GB2410946A - Luminescence emitting lanthanide organic ternary complexes comprising a bis(sulphonyl)imide ligand & a bi- or tri- dentate heterocyclic ring (system) - Google Patents

Abstract

A method for obtaining an intense luminescence, [said method] comprises the steps of preparing a complex comprising a lanthanide, 1 or more bis(sulfonyl)imide ligands and 1 or more bidentate or tridentate heterocyclic rings and irradiating the complex with a wavelength in the range of 25 nm above or under the maximum of the excitation spectrum of said complex measured in the range of the luminescence wavelength of the lanthanide, hereby excluding the direct excitation in the lanthanide of said complexes. Such a lanthanide organic ternary complex may be used as luminescence emitting complexes in advanced optically amplifying material for data communications and telecommunications applications. They exhibit near-IR and visible light luminescence. A lanthanide organic ternary complex according to following formula I are claimed per se, wherein: <EMI ID=1.1 HE=47 WI=50 LX=721 LY=1118 TI=CF> <UL ST="-"> <LI>the dotted lines represent one double bond, which is dispersed over several bonds; <LI>n is any integer from 1, 2, 3 or 4; <LI>L is selected from the group of lanthanides; <LI>B is selected from neutral bidentate and tridentate heterocyclic rings, optionally substituted with one or more R<8>; </UL> R<1>, R<2>, X & Y are as defined in claim 1; and with the proviso that: at least one of R<1,> R<2>, X or Y contains hydrogen.

Description

I

24 10946

INTENSE LUMINESCENCE

FIELD OF THE INVENTION

The present invention relates to new near-IA and/or visible light luminescence emitting lanthanide organic ternary complexes, compositions thereof and to the use of said lanthanide organic ternary complexes In particular, the erbium organic complex shows an intense near- infrared luminescence which can be used for amplifications of telecommunication signals The present invention also relates to a method for obtaining intense near-lR or visible light luminescence, said method comprising the use of the lanthanide organic ternary complex of the invention and comprising indirect excitation of the lanthanide through its ligands

BACKGROUND OF THE INVENTION

Near-IR and visible light luminescence emitting complexes are very useful in a lot of fields Luminescence emitting molecules can be used in the field of security documents or articles, in order to be able to determine the authenticity of such documents or articles, or in the field of Organic Light Emitting Diodes (OLED) or in other application fields More in particular, near-lR luminescence emitting complexes can for example be applied in the telecommunication sector as optical amplifiers The increasing demand for high-speed information transfer is driving the switch from electrical to optical communication systems for which the amplification of telecommunication signals forms a very important application Rare-earth metal ions, with relatively long luminescence lifetimes, are commonly applied in this field In optical amplification the long excited-state lifetime makes it easier to obtain population inversion, a requirement for effective stimulated emission Unfortunately the absorption cross section of rare-earth ion transitions is extremely low For optical amplification, the wavelength regions around 1300 and 1550 nm, which can be covered with neodymium and erbium complexes, respectively, are the most important for applications in optical telecommunication Amplification of telecommunication signals is currently achieved by using erbium-doped glass fibre amplifiers These amplifiers are based on the infrared photoluminescence of the trivalent erbium ion around 1550 nm This technology is well-established, but the cost per unit is extremely high Such costs will hold back the implementation of more evolved networks in coming years, which is likely to require a far greater density of amplifiers Besides the high cost, erbium-doped glasses have the disadvantage that only low doping concentrations can be achieved (often as low as 01 mol %) An erbium-doped polymer material would provide in principle a lower cost, more versatile system for amplification in the 13-16 micron range Much higher doping concentrations can be obtained with erbium- doped polymers than with erbium-doped glasses Erbium-doped polymer materials are potentially simpler to prepare and to process than erbiumdoped silicon, which is currently generating a lot of interest However, most of the presently known luminescent erbium systems are based on inorganic systems, such as monocrystals, powders or glasses These materials are not compatible with polymeric matrices, in the sense that these materials have a very low solubility in a polymer matrix and it is very difficult to disperse them in the polymer . . . ë On the other hand, lanthanide complexes with organic ligands are compatible with polymer matrices.

During the last years, by using rare-earth metals in combination with sensitized excitation by means of a suitable organic molecule, efficient excitation can be obtained The advantages of this approach are manifold Low-cost light sources are available for the visible part of the spectrum, and interferences from the matrix (scatter, absorption) are minimal Detection in the near-lR is almost interference-free Considerable efforts have been made to obtain lanthanide-containing complexes which show luminescence in the infrared However, most of these studies have been limited to neodymium(III) and ytterbium(III) complexes, because observing the 1550 nm luminescence of erbium(llI), is a much greater challenge. Slooff et al described the encapsulation of Er3+ in a polydentate cage [1] This complex shows room temperature photoluminescence at 1540 nm, after direct excitation into one of the 4f' levels (488 nm) or after indirect excitation at 287 rim via de aromatic part of the polydentate ligand For excitation, a laser source was used The full width at half maximum of the luminescence band was 70 nm Although this system shows rather good luminescence properties, its main disadvantage is that a long multistep synthesis is required to obtain the ligand Curry and Gillin measured infrared electroluminescence of the tris(8-hydroxyquinolinato)erbium(III) complex [2], but the luminescence intensities were rather low Yanagida and coworkers described an interesting approach for intensifying the nearinfrared luminescence of Nd3+, by using bis(perfluoroalkanesulfonyl) imides as ligand [3,4]. The authors obtained complexes with inorganic chelate rings in which no C-H, N-H or O-H vibrations can occur close to the neodymium ion. The presence of these chelate rings reduces the amount of radiationless deactivation. The composition of the complexes is assumed to be a tris complex (three ligands for one neodymium ion) Typically, the neodymium(llI) is excited by direct excitation in a 4f3 level (585 nary). These tris complexes and the formation of ternary complexes of these ligands with Lewis bases have been described in the patent applications WO 9840388 (US6300481 and EP0970959), WO 0222566 (EP1318143) In EP 1318148, the complexes [Ln(PMS)3(Phen)4] where Ln = Nd, Eu, PMS is bis(perfluoromethylsulfonyl)imide and Phen is 1,10 phenanthroline, are described and are typically excited directly into the lanthanide in order to obtain luminescence Previously also Hofstraat et al have shown that excitation in the visible part of the spectrum can be used to excite rareearth ions which luminesce in the near-IA, such as ytterbium, neodymium, and erbium, via a fluorescein-derivative as sensitizer [5] These complexes show however a low quantum yield and the ligands are difficult to synthesise Tn the field of the document security or articles, luminescent compounds are well known for the protection of banknotes, valued papers and other security articles Such compounds, known to include for example europium, terbium, ytterbium, thulium or erbium doped materials, may be incorporated into the security article's substrate, printed onto security articles via an ink, or affxed to security articles in the form of a security thread, a foil or a label carrying them Also the detection of luminescent security elements is well known in the art, but a particular problem herein is the discrimination of the weak luminescence signal from the often much stronger background signals, which are mostly due to environmental light The use of modulated excitation and synchronous detection has been proposed as a possibility to overcome this difficulty and improved detection apparatuses are described in the prior art However, a luminescent complex with high near- TR luminescent intensity would be very helpful! in this field, in order to overcome problems of detection C C C 1 C t C C C C C C C Summarising, there are already several lanthanide and more in particular erbium organic complexes described and prepared for their near-IA luminescence properties and also methods for obtaining luminescence are described, but all existing complexes and methods still encounter problems like a low output intensity or difficult synthesis Another problem is the fact that coordinating solvents have to be avoided when working with these complexes and that the complexes have a low luminescence when dissolved in non-deuterated organic solvents Therefore, in view of the importance of the near-IA or visible light intense luminescence complexes for communication systems and other fields, there is a need for new rare-earth complexes with an intense near-lR luminescence and which are easily available and for new methods obtaining this intense near-IA luminescence

