+ complexes having applications in photovoltaic and display devices.

In this work, six reddish orange Sm3+ complexes were synthesized using organic ligand (L) and secondary ligands having hetero atoms by a one-step significant liquid-assisted grinding method and were characterized by spectroscopic techniques. The Urbach energy and band gap energy of the complexes were inspected by a linear fit. Using a least square fitting method, the Judd-Ofelt parameter and radiative properties were also determined. Thermal analysis, colorimetric analysis, luminescence decay time and anti-microbial properties of complexes were studied. The luminescence emission spectra of binary and ternary complexes displayed three characteristic peaks at 565, 603 and 650 nm in the powder form and four peaks at 563, 605, 646 and 703 nm in a solution phase due to 4G5/2 → 6H5/2, 4G5/2 → 6H7/2, 4G5/2 → 6H9/2 and 4G5/2 → 6H11/2 transitions respectively. The most intense transition in the solid phase (4G5/2 → 6H7/2) is accountable for orange color, and in the solution form, the highly luminescent peak (4G5/2 → 6H9/2) is responsible for reddish orange color of Sm3+ complexes. PXRD and SEM analyses suggested that the complexes possess a nanoparticle grain size with crystalline nature. The decent optoelectrical properties of title complexes in the orangish-red visible domain indicated possible applications in the manufacturing of display and optoelectronic devices.