Divalent Europium Complexes with Phenochalcogenato Ligands: Syntheses, Crystal Structures, and Luminescence Properties

Divalent europium complexes have attracted significant attention in various fields due to the unique electronic configuration of the Eu(II) ion. Given the high sensitivity of the 5d → 4f emission of Eu(II) ions to the ligand field, it is crucial to explore the relationship between ligands and this emission in Eu(II) complexes. However, the heavy-atom effects on the 5d → 4f emission of Eu(II) complexes coordinated with non-metal elements in the same group remain unclear. In this study, five mononuclear Eu(II)-chalcogenide complexes, Eu[H3B·EPh-κE,H,H]2(DME)2 (E = S for 1 and Se for 2; DME = 1,2-Dimethoxyethane) and Eu[EPh]2(18-C-6) (E = S for 3, Se for 4, and Te for 5; 18-C-6 = 1,4,7,10,13,16-Hexaoxacyclooctadecane), were synthesized via reduction of diphenyl disulfide chalcogenide analogs with Eu(BH4)2(THF)2 or NaH. The structures of these complexes were investigated by single-crystal X-ray diffraction, and their properties were characterized by thermogravimetric analysis and photophysical property tests. Complexes 1 and 2 are isomorphous and show similar yellowish-green luminescence, while complexes 3–5 have similar structures but crystallize in different space groups with bluish-green luminescence. This research reveals the influence of chalcogenide ligands on the 5d → 4f emission of Eu(II) complexes, providing a theoretical basis and new research ideas for the application of Eu(II) complexes in various fields, including luminescent materials, cryogenic refrigerants, and magnetic materials.