SUMMARY OF THE INVENTION

In the present invention, a new rare earth organic ternary complex is provided The present invention demonstrates also that lanthanide organic ternary complexes show an intense luminescence, when excited indirectly through the ligands of the lanthanide Therefore, they can for example be applied for amplifications of telecommunication signals or in securing documents, depending on the emission wavelength The present invention relates to a new rare-earth organic ternary complex, more in particular containing a lanthanide, yet more in particular containing erbium, ytterbium, thulium, holmium or neodymium The invention also relates to compositions comprising said new rare-earth organic ternary complex The invention further relates to the use of said new rare- earth organic ternary complex and composition thereof. The present invention furthermore relates to the process for preparing said new rare- earth organic ternary complex The present invention also relates to a method for obtaining intense luminescence by using the new rare- earth organic ternary complex and by indirectly exciting the rare-earth element through its lizards A first aspect of the invention relates thus to new rare earth organic ternary complexes. In a particular embodiment of the present invention, the rare earth element is of the lanthanide series In a more particular embodiment, the lanthanide possesses near-IA luminescence capabilities The near-lR luminescence emitting rare earth element is more in particular selected from erbium (Er), neodymium (Nd), ytterbium (Yb), dysprosium (Dy), thulium (Tm) and holmium (Ho) In a more particular embodiment of the invention, the rare earth element is erbium, a trivalent erbium ion (Er3+) One part of the rare-earth organic ternary complex is formed by one or more bis(sulfonyl)imide molecules so that the rare-earth element is surrounded by bidentate bis(sulfonyl)imide ligands, more in particular by negatively charged bidentate bis(sulfonyl)imide ligands Another part of the rare earth ternary complex is formed by a heterocyclic compound, more in particular a neutral heterocyclic compound, bidentate or tridentate In a more particular embodiment, the neutral heterocyclic compound is selected from 1,1 0-phenanthroline (phen), 2,2'-bipyridine (bipy), 2,2',6',2"- terpyridine (terpy) or 2-(2- pyridyl)benzamidazole and derivatives 8 He c c r 8 8 8 a 868..

8 c. . another particular embodiment, the present invention relates to complexes which according to the general embodiment of the invention correspond to complexes according to the general formula 1, salts, tautomers, solvates or isomers thereof, wherein Y-s o N\/, J \L B O n the dotted lines represent one double bond, which is dispersed over several bonds, n is any integer from 1, 2, 3 or 4, each X and Y is independently selected from the group consisting of a single bond or a divalent, saturated or unsaturated, substituted or unsubstituted C-Co hydrocarbon group optionally including one or more heteroatoms in or at the ends of the carbon atom chain, said heteroatoms being selected from the group consisting of O. S. and N (provided that said heteroatom is not linked to the S of the sulfonyl), such as C-6 alkylene, C26 alkenylene, C2 6 alkynylene, -O(CH2) 5-, -(CH2) 4-O-(CH2) 4-, -S-(CH2) 5-, -(CH2)' 4-S(CH2) 4-, -NR' t-(CH2) 5-, -(CH2) 4-NR'-(CH2) 4-and C3 '0 cycloalkylidene, each of said C'-C0 hydrocarbon group is optionally substituted with one or more R9; each R' and R2 can independently be perfluorinated, partially or not fluorinated and is independently selected from C224 alkyl, C3,o cycloalkyl, C224 alkenyl; C3 o cycloalkenyl, C2 24 alkynyl, C3 0 cycloalkynyl, each of said C2 24 alkyl, C3 '0 cycloalkyl, C2.24 alkenyl, C3 '0 cycloalkenyl, C2 24 alkynyl, C3 o cycloalkynyl optionally includes one or more heteroatoms in the carbon-atom chain or at the ends of said chain, said heteroatoms being selected from the groups consisting of O. S and N. aryl, arylalkyl, heterocyclic ring, and each of said C2 24 alkyl, C3 '0 cycloalkyl, C2 24 alkenyl, C3 0 cycloalkenyl, C2 24 alkynyl, C 0 cycloalkynyl, aryl, arylalkyl, heterocyclic ring is optionally substituted with one or more R3, Each R3, R8 and R9 can independently be perfluorinated, partially or not fluorinated and are independently selected from the group consisting of hydrogen, halogen, C, 24 alkyl, C2 24 alkenyl, C2 24 alkynyl; C3 0 cycloalkyl; C3 0 cycloalkenyl, C3 0 cycloalkynyl, each of said C 24 alkyl, C3 '0 cycloalkyl, C2 24 alkenyl, C3 o cycloalkenyl, C2 24 alkynyl, C3 0 cycloalkynyl optionally includes one or more heteroatoms in the carbon-atom chain or at the ends of said chain, said heteroatoms being selected from the groups consisting of O. S and N. oR4, SR4 CN, isocyano, thiocyano, isothiocyano, nitroso, NO2; NR5R6, sulfonate, haloalkyl, C(=o)R7, C(=S)R7, aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy (optionally a oxybenzyl), arylalkylthio (optionally a benzylthio), heterocyclic ring, oxyheterocyclic ring, thioheterocyclic ring, alkyl-heterocyclic ring, oxyalkyl- heterocyclic ring, thioalkyl- heterocyclic ring, Each R. R5, and R6 can independently be perfluorinated, partially or not fluorinated and are independently selected from the group consisting of H. OH, C 24 alkyl, C, 24 alkenyl, aryl; C 0 cycloalkyl, C4 0 cycloalkenyl, 5-6 membered heterocyclic ring, c a Each R7 can independently be perfluorinated, partially or not fluorinated and is independently selected from the group consisting of H. OH, Cat s alkyl, Cal 24 alkenyl, Cat 24 alkoxy; C,24 alkylthio, C3 it, cycloalkyl, C4,0 cycloalkenyl, aryl, 5-6 membered heterocyclic ring, L is selected from the group of lanthanides, B is selected from neutral bidentate and tridentate heterocyclic rings, optionally In a particular embodiment, the present invention relates to complexes of Formula I with the proviso that at least one of Ret, R2, X or Y contains hydrogen or at least one hydrogen is present in R', R2, X or Y In another particular embodiment, the present invention relates to complexes of Formula I wherein R'-Y and R2-X comprise at least 3 or 4 carbon atoms In another embodiment, L of the formula l is selected from the group consisting of erbium, neodymium, ytterbium, dysprosium and holmium In yet another embodiment, in the formula I, n is equal to 3 Optionally, the compounds of this invention do not include the compounds expressly disclosed in EP1318143, WO 98/40388, US 6300481 and WO 02/22566 or disclosed in the following articles K Sogabe et al Chem. Lett. (2000), 944 [6], Y Hasegawa, et al, Angew.

