WO2012120175A1

WO2012120175A1 - Optically active octacoordinated ternary complexes of erbium (iii) or ytterbium (iii) and production method

Info

Publication number: WO2012120175A1
Application number: PCT/ES2012/070143
Authority: WO
Inventors: Jesús MARTÍN GIL; Pablo MARTÍN RAMOS; Pedro CHAMORRO POSADA; Luis Manuel Navas Gracia; Ana María MATOS BEJA; Manuela RAMOS MARQUÉS DA SILVA; Ángel Luis ALVAREZ CASTILLO; María del Carmen COYA PÁRRAGA
Original assignee: Universidad De Valladolid
Priority date: 2011-03-10
Filing date: 2012-03-07
Publication date: 2012-09-13
Also published as: ES2388091A1; ES2388091B1

Abstract

The present invention relates to an optically active ternary complex of lanthanides in which the lanthanide ion is coordinated with three beta-diketonate ligands and with a Lewis-base ligand in accordance with the following general formula: [Ln β-diketone)₃(N,N-donor)], in which Ln is Er (erbium) or Yb (ybterbium); (β-diketone)₃ represents three beta-diketonate ligands; and (N,N-donor) represents a Lewis-base ligand. A further subject matter of the present invention is the method for synthesis of the complexes described and also the multiple uses thereof in telecommunications and optoelectronic engineering devices, principally as doping material in NIR-OLEDs, EDFA/YEDFAs, security inks, doped transparent films for greenhouses, liquid crystal screens and NMR shift reagents or solar cells, amongst other devices.

Description

OCTACOORDINATED TERNARY COMPLEXES OF ERBIO (III) OR ITERBIO (III) OPTICALLY ACTIVE AND METHOD OF OBTAINING

FIELD OF THE TECHNIQUE

The present invention belongs to the field of the synthesis of new ternary complexes of lanthanides (III) comprising different ligands and, specifically, to octacoordinated complexes of erbium (III) and ytterbium (III) optically active, in which the lanthanide ion is found coordinated with three betadicetonate ligands and a Lewis base ligand; and its use as film dopants, inks, OLED and NIR-OLED devices, EDFA / YEDFAs and solar cells.

STATE OF THE TECHNIQUE

In general, ternary complexes of lanthanides (I I I) with different ligands are considered useful as emitters. Also known are problems due to extinguishing that may occur, due to hydration and other causes, and that lead to minimize (or invalidate) its application in engineering devices. Favorable results are obtained when fluorinated betadicetonate ligands and Lewis bases are used. Such ternary complexes are well known in the case of europium (III) but not in the case of erbium (III) and ytterbium (III), infrared emitters (K. Binnemans. Rare earth beta-diketonates. Chapter 25. Handbook on the Physics and Chemistry of Rare Earths. Vol 35, ed KA Gschneider, J-CG Bünzli and VK Pecharsky. 2005 Elsevier BV). The cause must be sought in that the characterization of the infrared emission requires instrumental equipment not always available.

In fact, the series of complexes tris (dicetone) mono (Lewis base) lanthanide (III), [Ln ^ -dicetone) 3 (N, N-donor)], object of claim, is entirely new and only the following background They have appeared after exhaustive bibliographic searches: an analogue of the tris complex (6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedione) mono (5-nitro-l, 1- phenanthroline) erbium (111) , [Er (Hfod) ₃ (5 0 ₂ p in)], which includes bipyridine instead of 5 Ü ₂ p as a donor ligand, published by Iftikhar, K; M. Sayeed M; Ahmad, N. in Inorg. Chem., 1982, 21:80, and that does not exhibit luminescent properties;

the erbium and iterbium analogs of the tris (dibenzoylmethane) mono (2,2'-bipyridine) erbium (III) complex,

[Er (Hdbm) ₃ (bipy)], which include the batophenanthroline ligand instead of pyridine, reported by Kawamura Y; Wada, Y; Yanagida, S. in Jpn. J. Appl. Phys. 2001, 40: 350-356; Y

the Er (Hfac) ₃ bipy complex, published by Van Staveren, DR; van Albada, GA; Haasnoot, JG; Kooijman, H. et al. in Inorg. Chim. Acta, 2001, 315: 163.

