Complexes emitting in the blue spectral region are attractive materials for developing white-colored light sources. Here, we report the luminescence properties of novel coordination compounds based on the trivalent group 3, 13 metals, and the 1-phenyl-3-methyl-4-cyclohexylcarbonyl-pyrazol-5-onate (Q^CH) ligand. [M(Q^CH)₃] (M = Al, Ga, and In), [M(Q^CH)₃(H₂O)] (M = Sc, Gd, and Lu), [Lu(Q^CH)₃(DMSO)], and [La(Q^CH)₃(H₂O)(EtOH)] complexes were synthesized and structurally characterized by a single-crystal X-ray diffraction study. It has been found that the luminescence quantum yields of the ligand increase by one order of magnitude upon metal coordination. A significant correspondence between the energies of the ligand’s excited states and the luminescence quantum yields to the metal ion’s atomic numbers was found using molecular spectroscopy techniques. The replacement of the central ion with the heavier one leads to a monotonic increase in singlet state energy, while the energy of the triplet state is similar for all the complexes. Time-resolved measurements allowed us to estimate the intersystem crossing (ISC) rate constants. It was shown that replacing the Al³⁺ ion with the heavier diamagnetic Ga³⁺ and In³⁺ ions decreased the ISC rate, while the replacement with the paramagnetic Gd³⁺ ion increased the ISC rate, which resulted in a remarkably bright and room-temperature phosphorescence of [Gd(Q^CH)₃(H₂O)].

The influence of the degree of π-conjugation in biaroylmethane ligands upon Eu³⁺ luminescence efficiency in corresponding neutral tris-complexes was investigated in depth. The data obtained by both steady-state and time-resolved luminescence measurements gave an inside into electronic energy transfer mechanisms in the abovementioned complexes. It was shown that extension of the π-system in the naphthalene moiety in comparison to the phenyl one lead to a substantial decrease of both the S₁ and T₁ energy of the corresponding symmetrical β-diketones, which, in turn, led to a decrease of the total quantum yield of respective Eu³⁺ complexes. The obtained results are of interest for the rational design of highly luminescent complexes with NIR-emitting lanthanides, as the resonant levels energies are low and can hardly be sensitized by common ligands.

Achieving high quantum yields for Yb³⁺ ion emission in complexes with organic ligands is a challenging task, as most Yb³⁺ complexes with such ligands typically exhibit efficiencies below 3.5%. Our research demonstrates that the introduction of heavy atom-containing ancillary ligands, such as TPPO or TPAO, along with the careful engineering of the main β-diketone ligand, can increase the luminescence efficiency up to 20-fold by the alteration of the energy migration pathway. It is demonstrated that the combination of two distinct organic ligands leads to the blockage of singlet–triplet intersystem crossing (ISC), alongside electronic energy transfer from β-diketone to Yb³⁺ ions through charge transfer states. The synthesized complexes exhibit quantum yields of 6.5% and 7.0% in the solid state, which places them at the top globally among this class of materials with simple non-deuterated and non-fluorinated ligands.

Six new complexes of the ligand HQ^cy (-4-(cyclohexanecarbonyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one) and Ln³⁺ ions with emission in the near-infrared (Nd³⁺) or visible and near-infrared (Sm³⁺, Pr³⁺) spectral regions were synthesized and characterized using various methods, including single crystal X-ray diffraction. The study demonstrated that both tris complexes [LnQ^cy₃(H₂O)(EtOH)] and tetrakis-acids [H₃O][LnQ^cy₄] can be synthesized by varying the synthetic conditions. The photochemical properties of the complexes were investigated experimentally and theoretically using various molecular spectroscopy techniques and Judd–Ofelt theory. The objective was to quantitatively and qualitatively disclose the influence of complex stoichiometry on its luminescence properties. The study showed that the addition of an extra ligand molecule (in the tetrakis species) increased molar extinction by up to 2 times, affected the shape of photoluminescence spectra, especially of the Pr³⁺ complex, and increased the quantum yield of the Sm³⁺ complex by up to 2 times. The results obtained from this study provide insights into the luminescent properties of lanthanide coordination compounds, which are crucial for the design and development of novel photonic materials with tailored photophysical properties.

A series of cyclometalated complexes of ruthenium (II) with four different substituents in the aryl fragment of benzimidazole was synthesized in order to study the effect of substituent donation on the electronic structure of the substances. The resulting complexes were studied using X-ray diffraction, NMR spectroscopy, MALDI mass spectrometry, electron absorption spectroscopy, luminescence spectroscopy, and cyclic voltammetry as well as DFT/TDDFT was also used to interpret the results. All the complexes have intense absorption in the range of up to 700 nm, the triplet nature of the excited state was confirmed by measurement of luminescence decay. With an increase in substituent donation, a red shift of the absorption and emission bands occurs, and the lifetime of the excited state and the redox potential of the complex decrease. The combination of these properties shows that the complexes are excellent dyes and can be used as photosensitizers.