Synthesis, Structures, and Luminescent Properties of Chloride and Nitrate LnIII Complexes Coordinated by tris(Pyrazolyl)methane

• Published in: European journal of inorganic chemistry Vol. 26; no. 25
• Main Authors: Lyubov, Dmitry M., Mahrova, Tatyana V., Cherkasov, Anton V., Fukin, Georgy K., Fedorov, Yury V., Trifonov, Alexander A.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.09.2023
• Subjects: Chlorides; coordination compounds; Dysprosium; Europium; Inorganic chemistry; lanthanides; Luminescence; Methane; Optical properties; Single crystals; structure elucidation; Synthesis; Terbium; tripodal ligands; Ytterbium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.202300292

We report the synthesis of Ln3+ nitrate [Ln(Tpm)(NO3)3] ⋅ MeCN (Ln=Yb (1Yb), Eu (1Eu)) and chloride [Yb(Tpm)Cl3] ⋅ 2MeCN (2Yb), [Eu(Tpm)Cl2(μ‐Cl)]2 (2Eu) complexes coordinated by neutral tripodal tris(3,5‐dimethylpyrazolyl)methane (Tpm). The crystal structures of 1Ln and 2Ln were established by single crystal X‐ray diffraction, while for 1Yb high resolution experiment was performed. Nitrate complexes 1Ln are isomorphous and both adopt mononuclear structure. Chloride 2Yb is monomeric, while Eu3+ analogue 2Eu adopts a binuclear structure due to two μ2‐bridging chloride ligands. The typical lanthanide luminescence was observed for europium complexes (1Eu and 2Eu) as well as for terbium and dysprosium analogues ([Ln(Tpm)(NO3)3] ⋅ MeCN, Ln=Tb (1Tb), Dy (1Dy); [Ln(Tpm)Cl3] ⋅ 2MeCN, Ln=Tb (2Tb), Dy (2Dy)). New nitrate and chloride LnIII complexes based on the neutral Tpm ligand were structurally characterized. The high‐resolution SC XRD study of Yb nitrate complex allowed to obtain the experimental data on the electron density distribution and the nature of the metal‐ligand bonding in this compound. The typical photoluminescence of Eu, Tb and Dy ions were revealed due to direct excitation in the f‐f transitions.