Luminescent europium-dibenzoylmethane complexes and their Langmuir-Blodgett films

doi:10.1016/0925-8388(95)02159-0

Journal of Alloys and Compounds

Volume 235, Issue 2, 15 March 1996, Pages 156-162

https://doi.org/10.1016/0925-8388(95)02159-0 Get rights and content

Abstract

Two strong fluorescent amphiphilic europium-dibenzoylmethane complexes, hexadecyltrimethyl ammonium tetrakis (dibenzoylmethane) europium (A) and octadecyltriethyl ammonium tetrakis (dibenzoylmethane) europium (B), were synthesized and characterized by FT-IR, UV-vis, DTA-TG analysis and X-ray diffraction. Both of them could form stable Langmuir films at the air-water interface and the Langmuir film of A can be easily transferred onto hydrophilic substrates to build up Langmuir-Blodgett (LB) films. The LB film of A has a good layered structure, as confirmed by its low-angle X-ray diffraction. The fluorescence spectra and fluorescence lifetimes of the LB films were quite different from those of their corresponding solid powders and solutions.

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Langmuir–Schaefer films based on highly hydrophobic Eu<sup>3+</sup> tetrakis-β-diketonate complexes containing amphiphilic counterions
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Eu3+ tetrakis-β-diketonate complexes have excelled in the fabrication of Langmuir films due to their bright luminescence, and the presence of an amphiphilic counterion favors the organization of the luminescent anionic complex on the substrate interface.[5] Although the fabrication of thin films based on Eu3+ tetrakis-β-diketonate complexes has already been reported [5,6,7] some challenges still need to be addressed, such as the organization of the europium complex in the film, the counterion influence on the film organization, and the optimization of the luminescent properties. Therefore, to overcome such issues, we have chosen [Q][Eu(dbm)4)] complexes — where dbm = 1,3-diphenyl-1,3-propanedionate, Q = C26H56N+ (Q1), C19H42N+ (Q2), or C17H38N+ (Q3) —, whose syntheses have recently been reported by our research group.[8].
Langmuir-Schaefer (LS) films based on [Q][Eu(dbm)₄)] complexes — where dbm⁻ = 1,3-diphenyl-1,3-propanedionate, Q = C₂₆H₅₆N⁺ (Q1), C₁₉H₄₂N⁺ (Q2), or C₁₇H₃₈N⁺ (Q3) — using amphiphilic counterions (Q) to organize the luminescent anionic complex on the subtract have been investigated. The amphiphilic counterions play an important role in the film fabrication by increasing the surface homogeneity and deposition quality as the carbonic chain increases, especially for the [Q1][Eu(dbm)₄)] film, which showed root mean square surface roughness of 37.8 nm. All films displayed the characteristic Eu³⁺ red-light emission under excitation at 367 nm, and the best intrinsic emission quantum yield was achieved for the [Q1][Eu(dbm)₄)] film (27.5%), confirming that the counterion also influences the luminescent features of the films due to changes in the anionic complex conformation compared to the respective bulk complexes.
Luminescence properties of 2-benzoyl-1,3-indandione based Eu<sup>3+</sup> ternary and tetrakis complexes and their polymer films
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The first stage can be signed to loss of counterion (N+(Bu)4) and one MBID molecule and second stage – to one MBID molecule. Similar destruction pattern was reported for tetrakis Eu3+ complexes with dibenzoylmethane ligands and hexadecyltrimethyl ammonium or octadecyltriethyl ammonium counterions [23]. In the end of TGA (at 890 °C) high residual weight of tetrakis complexes (40–48%) are obtained similarly than for ternary complexes.
Six new Europium (III) complexes with ternary and tetrakis structures - Eu(BID)₃(PHEN), Eu(MBID)₃(PHEN), [Eu(BID)₄]⁻N⁺(Et)₄, [Eu(MBID)₄]⁻N⁺(Et)₄, [Eu(BID)₄]⁻N⁺(Bu)₄, and [Eu(MBID)₄]⁻N⁺(Bu)₄ (BID – 2-benzoyl-1,3-indandionate, MBID - 2-(4-methylbenzoyl)-1,3-indandionate and PHEN – 1,10-phenantroline) are synthesized, characterized, and incorporated into poly-N-vinylcarbazole (PVK) and poly methyl methacrylate (PMMA) matrices. Complex structure shows significant effect on thermal properties and emission properties of complexes in solid-state. Used countercations (N⁺(Et)₄ or N⁺(Bu)₄) greatly affects complex solubility in solvents, absolute photoluminescence quantum yields and photoluminescence lifetimes in solid-state. Complexes exhibit red-light emission attributed to ⁵D₀→⁷F_J (J = 0–4) transitions of Eu³⁺ ion with moderate to high quantum yields (0.06–0.60), bi-exponential lifetimes and pure red-light CIE chromaticity coordinates (x = 0.670; y = 0.330) in solid-state. Incorporation of synthesized complexes in PVK matrices leads to significant emission intensity and quantum yield decrease.
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Citation Excerpt :
Eu(pmbp)4]−(N-hexadecylpyridinium)+ has better film forming properties, but the complex is only weakly luminescent (Huang et al., 1991). Zhou et al. (1996) investigated the luminescence of [Eu(dbm)4]−(Et3NC18H37)+ and [Eu(dbm)4]−(Me3NC16H33)+ in LB-films. [ Eu(tta)4]−(Me3NC16H33)+ cannot form a stable monolayer on a pure water surface, because of dissolution (Liu et al., 1998).
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Luminescent hybrid Langmuir–Blodgett (LB) films of polyoxometaloeuropate (Na₉EuW₁₀O₃₆) were successfully prepared. Low-angle X-ray diffraction data demonstrate that the LB films have a well-defined lamellar structure. The hybrid LB films can exhibit strong luminescence under UV irradiation, which can be observed by the human eye. The effect of the lipid octadecylamine on the luminescence of polyoxometaloeuropate was discussed and compared with that of the lipid dimethyldioctadecylammonium bromide. It is found that the intensity ratio for the ⁵D₀→⁷F₂ transition to the ⁵D₀→⁷F₁ transition of europium in two kinds of LB films is quite different. The X-ray photoelectron spectra data verify that there exist different interactions between two lipids and the inorganic polyanions. The different interactions between two lipids and the polyanions may result in the distortion of the site symmetry for europium to a different extent, which may account for the difference in luminescent behavior between the two kinds of LB films.

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ChemistryLuminescent europium-dibenzoylmethane complexes and their Langmuir-Blodgett films

Abstract

Solid State Commun.

Solid State Commun.

J. Inorg. Nucl. Chem.

Inorg. Chim. Acta

J. Am. Chem. Soc.

Chin. Chem. Lett.

Langmuir

Chem. Mater.

Langmuir

Chem. J. Chin. Univ.

Acta Phys. Chem. Sin.

Chem. Lett.

Appl. Phys. Lett.

Chemistry
Luminescent europium-dibenzoylmethane complexes and their Langmuir-Blodgett films