Research paperStructure, stability and spectroscopic features of the neodymium(III) complex of the octadentate polypyridine ligand 6,6′-bis[bis(2-pyridylmethyl)aminomethyl]-2.2′-bipyridine

Add time:08/31/2019    Source:sciencedirect.com

The synthesis, crystal structure and spectroscopic properties of the neodymium(III) complex [Nd(btpa)Cl2]Cl·5H2O with btpa being the octadentate polypyridine ligand 6,6′-bis[bis(2-pyridylmethyl)aminomethyl]-2.2′-bipyridine are reported. The structure shows that the Nd3+ ion is coordinated to seven nitrogen atoms of btpa and two chloride ions, leaving one uncoordinated pyridine group. The coordination polyhedron is best described as a monocapped cube. The btpa ligand forms a stable 1:1 complex with Nd(CF3SO3)3 and other selected triflates of the lanthanides(III) ions (Ln) in anhydrous acetonitrile. The stability constants of the Ln(btpa)3+ complexes are quite similar along the series, due to a compensation between ligand-metal interaction and lanthanide desolvation. High resolution absorption spectroscopy at 4 K shows one equivalent crystallographic position of the Nd3+ ion in the structure. The Nd-btpa complexes in the solid-state and in AN solution upon excitation wavelength from the range of ligands absorption bands display NIR luminescence with the characteristic 4F3/2 → 4IJ (J = 9/2, 11/2 and 13/2) transitions of the Nd3+ ion. The decay times of the 4F3/2 state of Nd3+ equal 1.4 (293 K) and 2.3 μs (77 K) (λexc = 350 nm) for the complexes in the solid-state as well as 0.43 (293 K) and 0.46 μs (77 K) (λexc = 266 nm) for AN solution.

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