DESCRIPTION OF THE INVENTION

General description

The main objective of this invention is to describe a series of octacoordinated complexes of erbium and iterbium and to provide some of their structures, their luminescent properties and their engineering applications in Optoelectronics, as well as to disclose a general method (together with some variants) of preparing said complex. This invention concerns new ternary complexes of lanthanides (III) comprising different ligands, specifically of optically active erbium (III) or yerbium (III) complexes, in which the lanthanide ion is coordinated with three betadicetonate ligands and one base ligand from Lewis. These complexes have photoluminescent and non-linear optical properties. The present invention also relates to the versatile use of the complexes described as doping material in many different devices, such as OLED and NIR-OLEDs, EDFAs / YEDFAs, solar cells and any other device. that changes its optical state under irradiation or voltage application.

Specifically, the invention corresponds to optically active octacoordinated ternary complexes of erbium (III) or iterbium (III) having the general formula:

[Ln ^ -dicetone) _x (N, N-donor)] where Ln is Er (erbium) or Yb (ytterbium); (β-diketone) 3 represents three betadicetonate ligands; and (N, N-donor) represents a Lewis base ligand.

Another method of the present invention is the method of preparing the erbium (III) or iterbium (III) complexes described above. Said process is characterized in that it comprises the mixing, in solution and stirring, of molecular amounts of compounds that ensure the presence of erbium or ytterbium, diketone and Lewis base ligand in 1: 3: 1 proportions.

Detailed description

As for the claimed family of compounds, the β-diketonate ligand (which, in number of 3 coordinates to the central ion) can be fluorinated or not; and the N, N-donor or Lewis base ligand is preferably, and interchangeably, 5-nitro-1, 10-phenanthroline, batophenan-troline or 2,2-bipyridine.

The most representative erbium (III) or ytterbium (III) complexes of those disclosed herein, although not the only ones possible within the exposed combinations, are the tris (diketone) mono (Lewis base) lanthanide (I I):

tris (dibenzoylmethane) mono (2,2'-bipyridine) erbium (III), tris (acetylacetone) mono (batophenanthroline) erbium (III), tris [3-tri fluoromethylhydroxymethylene) -d-camphor] mono (2, 2 '- bipyridine) erbium (III),

tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (batophenantroline) erbium (III),

tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (2,2'-bipyridine) erbium (III), tris (1, 1, l-trifluoro-2, 4-pentanedione) mono (2, ^2' -bipyridine) erbium (III),

tris (1, 1, l-trifluoro-5, 5-dimethyl-2, 4-hexanedione) mono (5- nitro-1, 10-phenanthroline) erbium (III),

tris (1, 1, 1,5,5, 6, 6,7,7,7-decafluoro-2,4-heptanedione) mono (5-nitro-l, 10-phenanthroline) erbium (III),

tris (6,6,7,7,8,8, 8-heptafluoro-2, 2-dimethyl-3, 5- octanedione) mono (5-nitro-l, 10-phenanthroline) erbium (III), and their corresponding Ytterbium complexes.

The structural elucidation of most ternary complexes of erbium (III) or ytterbium (III) with / 3-diketonates constituting the claimed series has been obtained by X-ray diffraction. None of the structures obtained responds to the forecast of the proposed coordination polyhedra (a dodecahedron with Ü2d symmetry or a square antiprism with D _4d symmetry), because such coordination polyhedra are so seriously distorted that it is not possible to decide the analogy with one or other prototype. Normally, the symmetry around a rare earth ion is Ci (without symmetry elements). Two of the complexes belonging to the claimed series have the structures and packaging that appear in Figure 1.

Although in all structures the coordination polyhedron consists of two terminal β-diketonate oxygens and two terminal pyridyl nitrogen, the arrangement of monomeric species in the crystalline network is very different throughout the series of complexes studied. These differences are due to the variation of the nature and properties of the ligands: stiffness of the molecule Ν, Ν-donora (greater for batophenantroline than for 2, ^2'- bipyridine); electroaceptor capacity of ligand / 3-diketonate (higher in fluorinated ligands due to the inductive effect of CF3 groups) or others and that are the cause of the versatility of the physical properties (and applications) shown by the claimed series of complexes.

