Synthesis, structure, thermal and spectroscopic properties of two new series of cationic Ln(III) complexes of the type [Ln(L)2(bpy)2]BPh4

Struhatska, Mariia B. and Kariaka, Nataliia S. and Trush, Viktor O. and Dyakonenko, Viktoriya V. and Shishkina, Svitlana V. and Dömötör, Orsolya and Arion, Vladimir and Lipa, Aneta and Gawryszewska, Paula and Lazarenko, Maxim M. and Amirkhanov, Volodymyr M. (2025) Synthesis, structure, thermal and spectroscopic properties of two new series of cationic Ln(III) complexes of the type [Ln(L)2(bpy)2]BPh4. JOURNAL OF MOLECULAR STRUCTURE, 1348. ISSN 0022-2860 (print); 1872-8014 (online)

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Abstract

Two new series of cationic lanthanide complexes, namely [Ln(L1)2(bpy)2]BPh4 (Ln1) and [Ln(L2)2(bpy)2]BPh4 (Ln2), where Ln = La, Nd, Eu, Gd, Tb, Lu, HL1 = Cl3C(O)NHP(O)(OCH3)2, HL2 = PhS(O2)NHP(O)(OCH3)2, and bpy is 2,2 '-bipyridine, were synthesized. They were studied by elemental analysis, single crystal X-ray diffraction (for Eu1, Tb1, and Eu2), powder X-ray diffraction, thermal analysis, IR, NMR, reflection, absorption, and luminescence spectroscopies. The LnIII in these complexes are eight-coordinate, with a coordination core LnO4N4. The coordination polyhedra can be described as a square antiprism for Eu1, Tb1 or an intermediate between a square antiprism and a triangular dodecahedron for Eu2. The Ln2 complexes were found to be thermally more stable than Ln1. Effective energy transfer from the ligands to the TbIII ion was demonstrated. However, sensitization of EuIII luminescence was less efficient. The f-f luminescence of the europium(III) and terbium(III) complexes is characterized by an emission decay time of 1.70-1.85 ms at 77 and 298 K.

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