Them. 112 (2000) 365 [3], M Ryo, et al., J. Mater. C.hem. 12 (2002) 1748 [4], and Y Hasegawa et al, J. L?lmn. 101 (2003) 235 [7] In a particular embodiment, the invention relates to near-IA luminescence emitting complexes containing erbium, multiple (2 or 3), in particular 3, bis(sulfonyl)imide ligands and at least one bidentate or tridentate heterocyclic ring In a particular embodiment, the present invention relates to the complex of formula I where L is erbium and Z is 1,10phenanthroline or substituted analogues of 1,10-phenantroline like 4,7-diphenyl- 1,10-phenantroline, 2-biphenyl-imidazo[4,5-f] 1,10phenantroline and dipyrido[3,2-a 2',3'-c]phenazine. In yet a more particular embodiment, the ternary organic lanthanide complex is selected from the group consisting of tris(bi s(nonafluorobutylsulfonyl)imide)(1, 10-phenanthroline)erbium(III) [Er(N(SO2C4Fs)2)3 C 2HsN2], tris(bis(heptadecafluoroocylsulfonyl)imide)(1, 10phenanthroline)erbium(III) [Er(N(SO2CxF7)2)3 C2HxN2], tris((heptadecafluoroocylsulfonyl) (nonafluorobutylsulfonyl)imide)( l,10-phenanthroline)erbium(III) [Er((SO2CsF7)N(SO2C4Fg))3 C2HgN2], tris((pentafluorophenylsulfonyl)imide) (1,10- phenanthroline)erbium(lTI) [Er(N(SO2CGFs)2)3 C'2HsN2], tris(bis(nonafluorobutylsulfonyl)imide)(4,7-diphenyl- 1,10-phenanthroline) erbium(Ill) [Er(N(SO2C4F')2)3 C 2H6N2(C6H5)2], tris(bis(nonafluorobutylsulfonyl)imide) (1,10phenanthroline)neodymium(III) [Nd(N(SO2C4Fs)2)3 C'2HsN2], tris(bis(heptadecafluoroocylsulfonyl)imide)( l,10-phenanthroline) ytterbium(III) In a particular embodiment, the complexes of the present invention exhibit near-lR luminescence, more in particular between wavelenghts of 800 nm and 1700 nm, yet more in particular between 1500 nm and 1600 nm, yet more in particular in the range of 1550 nm A second aspect of the present invention relates to the use of complexes according to formula I as intense luminescence emitting complexes, intense visiblelight emitting complexes or intense near-lR emitting complexes. In a particular embodiment, the complexes can be used in optoelectronics applications, security documents or articles or for example in Organic Light Emitting Diodes (OLEDs) c c c c c ace c cec

C C

C C C C In a particular embodiment, the invention relates to the use of complexes as intense near-IA luminescence emitting complexes, which according to the general embodiment of the invention correspond to complexes according to the general formula II, salts, tautomers, solvates or isomers thereof, wherein

O

R Y-S O

N/' \L B R2 X-ISI -- O O n the dotted lines represent one double bond, which is dispersed over several bonds, n is any integer from 1, 2, 3 or 4, each X and Y is independently selected from the group consisting of a single bond or a divalent, saturated or unsaturated, substituted or unsubstituted C,-C,0 hydrocarbon group optionally including one or more heteroatoms in or at the ends of the carbon atom chain, said heteroatoms being selected from the group consisting of O. S. and N (provided that said heteroatom is not linked to the S of the sulfonyl), such as C,-6 alkylene, C26 alkenylene, C2 6 alkynylene, -O(CH2), 5-, -(CH2) 4-O-(CH2) 4-, -S-(CH2), 5-, -(CH2)' 4-S- (CH2)' 4-, -NR'-(CH2) 5-, -(CH2)' 4-NR'-(CH2) 4-and Cal,0 cycloalkylidene, each of said C-Co hydrocarbon group is optionally substituted with one or more R9, each R' and R2 can independently be perfluorinated, partially or not fluorinated and is independently selected from C224 alkyl; C3,0 cycloalkyl, C224 alkenyl, C3,0 cycloalkenyl, C2 24 alkynyl, C3,0 cycloalkynyl, each of said C2 24 alkyl, C3,0 cycloalkyl, C2 24 alkenyl, C3,0 cycloalkenyl, C2 24 alkynyl, C3,0 cycloalkynyl optionally includes one or more heteroatoms in the carbon-atom chain or at the ends of said chain, said heteroatoms being selected from the groups consisting of O. S and N. aryl, arylalkyl, heterocyclic ring, and each of said C2 24 alkyl, C3,0 cycloalkyl, C2 24 alkenyl, C3,0 cycloalkenyl, C224 alkynyl, C3,0 cycloalkynyl, aryl, arylalkyl, heterocyclic ring is optionally substituted with one or more R3; Each R3, R and R9 can independently be perfluorinated, partially or not fluorinated and are independently selected from the group consisting of hydrogen, halogen, C 24 alkyl, C2 24 alkenyl, C2 24 alkynyl, C3,0 cycloalkyl; C3 0 cycloalkenyl, C3 o cycloalkynyl, each of said C 24 alkyl, C3,0 cycloalkyl, C2 24 alkenyl, C3 0 cycloalkenyl, C2 24 alkynyl, C3,o cycloalkynyl optionally includes one or more heteroatoms in the carbon-atom chain or at the ends of said chain, said heteroatoms being selected from the groups consisting of O. S and N. oR4, SR4 CN, isocyano, thiocyano, isothiocyano, nitroso, NO2, NR5R6, sulfonate, haloalkyl, C(=o)R7, C(=S)R7, aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy (optionally a oxybenzyl), arylalkylthio (optionally a benzylthio), heterocyclic ring, oxyheterocyclic ring, thioheterocyclic ring, alkyl-heterocyclic ring, oxyalkyl- heterocyclic ring, thioalkylheterocyclic ring, Each R4, R5, and R6 can independently be perfluorinated, partially or not fluorinated and are independently selected from the group consisting of H. OH, C, 24 alkyl, C, 24 alkenyl, aryl; C3,0 cycloalkyl, C4 0 cycloalkenyl, 5-6 membered heterocyclic ring, t t t , t t t t ' t t # t t t t t t t t t t t t ' t t t Each R7 can independently be perfluorinated, partially or not fluorinated and is independently selected from the group consisting of H. OH, Cat s alkyl, Cat 24 alkenyl, Cat 24 alkoxy, Cat 24 alkylthio, C3 0 cycloalkyl, C4 '0 cycloalkenyl; aryl, 5-6 membered heterocyclic ring, L is selected from the group of lanthanides, B is selected from neutral bidentate and tridentate heterocyclic rings, optionally In a particular embodiment, the invention relates to the use of complexes according to formula I, wherein the complex, more in particular the bis(sulfonyl)imide ligands are perfluorinated A particular embodiment of the present invention relates to the use of complexes according to formula II, wherein L is erbium and wherein the complexes are irradiated with light of between 300 rim and 350 nm, more in particular 333 nm, in order to obtain an intense near-IA luminescence, more in particular around 1550 nm.

