Mononuclear lanthanide complexes with tetradentate bis(phosphorylamino)- substituted 1,8-naphthyridine ligand: Synthesis and structural studies

摘要

The complexes of 2,7-bis(diphenylphosphorylamino)-1,8-naphthyridine (L) with lanthanide nitrates Ln(NO _3) _3 (Ln = Nd, Lu) were investigated to elucidate the coordination ability of a novel type of potentially tetradentate ligands - bis(phosphorylamino) substituted naphthyridines. Mononuclear complexes of 1:1 and 1:2 composition, namely, [Nd(L)(NO _3) _3] (1a), [Nd(L)(NO _3) _3]·H _2O (1b), [Lu(L)(NO _3) _2(H _2O)](NO _3) (2), [Nd(L) _2(NO _3) _2(H _2O)](NO _3) (3), [Lu(L) _2(NO _3)(H _2O)](NO _3) _2·0.75CH _3CN·H _2O (4a) and [Lu(L) _2(NO _3)(H _2O)](NO _3) _2 (4b) were synthesized and studied by IR, Raman, and 31P NMR spectroscopy in solid state and in solution. Structures of the complexes 1b and 4a were determined by X-ray diffraction. According to X-ray crystallography, vibrational spectroscopy and C, H, N, P elemental analysis data in solid 1:1 complexes one neutral molecule of L serves most likely as O,O,N,N-tetradentate ligand while in the 1:2 complexes only one ligand molecule coordinates in the same O,O,N,N-tetradentate fashion, and the second one serves as O-monodentate one. In solution the coordination mode of the ligand is preserved in all complexes.