Lanthanide pentafluorophenolates. Synthesis, structure and luminescent properties
作者:Alexander A. Maleev、Anatoly A. Fagin、Vasily A. Ilichev、Mikhail A. Lopatin、Alexey N. Konev、Maksim A. Samsonov、Georgy K. Fukin、Mikhail N. Bochkarev
DOI:10.1016/j.jorganchem.2013.03.052
日期:2013.12
The pentafluorophenolates of lanthanides Ln(OC6F5)(3) (Ln = Nd (1), Tb (2), Er (3)) were prepared by the reactions of pentafluorophenol with appropriate silylamides Ln[N(SiMe3)(2)](3) in benzene or toluene solution. The same reactions in ether or methanol medium afforded the solvated complexes Ln(OC6F5) (3)(Et2O)(3) (Ln = Nd (4), Eu (5), Tb (6), Er (7), Gd (8)) or Nd(OC6F5)(3)(MeOH)(3) (9), respectively. The phenanthroline complexes Ln(C6F5O)(3)(phen) (Ln = Pr (10), Nd (11), Er (12)), Ln(OC6F5)(3)(phen) 2 (Ln = Sm (13), Tb (14), Ho (15), Ln(OC6F5)(3)(phen)(2)(Et2O) (Ln = Eu (16), Yb (17)), and Ln(OC6F5) 3(phen)(Et2O)(3) (Ln = Eu (18), Nd (19), Ce (20), Dy (21)), Ln(OC6F5) (3)(phen) (2)(H2O) (Ln = Sm (22), Ho (23)), and Gd(OC6F5)(3)(phen)(2)(MeOH) (24) were obtained when the reactions were carried out in the presence of 1,10-phenanthroline. The complexes with pyridine Tb(OC6F5)(3)(py) 5 (25) and 2,20-bipyridyl Ln(OC6F5)(3)(bpy)(2) (Ln = Tb (26), Yb (27)) were synthesized similarly. Compounds 7, 22, 23, and 24 were characterized by X-ray analysis. The complexes Ln(OC6F5)(3) decompose above 150 degrees C in vacuum to give lanthanide fluorides and octofluorodibenzo-p-dioxine. Phenanthroline derivatives are stable up to 310 degrees C. Luminescence spectra of all the obtained complexes in visible region contain a broad band of ligand-centered emission peaked at 405e415 nm. Spectra of samarium 13, europium 5, 16, 18 and terbium 14, 25, 26 derivatives display also the characteristic narrow bands of Sm3+, Eu3+ and Tb3+ ions. (C) 2013 Elsevier B. V. All rights reserved.