Another particular embodiment relates to the use of complexes according to formula Il.

wherein L is neodymium and wherein the complexes are irradiated with light of between 300 nm and 350 nm, more in particular 334 nm, in order to obtain an intense near-IA luminescence, more in particular around 1050 rim In a more particular embodiment of said aspect of the invention, complexes according to formula II are used as advanced optically amplifying materials and associated structures for data communications and telecommunications applications, more in particular as optical amplifiers, optically pumped planar waveguide based IR amplifiers, infrared OLEDs, polymer lasers, and/or light-conversion devices, in particular operating in the region of 1500-1600 nm In a yet more particular embodiment, said complexes are used as near-IA luminescence emitting complexes, therefore emitting light with a wavelength of around 800 and 1700 nm In another particular embodiment, the complexes are exhibiting intense luminescence in the 1500-1600 nm region, more in particular in the range of 1550 nm In another more particular embodiment of the present invention, the complexes of formula It can be used in security documents and articles Another aspect of the invention relates to compositions comprising the complexes of the invention In these compositions the complexes can be incorporated into sol-gel glasses or liquid crystals The complexes can be bound to animal or vegetal fibres (or to a fabric made thereof), including to the cellulose fibres of papers In another aspect, the complexes of the invention are blended with or coupled to a polymer.

Other compositions in which the complexes can be comprised are in inks and printed onto security documents or articles, or may be molded into plastic or laminated between sheets, for the production of foils, security threads, credit, identity or access cards, and the like Said security system may noteworthy be employed for protecting banknotes, valued documents, official documents, cards, transportation tickets, as well as branded goods of all kind.

Another embodiment of the present invention relates to mixtures of different complexes of the invention Several complexes can be mixed with each other or can be mixed with other components Another aspect of the invention relates to a method of preparing the complexes of the invention The method for preparing comprises the adding of a lanthanidehalogenide (I eq) (i.e ErCI3 6H2O) ethanol solution to the bis(sulfonyl)imide (2 95 eq) in ethanol, (prepared according to literature), cooling of the reaction mixture, filtering and adding the hi- or t - t 8 t t t t t t t t . t Err tt.

tridentate heterocyclic ring (1 eq) dissolved in ethanol to the filtratesolution, refluxing for 3 hours, cooling, adding of water, distilling the mixture to remove the ethanol, filtering, washing, recrystallization and drying for 12h at a temperature of 50 C, subsequently followed by drying for 24h at 105 C.

Another aspect of the invention relates to a method for obtaining an intense luminescence, comprising the preparation of and/or the use of a complex comprising a lanthanide, 1 or more bis(sulfonyl)imide ligands and l or more bidentate or tridentate heterocyclic rings and the indirect excitation of the lanthanide through excitation in the ligands of the lanthanide A particular embodiment of the invention relates to a method for obtaining an intense luminescence comprising the preparation of the lanthanide organic ternary complex of formula I and the indirect excitation of the lanthanide through excitation in the ligands of the lanthanides In a particular embodiment, the invention relates to a method for obtaining intense luminescence, more in particular near-lR luminescence, more in particular in the range of 800- 1700 nm, yet more in particular in the range of 1500- l 600 nm by using the new rare-earth organic ternary complex, yet more in particular containing erbium The best excitation wavelength is the one that corresponds to or is in the range of the maximum in the excitation spectrum The method thus comprises the excitation of the complex of the present invention through setting the wavelength of the excitation light equal to or in the range of a maximum in the excitation spectrum The method comprises the excitation of the complex with a wavelength corresponding to the maximum of the excitation spectrum of the complex, said excitation spectrum measured in the range of the wavelength of the luminescence of the lanthanide ion Said wavelength of excitation may be set to about 20 to 30 nm above or below the wavelength of a maximum in the excitation spectrum The method specifically excludes the excitation directly in the energy levels of the lanthanide of the organic ternary complex of the invention The method comprises the preparation of the new rare-earth organic ternary complex and irradiating the complex with light of a wavelength between 200 and 700 nm, more in partcicular between 300 and 450 nm) In another embodiment, the invention relates to a method for obtaining intense luminescence around 1550 nm, said method comprising the use of the erbium ternary organic complex of the invention and irradiating said complex with light of around 333 rim Another particular embodiment relates a method for obtaining intense luminescence around 1050 nm, said method comprising the use of the neodymium ternary organic complex of the invention and irradiating said complex with light of around 334 rim

BRIEF DESCRIPTION OF THE FIGURES

Figure l Erbium-centered luminescence upon excitation in the 2H' I/2 level of the erbium ion (520 nm) The figure shows that erbium-centered luminescence can be observed upon direct excitation in the 2Hi I/2 level The compound is tris(bis(heptadecafluorooctylsulfonyl)imide)(1,10-phenanthroline) erbium(lII) Figure 2 Erbium-centered luminescence upon excitation in the phenanthroline moiety This shows the erbium-centered luminescence upon excitation in the phenanthroline moiety at 333 rim The integrated emission is over 20 times more intense than that in figure 1 The compound is tris(bis(heptadecafluorooctylsulfonyl)imide)(1,10-phenanthroline) erbium(III) c c c c c c c c c c c c c c c c. * c.

