Citation: Yahui HAN, Jinjin ZHAO, Ning REN, Jianjun ZHANG. Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(5): 969-982. doi: 10.11862/CJIC.20240395 shu

Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes

Yahui HAN ¹ ,
Jinjin ZHAO ^1,, ,
Ning REN ^2,, ,
Jianjun ZHANG ^1,,

1.
Testing and Analysis Center, College of Chemistry & Material Science, Hebei Normal University, Shijiazhuang 050024, China
2.
Hebei Key Laboratory of Heterocyclic Compounds, College of Chemical Engineering & Material, Handan University, Handan, Hebei 056005, China

Corresponding author: Jinjin ZHAO, jjzhang6@126.com Ning REN, ningren9@163.com Jianjun ZHANG, zhaojinjin@hebtu.edu.cn
Received Date: 4 November 2024
Revised Date: 18 March 2025

Figures(17)

Two novel lanthanide complexes, [Sm₂(BA)₆(4-OH-terpy)₂]·2H₂O·2EtOH (1) and [Pr₂(BA)₆(4-OH-terpy)₂ (H₂O)₂]·HBA·H₂O (2), where HBA=benzoic acid, 4-OH-terpy=4-hydroxy-2, 2'∶6', 2″-terpyridine, were successfully synthesized using ultrasonic dissolution and the conventional solution method with two mixed ligands HBA and 4OH-terpy. During the synthesis, 4-OH-terpy was involved in the reaction as a neutral ligand, while HBA, in its deprotonated form (BA^-), coordinated with the lanthanide ions as an acidic ligand. The crystal structures of these two complexes were precisely determined by single crystal X ray diffraction. Elemental analysis, infrared and Raman spectroscopy, and powder X-ray diffraction techniques were also employed to further explore the physicochemical properties of the two complexes. The single-crystal X-ray diffraction data indicate that, despite their structural differences, both complexes belong to the triclinic crystal system $P \overline{1}$ space group. The central lanthanide ions have the same coordination number but exhibit different coordination environments. To comprehensively evaluate the thermal stability of these two complexes, comprehensive tests including thermogravimetric analysis, differential thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, and mass spectrometry were conducted. Meanwhile, an in depth investigation was conducted into the 3D infrared stacked images and mass spectra of the gases emitted from the complexes. In addition, studies of the fluorescence properties of complex 1 showed that it exhibited fluorescence emission matching the Sm³⁺ characteristic transition.
- lanthanide complexes,
- crystal structure,
- thermochemistry,
- fluorescence spectrum
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