With regard to the method of synthesis and obtaining of this family of compounds, and given its character of ternary complexes, its attainment may preferably be carried out well from the three basic constituents (erbium or yerbium salt, diketone and Lewis base) or from the binary trisbetadicetonate complex of erbium or iterbium and the Lewis base species. The first of these possibilities involves a process in two steps or stages while the second is a preferred case, achievable in a single step or stage.

In the two more preferred preferred embodiment, the preparation method comprises:

- mixing in a molecular ratio 1: 3: 3 a solution of a binary compound of erbium (III) or iterbium (III) in a suitable solvent, with a solution of a beta-diketone in a suitable solvent and an alkalizing agent in a suitable solvent ; Y

adding to said mixture a solution of a Lewis base ligand (preferably selected from the group consisting of 2,2'-bipyridine, batophenantroline and 1, 10-phenanthroline) in a suitable solvent and in molar proportion such that the molar ratio is obtained Binary salt: diketone: Lewis base = 1: 3: 1, and stir the final mixture.

Preferably, the binary compound of erbium or ytterbium to be used in the immediately described embodiment is a nitrate or a triflate. Also preferably, the preferred alkalizing agent is an alkali metal methylate (for example sodium or potassium) or an alkali metal hydroxide (for example cesium). Preferably, the solvent to be used for dissolution is an alcohol (for example, methanol or ethanol) or an acetonitrile. When a nitrate is used as the primary source of erbium or ytterbium (for example, Er (NO ₃ ) 3.9H ₂ 0 or Er (NO ₃ ) 3.9¾0), it is preferable to associate it with an alcoholic solution as a solvent (methanol or ethanol) and a methylate (for example, sodium or potassium) as an alkaline pH adjusting medium.

When an erbium (Er (CF3 S O3) 3) or ytterbium (Yb (CF3 S O3) 3) triflate is used as the primary source of erbium or iterbium, respectively, it is preferable to associate it with an acetonitrile solution and the use of hydroxide of cesium as alkalizing.

Preferably, the amount of alkalizing agent that is added to the 1: 3 mixture of binary compound of erbium or iterbium-betadicetone should be in a 25% concentration in the appropriate solvent.

In any of the above cases, the amounts to be used of the complex reagents or single salt of erbium or iterbium - betadicetone - Lewis base ligand, regardless of whether it is worked at a micromolar, millimolar, molar or kilomolar scale, keep the molar ratio 1 : 3: 1 reviewed.

When working on a millimolar scale, the amounts of solvent to be used for the 1: 3 mixture of binary compound of erbium or iterbium-betadicetone are between 10 and 40 mL, including both limits, and the amount of Lewis base ligand between 5 and 15 mL, including both limits. For higher or lower scales, the quantities to be used will be multiples or submultiples of the above.

The stirring time of the final mixture is preferably between 1 and 8 hours, more preferably 5 hours.

In the realization in one step, a case preferred for its simplicity and which presupposes the availability of the binary trisbetadicetonate complex, in which the erotic ion or Ytterbium is already linked to beta-diketone forming a complex that has a 1: 3 ratio, the preparation method comprises:

mixing in equimolecular amounts 1: 1 a solution of an erbium (III) or ytterbium (III) trisbetadicetonate complex in a solvent and an alkalizing agent in a solvent (which facilitates mixing and mixing with trisbetadicetonate) with a solution of a ligand Lewis base in a solvent. (Since the erbium or iterbium trisbetadicenate maintains a 1: 3 molar ratio between the erbium or iterbium complex and the betadicetonate, in this embodiment the desired 1: 3: 1 ratio is achieved).

Preferably in both solutions, both erbium or iterbium trisbetadiceonate and Lewis base, the solvent is alcohol, and more preferably the solutions are ethanol, that is, the solvent used in both cases is ethanol.

It should be understood from this text that the method of preparing erbium or iterbium complexes can encompass any of the possible combinations among all the alternatives offered.

Another purpose of the present invention is to provide new optically active (non-linear) materials for application in engineering Optoelectronics and Telecommunications devices, mainly NIR-OLEDs, EDFA / YEDFAs. These complexes can be advantageously used in other applications such as inks, transparent films doped for greenhouses, liquid crystal displays and NMR displacement reagents.