c. c . c c c c c c * c c Figure 3 Combined spectra showing the luminescence signal upon excitation at 520 nm (lower curve) and 333 rim (upper curve), the upper combined graph shows an enlarged view The combined spectra clearly indicate the dramatic increase of the erbium-centered luminescence when excitation occurs in the phenanthroline unit The upper part of the figure shows an enlarged view The compound is tris(bis(heptadecafluorooctylsulfonyl)imide)(l,l0phenanthroline)erbium(llI) Figure 4. Excitation spectrum, indicating a much higher luminescence intensity upon excitation in the UV The compound is tris(bis(heptadecafluorooctylsulfonyl)imide)(1,10phenanthroline)erbium(lII) Figure 5 Neodymium-centered luminescence upon excitation in the 4G5/2 level of the neodymium ion (586 nm) in tris(bis(heptadecafluoroocylsulfonyl)imide)(1, 10phenanthroline)neodymium(IIl) Figure 6. Neodymium-centered luminescence of tris(bis(heptadecafluoroocylsulfonyl)imide) (1, 10-phenanthroline)neodymium(III) upon excitation in the phenanthroline moiety (334 nm) Figure 7. Combined spectra showing the luminescence signalof tris(bis(heptadecafluoroocylsulfonyl)imide)(1,10phenanthroline)neodymium(lll)upon excitation at 586 rim (lower curve) and 334 rim (upper curve) Figure 8 Excitation spectrum of tris(bis(heptadecafluoroocylsulfonyl) imide)( l,10phenanthroline)neodymium(III) Figure 9 Ytterbium-centered luminescence upon excitation in the phenanthroline moiety (340 nm) of tris(bis(heptadecafluoroocylSulfonyl)imide)(1,10-phenanthroline) ytterbium(llI) Figure 10 Excitation spectrum of tris(bis(heptadecafluoroocylsulfonyl) imide)( l,10phenanthroline)ytterbium(II I)

