Crystal Structure and Highly Luminescent Properties Studies of Bis-β-diketonate Lanthanide Complexes

Abstract

A new bis(β-diketonate), 1,3-bis(4,4,4-trifluoro-1,3-dioxobutyl)phenyl (BTP), which contains a trifluorinated alkyl group, has been prepared for the synthesis of two series of dinuclear lanthanide complexes with the general formula Ln2(BTP)3L2 [Ln(3+) = Eu(3+), L = DME(1), bpy(2), and phen(3); Ln(3+) = Sm(3+), L = DME(4), bpy(5), and phen(6); DME = ethylene glycol dimethyl ether, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline]. The crystal structure of the free ligand has been determined and shows a twisted arrangement of the two binding sites around the 1,3-phenylene spacer. X-ray crystallographic analysis reveals that complexes 1, 2, 4, and 5 are triple-stranded dinuclear structures formed by three bis-bidentate ligands with two lanthanide ions. The room-temperature photoluminescence (PL) spectra of complexes 1-6 show that this bis-β-diketonate can effectively sensitize rare earths (Sm(3+) and Eu(3+)) and produce characteristic emissions of the corresponding Eu(3+) and Sm(3+) ions. In addition, two bidentate nitrogen ancillary ligands, 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen), have been employed to enhance the luminescence quantum yields and lifetimes of both series of Eu(3+) and Sm(3+) complexes.

The crystal structure of tris(μ2-1,3-bis(4,4,4-Trifluoro-3-oxido-1-(oxo)but-2-en-1-yl)phenyl-/κ4O,O′:O′′,O′′′)-bis(1,2-dimethoxyethane-O,O′)-diterbium(III)

“…The structural analysis reveals that complex, crystallizing in the monoclinic space group C2/c, is a triple-stranded dinuclear helicate featured by the coordination of three bisdiketonate ligands to two crystallographically equivalent Tb 3+ ions. The title structure is isostructural to some other lanthanide complexes [1,2]. Each crystallographically distinct Tb 3+ ion is ligated to six oxygen atoms from three bisdiketonate ligands and two oxygen atoms from one DME ligand, resulting in the distorted square antiprismatic geometry.…”

“…was synthesized following a literature method [1,2]. In a typical reaction, to a solution of 1,3-bis(4,4,4-tri uoro-1,3-dioxobutyl)phenyl (1 g, 2.8 mmol) in 10 ml methanol, NaOH (0.2 g, 5.6 mmol) was added, and the mixture was allowed to stir for 5 min.…”

The crystal structure of tris(μ2-1,3-bis(4,4,4-trifluoro-3-oxido-1-(oxo)but-2-en-1-yl)phenyl-κ4 O,O′:O′′,O′′′)-bis(1,2-dimethoxyethane-κ2 O,O′)dilutetium(III), C50H38F18Lu2O16

“…Some directly related structures of the title structure have been reported [3,[7][8]. In the title crystal structure, the bond distances and bond angles are all in normal range [9].…”

“…The title compound is easily synthesized by means of reported procedures [3]. To a methanol solution of 1,3-bis(4,4,4-trifluoro-1,3-dioxobutyl)phenyl (1 g, 2.8 mmol), NaOH (0.2 g, 5.6 mmol) was added, and the mixture was allowed to stir for 5 min.…”

Crystal structure of (Z)-6-methoxy-2-(2,2,2-trifluoro-1-hydroxyethylidene)-2,3-dihydro-1H-inden-1-one, C12H6F6O3

“…The title compound was synthesised following a literature method [1,2]. In a typical reaction, to a solution of 6-methoxy-2,3-dihydro-1H-inden-1-one (2.5 g, 11.57 mmol) in 60 mL dry tetrahydrofuran, ethyl 2,2,2-tri uoroacetate (2.46 g, 17.31 mmol) was added, and the mixture was allowed to stir for 45 min.…”