In this paper we review the spectroscopic properties of three transition metal ions - Mn⁴⁺, Cr³⁺ and Ni²⁺ - in crystals and establish a relationship between the energies of the lowest in energy spin-forbidden transitions and covalence of the “metal –ligand” chemical bonds. A new parameter (where (B, C (B₀, C₀) are the Racah parameters of the ions in a crystal (free state), respectively) is shown to determine the energy of the above-mentioned transitions. The considered ions can be used as reliable probes of the covalent effects in various hosts. Several practical recommendations on how to tune the spin-forbidden transitions energy to meet specific needs are suggested.

Luminescence methods for non-contact temperature monitoring have evolved through improvements of hardware and sensor materials. Future advances in this field rely on the development of multimodal sensing capabilities of temperature probes and extend the temperature range across which they operate. The family of Cr-doped oxides appears particularly promising and we review their luminescence characteristics in light of their application in non-contact measurements of temperature over the 5–300 K range. Multimodal sensing utilizes the intensity ratio of emission lines, their wavelength shift, and the scintillation decay time constant. We carried out systematic studies of the temperature-induced changes in the luminescence of the Cr³⁺-doped oxides Al₂O₃, Ga₂O₃, Y₃Al₅O₁₂, and YAlO₃. The mechanism responsible for the temperature-dependent luminescence characteristic is discussed in terms of relevant models. It is shown that the thermally-induced processes of particle exchange, governing the dynamics of Cr³⁺ ion excited state populations, require low activation energy. This then translates into tangible changes of a luminescence parameter with temperature. We compare different schemes of temperature sensing and demonstrate that Ga₂O₃-Cr is a promising material for non-contact measurements at cryogenic temperatures. A temperature resolution better than ±1 K can be achieved by monitoring the luminescence intensity ratio (40–140 K) and decay time constant (80–300 K range).