DETAILED DESCRIPTION OF THE INVENTION

Definitions In each of the following definitions, the number of carbon atoms represents the maximum number of carbon atoms generally optimally present in the substituent or linker, it is understood that where otherwise indicated in the present application, the number of carbon atoms represents the optimal maximum number of carbon atoms for that particular The term "Cat 24 alkyl" or "C224 alkyl" as used herein means respectively a C1-C24 or C2-C24 normal, secondary, or tertiary hydrocarbon Examples are methyl, ethyl, I-propyl, 2- propyl, I-butyl, 2-methyl-1-propyl(i-Bu), 2-butyl (s-Bu) 2-methyl-2- propyl (t-Bu), 1-pentyl (n-pentyl), 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 3- methyl- 1 -butyl, 2methyl-l-butyl7 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2pentyl, 4-methyl-2- pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3-dimethyl-2-butyl, 3,3- dimethyl-2-butyl, n- pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n- dodecyl, n-tridecyl, ntetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, nnonadecyl and n-icosyl ce.e As used herein and unless otherwise stated, the term ''C30 cycloalkyl" means a monocyclic saturated hydrocarbon monovalent radical having from 3 to 10 carbon atoms, such as for instance cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, or a C7 0 polycyclic saturated hydrocarbon monovalent radical having from 7 to carbon atoms such as, for instance, norbornyl, fenchyl, trimethyltricycloheptyl or adamantyl As used herein and unless otherwise stated, the term "C3 0 cycloalkylene" refers to a cyclic hydrocarbon radical of 3-10 carbon atoms, and having two monovalent radical centers derived by the removal of two hydrogen atoms from the same or two different carbon atoms of a parent alkane, i e the divalent hydrocarbon radical corresponding to the above defined C3 '0 cycloalkyl The terms "C2 24 alkenyl" and "C3 0 cycloalkenyl" as used herein is C2-C24 normal, secondary or tertiary and respectively C3-10 cyclic hydrocarbon with at least one site (usually I to 3, preferably 1) of unsaturation, i e a carbon-carbon, sp2 double bond Examples include, but are not limited to ethylene or vinyl (-CH=CH2), allyl (-CH2CH=CH2), cyclopentenyl (- C5H7), and 5-hexenyl (-CH2 CH2CH2CH2CH=CH2) The double bond may be in the cis or bans configuration The terms "C2 24 alkynyl" and "C3 0 cycloalkynyl" as used herein refer respectively C2-C18 normal, secondary, tertiary or the C3-10 cyclic hydrocarbon with at least one site (usually I to 3, preferably 1) of unsaturation, i e a carbon-carbon, sp triple bond Examples include, but are not limited to acetylenic (-C_CH) and propargyl (-CH2C--CH) The terms "C 24 alkylene" as used herein each refer to a saturated, branched or straight chain hydrocarbon radical of 1-18 carbon atoms, and having two monovalent radical centers derived by the removal of two hydrogen atoms from the same or two different carbon atoms of a parent alkane Typical alkylene radicals include, but are not limited to methylene (-CH2-) 1,2-ethyl (-CH2CH2-), 1,3-propyl (-CH2CH2CH2-), 1,4-butyl (-CH2CH2CH2CH2-) , and the like The terms "C2 24 alkenylene" and "C3 0 cycloalkenylene"as used herein refer to an unsaturated branched chain, straight chain, and respectively a cyclic hydrocarbon radical of 2-18 respectively 3-10 carbon atoms, and having two monovalent radical centers derived by the removal of two hydrogen atoms from the same or two different carbon atoms of a parent alkene, i e double carbon-carbon bond moiety Typical alkenylene radicals include, but are not limited to 1,2- ethylene (-CH=CH-) The terms "C2 24 alkynylene" and "C3 0 cycloalkynylene" as used herein refer respectively to an unsaturated, branched or straight chain of 2-18 carbon atoms or to a cyclic hydrocarbon radical of 3-10 carbon atoms respectively, having two monovalent radical centers derived by the removal of two hydrogen atoms from the same or two different carbon atoms of a parent alkyne, i e triple carbon-carbon bond moiety. Typical alkynylene radicals include, but are not limited to acetylene (-C_C-), propargyl (-CH2C-C-), and 4-pentynyl (- CH2CH2CH2C_C-) The term "aryl" as used herein means a aromatic hydrocarbon radical of 6-20 carbon atoms derived by the removal of hydrogen from a carbon atom of a parent aromatic ring system Typical aryl groups include, but are not limited to I ring, or 2 or 3 or 4 or 5 rings fused together, radicals derived from benzene (phenyl), naphthalene, spiro, anthracene, biphenyl, terphenyl, quaterphenyl, quinquephenyl, pentalene, indene, azulene, heptalene, bisphenylene, indacene, acenaphylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthrene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, tetracene, c c . c e c a c c c c c a c ec c c c cce C C C C C C C C C pleiandene, picene, perylene, pentaphene, pentacene, tetraphenylene, hexaphene, hexacene, rubicene, coronene, trinaphtylene, heptaphene, heptacene, pyranthrene, ovalene and the like "Arylalkyl" as used herein refers to an alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or Sp3 carbon atom, is replaced with an aryl radical Typical arylalkyl groups include, but are not limited to, benzyl, 2-phenylethan1- yl, 2-phenylethen- 1 -yl, naphthylmethyl, 2-naphthylethan- 1 -yl, 2naphthylethen- 1 -yl, naphthobenzyl, 2-naphthophenylethan-1-yl and the like The arylalkyl group comprises 6 to carbon atoms, e g the alkyl moiety, including C.24 alkyl, C2 24 alkenyl or C2 24 alkynyl groups, of the arylalkyl group is 1 to 6 carbon atoms and the aryl moiety is 5 to 14 carbon atoms The term "heterocyclic ring" as used herein means pyridyl, dihydroypyridyl, tetrahydropyridyl (piperidyl), thiazolyl, tetrahydrothiophenyl, sulfur oxidized tetrahydrothiophenyl, furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, tetrazolyl, benzofuranyl, thianaphthalenyl, indolyl, indolenyl, quinolinyl, isoquinolinyl, benzimidazolyl, piperidinyl, 4-piperidonyl, pyrrolidinyl, 2-pyrrolidonyl, pyrrolinyl, tetrahydrofuranyl, bis- tetrahydrofuranyl, tetrahydropyranyl, bis-tetrahydropyranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, octahydroisoquinolinyl, azocinyl, triazinyl, 6H1,2,5-thiadiazinyl, 2H,6H-1,5,2-dithiazinyl, thianthrenyl, pyranyl, isobenzofuranyl chromenyl, xanthenyl, phenoxathinyl, 2H-pyrrolyl, isothiazolyl, isoxazolyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, lH-indazoly, purinyl, 4H-quinolizinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, 4aHcarbazolyl, carbazolyl, B-carbolinyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, oxazolidinyl, benzotriazolyl, benzisoxazolyl, oxindolyl, benzoxazolinyl, benzothienyl, benzothiazolyl, isatinoyl, tellurophenyl, pteridinyl, naphtylridinyl, isophosphinolinyl, phenanthridinyl, phenazinyl, phosphoquinolinyl, isophosphindolyl, isoquinolinyl, isoxazolyl, perimidinyl, phenanthrolinyl, phosphindolyl, phthalazinyl, purinyl, quinolizinyl, selenophenyl, thiophenyl, pyrazinyl, pyridazinyl pyrimidinyl, pyrrolizinyl, quinolinyl and quinoxalinyl The term "bidentate or tridentate heterocyclic ring" means a bidentate or tridentate saturated, unsaturated or aromatic ring system including at least two N. O. S. or P and which can consist of 1, 2, 3, 4, 5, or more rings and the corresponding oxides thereof. This thus includes heteroaryl groups with at least two N. O. S. or P Examples of bidentate or tridentate heterocyclic rings include by way of example and not limitation 1,10phenanthroline, 2,2'- bipyridine, 2,2',6',2"-terpyridine, 2-(2-pyridyl)benzimidazole, 4,7- diphenyl-1,10- phenanthroline (bathophenanthroline, bath), 2-phenyl-imidazo[4,5-fl-1,10- phenanthroline, and the like "Alkyl-heterocyclic ring" as used herein refers to an alkyl radical in which one of the hydrogen atoms bonded to a carbon atom, typically a terminal or Sp3 carbon atom, is replaced with a heterocyclic ring radical Examples of alkyl-heterocyclic ring groups are 2pyridylethan-1-yl, 2-thiazolylethen-1-yl or 2-imidazolylmethyl The alkylheterocyclic ring group comprises 6 to 20 carbon atoms, e g the alkyl moiety, including alkanyl, alkenyl or alkynyl groups, of the alkylheterocyclic ring group is 1 to 6 carbon atoms and the heterocyclic ring moiety is 5 to 14 carbon atoms Heteroaryl means pyridyl, dihydropyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, s- triazinyl, oxazolyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, furanyl, thiofuranyl, thienyl, and pyrrolyl e e he e e e e e e e e e e e c # eve e e e e e e ece ce. Bee e e By way of example, carbon bonded heterocyclic rings are bonded at position 2, 3, 4, 5, or 6 of a pyridine, position 3, 4, 5, or 6 of a pyridazine, position 2, 4, 5, or 6 of a pyrimidine, position 2, 3, 5, or 6 of a pyrazine, position 2, 3, 4, or 5 of a furan, tetrahydrofuran, thiofuran, thiophene, pyrrole or tetrahydropyrrole, position 2, 4, or 5 of an oxazole, imidazole or thiazole, position 3, 4, or 5 of an isoxazole, pyrazole, or isothiazole, position 2 or 3 of an aziridine, position 2, 3, or 4 of an azetidine, position 2, 3, 4, 5, 6, 7, or 8 of a quinoline or position 1, 3, 4, 5, 6, 7, or 8 of an isoquinoline Still more typically, carbon bonded heterocycles include 2-pyridyl, 3-pyridyl, 4-pyridyl, 5-pyridyl, 6- pyridyl, 3-pyridazinyl, 4pyridazinyl, 5-pyridazinyl, 6-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6- pyrimidinyl, 2-pyrazinyl, 3-pyrazinyl, 5-pyrazinyl, 6-pyrazinyl, 2- thiazolyl, 4-thiazolyl, or 5- thiazolyl By way of example, nitrogen bonded heterocyclic rings are bonded at position I of an aziridine, azetidine, pyrrole, pyrrolidine, 2-pyrroline, 3-pyrroline, imidazole, imidazolidine, 2- imidazoline, 3-imidazoline, pyrazole, pyrazoline, 2-pyrazoline, 3- pyrazoline, piperidine, piperazine, indole, indoline, IH-indazole, position 2 of a isoindole, or isoindoline, position 4 of a morpholine, and position 9 of a carbazole, or 13-carboline Still more typically, nitrogen bonded heterocycles include 1-aziridyl, 1-azetedyl, 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl, and l-piperidinyl "Carbocycle" means a saturated, unsaturated or aromatic ring system having 3 to 7 carbon atoms as a monocycle or 7 to 12 carbon atoms as a bicycle Monocyclic carbocycles have 3 to 6 ring atoms, still more typically 5 or 6 ring atoms Bicyclic carbocycles have 7 to 12 ring atoms, e g arranged as a bicyclo [4,5], [5,5], [5,6] or [6,6] system, or 9 or 10 ring atoms arranged as a bicyclo [5,6] or [6,6] system Examples of monocyclic carbocycles include cyclopropyl, cyclobutyl, cyclopentyl, I -cyclopent- I -enyl, I - cyclopent-2-enyl, 1- cyclopent-3-enyl, cyclohexyl, 1 -cyclohexI -enyl, l -cyclohex-2-enyl, 1 -cyclohex-3 -enyl, phenyl, spiryl and naphthyl Carbocycle thus includes some aryl groups As used herein and unless otherwise stated, the terms "C- 8 alkoxy", "C' x alkylthio" "C3 0 cycloalkoxy", "aryloxy", "arylalkyloxy", "oxyheterocyclic ring", "thio Ct 7 alkyl", "thio C3'0 cycloalkyl", "arylthio", "arylalkylthio", "oxyalkylheterocyclic ring", "thioalkyl- heterocyclic ring" and "thioheterocyclic ring" refer to substituents wherein a C x alkyl radical, respectively a C:; O cycloalkyl, aryl, arylalkyl, alkyl-heterocyclic ring or heterocyclic ring radical (each of them such as defined herein), are attached to an oxygen atom or a sulfur atom through a single bond, such as but not limited to methoxy, ethoxy, propoxy, butoxy, thioethyl, thiomethyl, phenyloxy, benzyloxy, mercaptobenzyl and the like.