Because in most of the complexes studied, non-symmetry is preserved throughout the physical dimensions of the global structure, It claims here for the entire series of compounds their potential and use as non-linear optical materials (NLO materials) and their applications as such in areas such as Optoelectronics and Photonics. In relation to the second-order response and in aspects of operating conditions, the favorable influence of chloroform vapors in the generation of the second harmonic is claimed. Regarding the third-order NLA response, its application is claimed as a support for the propagation of spatial optical solitons.

The present invention also encompasses the versatile use of the complexes described as doping elements, preferably in very different devices such as films, security inks, organic light emitting diodes (OLEDs) and emitting in the NIR (NIR-OLEDs), EDFAs / YEDFAs, solar cells and any other device that changes its optical state under irradiation or voltage application. The present invention also relates to the use in horticulture of the claimed complexes; The mixture of several of these complexes, some emitters in the blue and other emitters in the red and the near infrared, can be used as a dopant in plastics for greenhouses because they produce an increase in their average service life and more efficient use of your solar energy.

Obviously, any of the devices described comprising any of the erbium or iterbium complexes described is also subject to protection of the present application; a solar cell, a security ink, a NIR-OLEDs device, an EDFA / YEDFAs device, a film such as the doped transparent ones used for greenhouses, liquid crystal displays and NMR displacement reagents, etc.

BRIEF DESCRIPTION OF THE FIGURES (y.U5.2ül2

FIGURE 1 . Structure and packaging of two erbium and iterbium complexes obtained in Example 1: [Er (Hacac) ₃ bath] (left graphs) and

[Yb (Hfhd) ₃ (5N0 ₂ phen)] (right graphics).

FIGURE 2 Emission spectra in methanol after excitation at 522 nm for the compounds [Er (Hhfc) ₃ (bath)] (upper graph) and [Er (Hfhd) ₃ (5N0 ₂ phen)], [Er (Htpm) ₃ (5N0 ₂ phen)] and [Er (Hfod) ₃ (5N0 ₂ phen)] (bottom chart).

FIGURE 3. Evaluation of the photoluminescence of the samples in the NIR region after excitation at 350 nm and 522 nm. for the complexes [Er (Hacac) ₃ (bath)] (upper graph) and [Er (Hfhd) ₃ (5N0 ₂ phen)] (lower graph).

EXAMPLES OF EMBODIMENT OF THE INVENTION

The following describes, by way of example and not limitation, a specific embodiment of the invention, where the preferred preparation of some of the claimed complexes is shown, and both its luminescent properties and its potential engineering applications in Optoelectronics are analyzed.

Example 1 . Preparation of octacoordinated complexes of erbium (III) or ytterbium (III) optimally active in accordance with the present invention.

Various optically active octabordinate complexes of erbium (III) and ytterbium (III) have been prepared from the following procedure:

Er (N0 ₃ ) ₃ .9H ₂ 0 -or its corresponding ytterbium nitrate- (0.451 g, 1 mmol) is mixed with a β-diketone (3 mmol) in methanol (20 mL) and an equimolecular amount of methylate solution Potassium (0.841 g, 3 mmol) at 25% in methanol and the subsequent addition, to the previous mixture (25 mL), of 10 mL of a 2,2'-bipyridine, batophenantroline or 1, 10-phenanthroline methanol solution (1 mmol). This reaction mixture is stirred at reflux for 5 hours. If a white precipitate (potassium nitrate) appears during stirring, decant repeatedly. The solution

REPLACEMENT SHEET (Rule 26) clear thus obtained provides pinkish-yellow microcrystals.

