Dynamics of the Ligand Excited States Relaxation in Novel β-Diketonates of Non-Luminescent Trivalent Metal Ions.

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 (H ₂ O)] (M = Sc, Gd, and Lu), [Lu(Q ^CH ) ₃ (DMSO)], and [La(Q ^CH ) ₃ (H ₂ O)(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 Al ³⁺ ion with the heavier diamagnetic Ga ³⁺ and In ³⁺ ions decreased the ISC rate, while the replacement with the paramagnetic Gd ³⁺ ion increased the ISC rate, which resulted in a remarkably bright and room-temperature phosphorescence of [Gd(Q ^CH ) ₃ (H ₂ O)].