As used herein and unless otherwise stated, "perfluorinated" means that all hydrogen atoms of a certain group or molecule are modified in fluorine. Examples of perfluorinated groups include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, nonadecafluorononyl, heneicosafluorodecyl, tricosafluoroundecyl, pentacosafluorododecyl' heptacosafluorotridecyl, nonacosafluorotetradecyl and the like As used herein and unless otherwise stated, the term halogen means any atom selected from the group consisting of fluorine, chlorine, bromine and iodine As used herein and unless otherwise stated, the term "lanthanides" as used herein refers to lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu) Any substituent designation that is found in more than one site in a compound of this invention shall be independently selected The terms "direct excitation" and "indirect excitation" shall refer respectively to the excitation of the lanthanide organic ternary complex with light sent directly in the excited energy levels of the lanthanide of the complex or to the excitation of the lanthanide indirectly through the ligands of the lanthanide The present invention relates to new visible-light or near-IA luminescence emitting lanthanide organic ternary complex, compositions thereof and to the use of said lanthanide organic ternary complex, more specifically to the use as an optically functional material or in security documents or articles Particular lanthanide complexes show an intense near-infrared luminescence when excited indirectly (so not by exciting directly in the lanthanide).

As an example, the present invention relates to erbium complexes, consisting of a trivalent erbium ion (Erg) surrounded by three negatively charged bidentate bis(sulfonyl)imide ligands A and one neutral bidentate or tridentate ligand B. like derived from l, l 0-phenanthroline (phen), 2,2'-bipyridine (bipy), 2,2',6',2"-terpyridine (terpy) or 2-(2pyridyl)benzimidazole The erbium complexes are electrically neutral (contain no counter ions in the second coordination sphere) and can be represented by the general formula [ErA3B] The coordination number of the erbium ion is assumed to be eight (six oxygen atoms from the bis(sulfonyl) imides and two atoms from the bidentate ligand B). In the case that B is a tridentate ligand, the coordination number will be nine The near- infrared photoluminescence of the trivalent erbium ions is due to the 4I3/2 415/2 transition, with the emission maximum located around l 550 rim (i e. 6450 cm') Because of the relatively small energy gap between the excited state 4I'3/2 and the ground state 4I5/2, the excited state is efficiently quenched by the presence of O-H, N-H or C-H bonds in the neighbourhood of the Er + ion. These bonds have a vibrational energy and can accept the energy of excited electronic states by vibronic coupling. When no precautions are taken to reduce the contribution of these radiationless deactivation processes, the erbium complexes will have a low luminescence quantum yield, or will not show photoluminescence at all A strategy for the design of luminescent erbium complexes is to exclude water from the first coordination sphere by embedding the Er3+ ion in a cage-like ligand Another approach is the use of low vibrational frequency ligands having C-F or C-D bonds instead of C-H bonds The interesting feature of the compounds of the invention is that no C-H bonds are present in the chelate rings formed around the lanthanide. The six- membered inorganic chelate rings are formed by one lanthanide atom, two oxygen atoms, two sulphur atoms and one nitrogen atom One could think of designing near-infrared luminescent erbium complexes based on these ligands. The three bis(sulfonyl)imide ligands cannot saturate the coordination sphere and the erbium ion can easily form adducts with solvent molecules containing O- or N-donor atoms, including water Because the bis(sulfonyl)imide ligands do not absorb light in the ultraviolet and visible part of the spectrum, the excited states of the lanthanide ion cannot be populated by energy transfer from an excited ligand, but only via direct excitation of the 4f-levels Because the molar absorptivities of the 4f-4f transitions are small, not much light can be absorbed, and therefore the luminescence intensities will be low.

The bis(sulfonyl)amines that are transformed into the bis(sulfonyl)imides (ligand A) by extraction of the proton of the central nitrogen atom can be represented by the general formula . a 1

H o 1 o

Rl s'Nll 2 11 11

O O

The substituents Ret and R2 can be identical or different Ret and R2 can be straight-chain or branched-chain alkyl groups with general formula CnH2n+ (n can be varied between l and 24), straight-chain or branched-chain partially fluorinated or perfluorinated alkyl groups with a number of carbons between 1 and 24), cycloalkyl rings with a ring size varying between 3 and 10 carbon atoms, partially fluorinated or perfluorinated cycloalkyl rings with a ring size varying between 3 and lO carbon atoms, poly(ethyleneoxide) chains ( CH3(0CH2CH2)nO, where n is varying between l and lO),aromatic groups, partially fluorinated or perfluorinated aromatic groups, heterocyclic rings, partially fluorinated or perfluorinated heterocyclic groups Aromatic groups can be for example unsubstituted or substituted phenyl, naphthyl, anthryl, phenanthryl, furyl, thienyl, quinolyl, isoquinolyl, pyridyl. The aromatic rings and heterocyclic rings can be substituted by one or more electron-donating or electron- withdrawing groups Examples of such substituents include fluoro, chloro, bromo, iodo, nitro, sulfonate, cyano, isocyano, thiocyano, isothiocyano, nitroso, amino, N-monosubstituted amino, N-disubstituted amino, acetyl, carboxylato, alkyl (CnH2n+, where n is varying between l and 24), alkoxy (OCnH2n+, where n is varying between l and 24), alkoxymethyl (CH20CnH2n: , where n is varying between l and 24), alkylthio (SCnH2n', where n is varying between l and 24), poly(ethyleneoxide) ( CH3(0CH2CH2) nO, where n is varying between l and lO) However, R'-Y and R2-X can certainly not simultaneously be composed of only l carbon, like a methyl, trifluoromethyl or substituted methyl, since in this case the method of the invention is not applicable. The stoichiometry of the components of the complex will be different than in the compounds of the invention and do not show an as high luminescence as the compounds of the invention. One of R-Y and R2-X needs to be at least 2 carbon atoms long All groups and substituents of R'-Y and R2-X can be perfluorinated, partially or not fluorinated The neutral bidentate and tridentate ligands (ligand B) are bidentate or tridentate heterocyclic rings such as l,lO-phenanthroline, 2, 2'-bipyridine, 2,2',6',2"-terpyridine, 2-(2 pyridyl)benzamidazole and derivatives thereof, unsubstituted or substituted Examples of such substituents include fluoro, chloro, bromo, iodo, nitro, sulfonate, cyano, isocyano, thiocyano, isothiocyano, nitroso, amino, N- monoalkylsubstituted amino, N-dialkylsubstituted amino, acetyl, carboxyl (-COOH), hydroxy, alkyl (CnH2n+, where n is varying between 1 and 24), alkoxy (OCnH2n+', where n is varying between l and 24), alkoxymethyl (CH20CnH2n, where n is varying between l and 24), alkylthio (SCnH2n, , where n is varying between l and 24), poly(ethyleneoxide) ( CH3(0CH2CH2) nO, where n is varying between l and lO), arylakyloxy, alkenyl, alkynyl, aryl cycloalkyl and cycloalkenyl.