The complexes obtained are the following:

tris (acetylacetone) monkey (batophenantroline) erbium (III),

[Er (Hacac) ₃ (bath)];

tris (2, 4-hexanedione) mono (batophenantroline) erbium (III), [Er (h) ₃ (bath)];

tris (2,2,6,6, -tetramethyl-3, 5-heptanedione) mono (bato-phenanthroline) erbium (III), [Er (Hthd) 3 (bath)];

tris (2, 6-dimethyl-3, 5-heptanedione) mono (batophenantroline) erbium (III), [Er (Hdmh) ₃ (bath)];

tris (2, 6-dimethyl-3, 5-heptanedione) mono (5-nitro-l, 10-phenanthroline) erbium (III), [Er (Hdmh) 3 (5N02phen)];

tris (2, 6-dimethyl-3, 5-heptanedione) mono (2, 2-bipyridine) erbium (III), [Er (Hdmh) ₃ (bipy)];

tris (2,4-hexanedione) mono (2,2-bipyridine) erbium (III),

[Er (hd) 3 (bipy)];

tris (3, 5-heptanedione) mono (2, 2-bipyridine) erbium (III),

[Er (hpd) 3 (bipy)];

tris (octanedione) mono (2,2-bipyridine) erbium (III),

[Er (od) 3 (bipy)];

tris (nonanodione) mono (2,2-bipyridine) erbium (III),

[Er (nd) 3 (bipy)];

tris (methyl-2-oxocyclopentanecarboxylate) mono (2, 2- bipyridine) erbium (III), [Er (MCPC) 3 (bipy)];

tris (ethyl-2-oxocyclohexanecarboxylate) mono (2, 2- bipyridine) erbium (III) [Er (ECHC) 3 (bipy)];

tris (dibenzoylmethane) mono (2,2'-bipyridine) erbium (III),

[Er (Hdbm) ₃ (bipy)];

tris [3-trifluoromethylhydroxymethylene) -d-camphor] mono (2,2'-bipyridine) erbium (III), [Er (Hfacam) 3 (bipy)];

tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono

(batophenantroline) erbium (III), [Er (Hhfc) 3 (bath)];

tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (2,2'-bipyridine) erbium (III), [Er (Hhfc) 3 (bipy)]; tris (1, 1, l-trifluoro-2, 4-pentanedione) mono (2, 2'-bipyridine) erbium (III), [Er (Htfac) 3 (bipy)];

tris (1, 1, l-trifluoro-5, 5-dimethyl-2, 4-hexanedione) mono (5- nitro-1, 10-phenanthroline) erbium (III), [Er (Htpm) 3 (5NÜ ₂ p in )]; tris (1, 1, 1,5,5, 6, 6,7,7,7-decafluoro-2,4-heptanedione) mono (5-nitro-l, 10-phenanthroline) erbium (III),

[Er (Hfhd) 3 (5N0 ₂ phen)];

tris (6,6,7,7,8,8, 8-heptafluoro-2,2-dimethyl-3, 5- octanedione) mono (5-nitro-l, 1-phenanthroline) erbium (III),

[Er (Hfod) 3 (5N0 ₂ phen)];

and its corresponding iterbium complexes.

Example 2. Description of properties and applications of the erbium and iterbium complexes of Example 1.

In solution, the labile nature of the complexes, their proclivity to association and their susceptibility to the formation of adducts with solvent molecules do not favor the presence of monomeric species. The extent of self-association has the following solvent dependence: τι-hexane> carbon tetrachloride> benzene> chloroform = methanol. Consequently, it is necessary to resort to dissolution in the more polar solvents, chloroform or methanol, where the claimed complexes are preferably in monomeric form, to carry out the desired property study. In this way, the information on physical properties obtained both in solid state and in solution can be related.

It has been found that in most of the complexes studied, non-symmetry is preserved throughout the physical dimensions of the global structure, demonstrating its potential as non-linear optical materials (NLO materials) and their applications as such in areas such as Optoelectronics and Photonics. In relation to the second-order response and in aspects of operating conditions, the favorable influence of chloroform vapors in the generation of the second harmonic. Regarding the third-order NLA response, its application is claimed as a support for the propagation of spatial optical solitons.

The study of the excitation and emission spectra in chloroform for the [Er (Hacac) 3bath] and [Er (Hthd) ₃ bath] complexes shows down-conversion: after excitation at 350 nm emission is observed in the 365- 600 nm with maximums in bluish violet at 398 nm and 420 nm, respectively. This claim is claimed here and its application in horticulture because both radiations, red and blue, are essential for plant growth during all stages of development. The mixture of the two complexes mentioned (emitters in blue) with any of the other complexes in the series (emitters in red and near infrared) can be used as a dopant in plastics for greenhouses because they produce an increase in their life Medium service and more efficient use of your solar energy. The greater growth and development of plants under such plastic films is known as the Polysvetan effect. Currently, compounds containing europium (III) for dispersion in polymeric films are being marketed under the name Ksanta by Ranita (Regensburg, Germany) and polymeric films incorporating the Ksanta additive are commercially available under the name Redlight.

