Abstracts

There is a great scientific effort devoted to the design of new families of materials exhibiting a diversity of luminescent phenomena, including strong sensitized visible-to-NIR emission, pure or adjustable white-light emission (WLE), up-conversion luminescence (UCL), or circularly polarized luminescence (CPL), as well as the sensitivity of all these optical effects to external chemical and physical stimuli. Among various groups of inorganic, organic, or hybrid organic-inorganic materials considered tools for the generation of luminescent functionalities, the solids incorporating heavy metal ions, such as ruthenium(II), platinum(II), iridium(III), or rhenium(I or V), were found particularly attractive, especially in the contexts of high quantum yields of photoluminescence, related to their charge-transfer-type emissive electronic transitions, and processability to efficient electroluminescent devices (e.g., L. He, et al. Adv. Funct. Mater. 2020, 30, 1907169; Y. Zhang, C. Yang, et al. Adv. Mater. 2023, 35, 2303066).In this regard, recently we started a research program aimed at the design, synthesis, and characterization of a specific type of heavy transition metal complexes that combines the organic ligands inducing efficient luminescence with inorganic cyanido ligands which can generate the non-trivial ionic, supramolecular, or coordination systems responsible for tuning the optical effects by external stimuli (e.g., S. Chorazy, et al. J. Mater. Chem. C 2022, 10, 12054). As proofs-of-concept, we will present and discuss unique tetracyanido-nitrido-rhenate(V) complexes of the formula of [Re^V(CN)₄(nitrido)(organic ligand)]^2–, and the related solid luminophores demonstrating photoluminescence switchable by temperature and solvent vapors, as well as correlated with order-disorder phase transitions providing the simultaneous thermal switching of both electrical and optical properties of a material (S. Chorazy et al. Angew. Chem. Int. Ed. 2023, 62, e202308284). As a second example, we will present and discuss intrinsically chiral dicyanidoiridate(III) complexes of the formula of [Ir^III(CN)₂(pin-ppy-L)₂]^– (pin-ppy-L = ligand bearing a chiral pinene-based derivative of 2-phenylpyridine), and the related solid luminophores exhibiting luminescent thermometric effects co-existing with non-linear optical activity (S. Chorazy et al. Inorg. Chem. Front. 2024, 11, 1366).