The feature described above can also be applied in security inks. These inks are used as countermeasures to counterfeiting for the protection of bills, checks, cards and valuable documents. The security inks are invisible but they flash in different colors (they can do it in red, blue and infrared in the case of Er ³⁺ ) under irradiation with ultraviolet light. Euro bills

ΟOy..υu ^ j .. υuιi

they show, under ultraviolet irradiation, emitting fibers and diagrams in red, blue and green and although the exact composition of these security inks is kept secret for obvious reasons, it is very likely that the red color is due to the emission of a complex - europium diicetonate (III). The complex series is therefore claimed as an alternative to the Eu ³⁺ complexes in security inks.

The study of the emission spectrum in methanol after excitation at 522 nm (Figure 2) has helped establish the emission half-lives (τ) of the complexes studied and with them, the following sequence:

[Er (Hdbm) ₃ (bipy)] (5.4 s)> [Er (Hhfc) ₃ (bath)] (3 ps)>

[Er (Hfhd) ₃ (5N0 ₂ phen)] (1.45 μβ)>

[Er (Htpm) ₃ (5N0 ₂ phen)] (1.4 μβ) = [Er (Hfod) ₃ (5N0 ₂ phen)] (1.4 μβ) = [Er (Htfac) ₃ (bipy)] (1.4 με)> [ Er (Hthd) ₃ (bath)] (1.3 μβ)

> [Er (acac) ₃ (bath)] (1 με)

The photoluminescence (PL) of the complexes has been measured in the near infrared region (NIR) after excitation at wavelengths of 350 (UV-vis source) and 522 nm (Argon laser). In a study on the effect of the excitation of the previous wavelengths on the intensity of the luminescence for the complexes [Er (Hacac) ₃ (bath)] (sample 1; upper graph) and [Er (Hfhd) ₃ (5N0 ₂ phen)] (sample 2, lower graph), we have observed (Figure 3) that after excitation at 522 nm the intensity of the PL is half or one third of that achieved after excitation at 350 nm. This finding is claimed for its application to devices in which hosts of polymeric or vitreous nature are doped with ternary / 3-diketonate complexes to obtain emission in the region of 1532 nm region, the so-called third telecommunications window.

The study of PL efficiency in solution has only been carried out, to date, for tris (dibenzoylmethane)

REPLACEMENT SHEET (Rule 26) mono (2, 2'-bipyridine) erbium (III), [Er (Hdbm) 3 (bipy)], which has shown the classic narrow band due to ff transitions transitions in the NIR region at 980 and 1532 nm, with a result of cp _PL = 7.2><10 ^{~ 5} .

On the other hand, most of the complexes of the claimed series have been used as active components in light emitting organic diodes (OLEDs) that emit in the NIR (NIR-OLEDs). Here, NIR-OLEDs have been manufactured with the ITO / PEDOT configuration: PSS (50 nm) / active layer / Ca (20 nm) / Al. The characteristics of the current device (J) -voltaj e (V) have been measured using an Agilent 4155C semiconductor parameter analyzer and an Agilent 41501B SMU pulse generator. The J-V curves with the highest slope are those obtained for devices with [Er (Hhfc) 3 (bath)] and [Er (Hdbm) 3 (bipy)] in their emitter layers. These devices have potential in laser technology, optical sensors and telecommunications.

The phenomenon of up-conversion has been shown in many systems but, preferably, in those constituted by active ions of the lanthanides in a host material. For silicon solar cells, erbium (III) is a good choice as an active ion because it absorbs at wavelengths lower than the wavelength that corresponds to the silicon band gap (1.1 μιη) and emits within the range of absorption of silicon. A transparent vitreous material doped with lanthanide / 3-diketonate complexes is claimed that exhibits up-conversion efficiencies two orders of magnitude better than its precursor glasses. Bi- and tri- photonic absorption processes give rise to three emission bands in this material centered at 550, 650 and 980 nm under infrared excitation at 1480 nm. This material could be used to make high efficiency silicon solar cells. Mesoporous silica glass, ZBLAN fluorinated glass and fluorophosphate glass have been doped indistinctly with the complexes of the claimed series and their application for the manufacture of EDFA and YEDFA devices has been demonstrated. Based on the results, the addition of the new complexes with fluorinated ligands to phosphate-fluorinated glasses is claimed as a resource for the optimization of EDFAs and YEDFAs.

Claims

1. An octacoordinated ternary complex of erbium (III) or optically active iterbium (III), where the erbium or iterbium ion is coordinated with three betadicetonate ligands and one Lewis base ligand, according to the following general formula:

[Ln ^ -dicetonate) 3 (N, N-donor)] where Ln is Er or Yb; (β-diketonate) 3 represents three betadicetonate ligands; and (Ν, Ν-donor) a Lewis base ligand.

2. A complex according to claim 1, characterized in that the β-diketonate is fluorinated.

3. A complex according to any one of claims 1 or 2, characterized in that the ligand Ν, Ν-donor is selected from the group consisting of: 5-nitro-l, 10-phenanthroline, batophenantroline and 2,2-bipyridine. 4. A complex according to any one of the preceding claims, characterized in that it is selected from: tris (acetylacetone) mono (batophenanthroline) erbium (III),

[Er (Hacac) 3 (bath)];

tris (2,4-hexanedione) monkey (batophenantroline) erbium (III),

[Er (h) 3 (bath)];

tris (2,2,6,6, -tetramethyl-3, 5-heptanedione) mono

(batophenantroline) erbium (III), [Er (Hthd) 3 (bath)];

tris (2,6-dimethyl-3, 5-heptanedione) mono (2, 2-bipyridine) erbium (III), [Er (Hdmh) 3 (bipy)];

tris (2,4-hexanedione) mono (2,2-bipyridine) erbium (III),

[Er (hd) ₃ (bipy)]; tris (3, 5-heptanedione) mono (2, 2-bipyridine) erbium (III),

[Er (hpd) ₃ (bipy)];

tris (octanedione) mono (2,2-bipyridine) erbium (III),

[Er (od) ₃ (bipy)];

tris (nonanodione) mono (2,2-bipyridine) erbium (III),

[Er (nd) ₃ (bipy)];

tris (methyl-2-oxocyclopentanecarboxylate) mono (2, 2- bipyridine) erbium (III), [Er (MCPC) ₃ (bipy)];

tris (ethyl-2-oxocyclohexanecarboxylate) mono (2, 2- bipyridine) erbium (III) [Er (ECHC) ₃ (bipy)];

tris (dibenzoylmethane) mono (2,2'-bipyridine) erbium (III),

[Er (Hdbm) ₃ (bipy)];

tris [3-trifluornethylhydroxymethyl) -d-camphor] mono (2,2'-bipyridine) erbium (III), [Er (Hfacam) 3 (bipy)];

tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (batophenanthroline) erbium (III), [Er (Hhfc) 3 (bath)]; tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (2,2'-bipiridine) erbium (III), [Er (Hhfc) 3 (bipy)]; tris (1, 1, l-trifluoro-2, 4-pentanedione) mono (2, 2'-bipyridine) erbium (111), [Er (Htfac) 3 (bipy)];

tris (1, 1, l-trifluoro-5, 5-dimethyl-2, 4-hexanedione) mono (5- nitro-1, 10-phenanthroline) erbium (III), [Er (Htpm) 3 (5NÜ ₂ phen) ]; tris (1,1,1,5,5,6,6,7,7, 7-decafluoro-2,

4-heptanedione) mono (5-nitro-l, 10-phenanthroline) erbium (III),

[Er (Hfhd) 3 (5N0 ₂ phen)];

tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3, 5- octanedione) mono (5-nitro-1, 1-phenanthroline) erbium (III),

[Er (Hfod) 3 (5N0 ₂ phen)];

and its corresponding iterbium complexes.

5. Method of obtaining an erbium (III) or ytterbium (III) complex described in any one of the preceding claims, characterized in that it comprises mixing and stirring, in solution, molecular amounts of compounds that ensure the presence of erbium or ytterbium, diketone and Lewis base ligand in 1: 3: 1 ratios.

6. Method according to the preceding claim, characterized in that it comprises:

- mixing in a molecular ratio 1: 3: 3 a solution of a binary compound of erbium (III) or iterbium (III) in a solvent with a solution of a beta-diketone in a solvent and an alkalizing agent in a solvent, and - adding to said mixture a solution of a Lewis base ligand in a molar ratio solvent such that the 1: 3: 1 molar ratio is obtained, and stir the final mixture.

7. Method according to claim 6, characterized in that the compound of erbium or iterbium is a nitrate or an erbium or iterbium triflate.

8. Method according to any one of claims 6 or 7, characterized in that the solvent is selected from an alcohol and acetonitrile.

9. Method according to claim 8, characterized in that the alcohol is methanol or ethanol.

10. Method according to any one of claims 6 to 9, characterized in that the alkalizing agent is selected from alkali metal methylate and an alkaline hydroxide.

11. Method according to claim 10, characterized in that the methylate is sodium or potassium and the hydroxide is cesium.

12. Method according to any one of claims 7 to 11, characterized in that when the erbium or iterbium compound is a nitrate, the solvent is methanol or ethanol and the alkalizing agent is sodium or potassium methylate.

13. Method according to any one of claims 7 to 11, characterized in that when the erbium or iterbium compound is a triflate, the solvent is acetonitrile and the alkalizing agent is cesium hydroxide.

14. Method according to any one of claims 6 to 13, characterized in that the concentration of alkalizing agent in the solvent is 25%.

15. A method according to any one of claims 5 or 6, characterized in that the compound of erbium or iterbium is erbium or iterbium trisbetadicetonate, wherein the erbium or iterbium complex is bound to betadicetone in a 1: 3 ratio.

16. Method according to claim 15, characterized in that it comprises:

Mix in equimolecular amounts 1: 1 a solution of an erbium (III) or ytterbium (III) trisbetadicetonate complex in a solvent and an alkalinizer in a solvent with a solution of a Lewis base ligand in a solvent.

17. Method according to claim 16, characterized in that the solvent in the two solutions is ethanol.

18. Method according to any one of claims 6 to 17, characterized in that, when It works on a millimolar scale, the amount of solvent to be used for the mixture that contains the erbium or iterbium and betadicetonate ions is between 10 and 40 mL, including both limits, and that which contains the Lewis base ligand between 5 and 15 mL , including both limits.

19. Method according to any one of claims 6 to 18, characterized in that the stirring time of the final mixture is between 1 and 8 hours.

20. Use of an erbium (III) or ytterbium (III) complex as described in any one of claims 1 to 4 as a non-linear optical material.

21. Use of an erbium (III) or ytterbium (III) complex as described in any one of claims 1 to 4 as a support for the propagation of spatial optical solitons.

22. Use of an erbium (III) or ytterbium (III) complex as described in any one of claims 1 to 4 as a doping material.

23. Use according to claim 22, characterized in that the erbium (III) or iterbium (III) complex is used as a doping material in one of the devices selected within the group consisting of: films, safety inks, emitting organic diodes of light, OLED diodes emitting in the NIR, EDFAs / YEDFAs, solar cells, liquid crystal displays and NMR displacement reagents, and any other device that changes its optical state under irradiation or voltage application.

24. Use according to claim 23, characterized in that the film is a transparent film doped for use in greenhouses.

25. Use according to claim 24 in Horticulture.

26. Security ink characterized in that it comprises the complex of erbium (III) or iterbium (III) described according to any one of claims 1 to 4.

27. Organic light emitting diode, OLED, characterized in that it comprises the erbium (III) or iterbium (III) complex described according to any one of claims 1 to 4.

28. Diode according to claim 27, characterized in that it is a diode emitting in the NIR.

29. Fiber optic amplifier characterized in that it comprises the erbium (III) or iterbium (III) complex described according to any one of claims 1 to 4.

30. Solar cell characterized in that it comprises the complex of erbium (III) or iterbium (III) described according to any one of claims 1 to 4.

31. Liquid crystal display characterized in that it comprises the complex of erbium (III) or iterbium (III) described according to any one of claims 1 to 4.