The function of the substituents is to improve the stability of the complexes, to increase the solubility in different matrices and to finetune the position of the excited states of the ligand (to shift the absorption maximum so that other wavelengths are absorbed and to ensure a more effcient energy transfer from the ligand to the erbium ion) and to tune the molar absorptivities of the ligands (to change the amount of light that can be absorbed at a given concentration of the complex) c e C, , , , Via functionalities in the substituents, it is also possible to covalently link the organic ternary complex to a polymer backbone or to a sol-gel glass network Furthermore, the bidentate and tridentate heterocyclic rings such as I,1 0-phenanthrolines, the 2,2'-bipyridine and the 2,2',6',2"-terpyridines can be transformed into the corresponding N- oxides Examples of the neutral ligands of type B are l,10-phenanthroline, 2,2'-bipyridine, 2,2', 6',2"-terpyridine, 5- nitroI, l 0-phenanthroline, 5-amino- l, l 0-phenanthroline, 4,7dimethylphenanthroline, 4,7- diphenyl-l,10-phenanthroline (bathophenanthroline, bath), 5,6-dihydro-1, 10-phenanthroline, l, l 0-phenanthroli nedi sulfonate, 2-phenyl-i midazo [4, 5 -f] - l, l 0phenanthroline, 2-(4 - dialkylaminophenyl)imidazo[4,5-f]- l, l 0-phenanthroline, 3-alkyl-2-(4' dialkylaminophenyl)imidazo[4,5-fl- l, 1 0-phenanthroline, 3,3'-dimethyl-2, 2'-bipyridine, 4,4' dimethyl-2,2'-bipyridine, 2-(2-pyridyl) benzimidazole and 1-alkyl-2-(2 pyridyl)benzimidazole A figure of an example erbium complex is : NO OR-S-O | \ The erbium complexes can be blended with a polymer to obtain a transparent or semi- transparent matrix Examples of such polymers include polyethylene, polypropylene, polybutylene, polymethacrylate (PMA), polymethylmethacrylate (PMMA), polyacrylate, polystyrene, polyvinylchloride, polyvinylalcohols, polyvinyl ethers, polyvinyl acetate, and their fluorinated analogues The polymer matrix can be highly fluorinated to reduce radiationless deactivation of the erbium ion Examples are poly(tetrafluoroethylene) (TEFLON), CYTOP (Cyclic Transparent Optical Polymer, commercialized by the Asahi Glass, Company, Japan) and other copolymerised perfluoro(alkenyl vinyl ethers), FLARES (commercialized by Raychem) and other fluorinated poly(arylethers) No restrictions are placed on the method of preparation of the erbium doped polymer matrices (l) The erbium complex and the polymer can be dissolved in an organic solvent and films can be prepared by spin-coating or dipcoating, (2) The erbium complex and the polymer can be dissolved in a solvent, the viscous solution is cast and a film is obtained after evaporation of the solvent, (3) The erbium complex is dissolved in the molten polymer matrix and the mixture is processed by casting, extruding, etc. (4) The erbium complex is mixed with polymer powder, and the resulting mixture is melted and processed by casting, extruding, etc. (5) An erbium complex with a polymerisable group can be copolymerised with a monomer to a polymeric composite matrix, (6) When the polymer is not soluble in organic solvents and cannot be melted, a composite matrix can be obtained by mixing the r ä 8 a a a a c, a a a . .. a.- a erbium complex with very Me powder of the polymer and applying high pressure to the mixture.

The erbium complex can be incorporated in a sol-gel glass matrix These sol-gel glasses can be obtained by hydrolysis of the precursors TMOS or TEOS The erbium complex can be dissolved in a liquid crystal matrix or in liquid-crystalline mixtures The total luminescence output not only depends on the luminescence quantum yield, but also on the amount of electromagnetic radiation (UV-visible wavelength range) that is absorbed Because the transitions in the absorption spectrum of the trivalent lanthanide ions (and thus of Er3+ as well) are very weak, the observed luminescence is weak upon direct excitation in the 4f" levels of Er34, even if the Er3+ ion is in an environment that limits radiationless deactivation Much intenser luminescence is obtained by the so-called "antenna-effect" Here the erbium ion is excited indirectly via the ligands and the excitation energy is transferred to the Er ion. Because these ligands can have a much stronger absorption of wavelengths in the UV-visible region, the photoluminescence will be much intenser, if the energy transfer is efficient and if radiationless deactivation of the excited erbium levels can be avoided It was found that the excited states of the Er3' ion can be populated by indirect excitation via the ligand B. also when the bis(sulphonyl)imide ligands do not contain an aromatic group Intense photoluminescence ofthe 413/2 Transition with an emission maximum around 1550 nm can be observed In the complexes of the invention, the gain in intensity is obtained (1) via the inorganic chelate ring, which decreases the radiationless deactivation of the excited state, (2) via efficient light absorption by the ligands and subsequent energy transfer to the erbium ion or other lanthanide ions The erbium complexes and the method of this invention delivers a luminescence output around 1550 nm that is at least a factor 5 to 10 higher than the luminescence output observed under the same experimental conditions for erbium complexes of the prior art, such as erbium B-diketonate complexes or through methods described in the prior art. The presence of the highly intense luminescence of the erbium complexes is shown through comparative studies and is furthermore evident from the high signal-to-noise ratio of the luminescence spectrum The materials and the methods described in this invention can be used for example in the telecommunication sector The complexes can be applied as active compounds in advanced optically amplifying materials and associated structures for data communications and telecommunications applications The erbium complexes can be applied in polymeric erbium- doped optical amplifiers, optically pumped planar waveguide based IR amplifiers, infrared OLEDs, polymer lasers, and light-conversion devices, all operating in the 1500-1600 nm region The complexes will be indirectly excited The compounds and the methods of the invention can also be applied in the sector of security documents and articles The complexes of the present invention can be formulated in security systems, possibly in a mixture with other components, and than can be detected by existing equipment. The compounds of the invention may be mixed with each other or with other compounds Said luminescent compounds or mixtures thereof may be incorporated in inks and printed onto security documents or articles, or may be molded into plastic or laminated between sheets, for the production of foils, security threads, credit, identity or access cards, and the like Said security system may noteworthy be employed for protecting banknotes, 8 6 .8d # ace e. ^ valued documents, official documents, cards, transportation tickets, as well as branded goods of all kind.

The excitation wavelength that leads to a maximum in luminescence output can be determined by measurement of the excitation spectrum of the ternary lanthanide complex, for example erbium complex in the medium and by choosing the wavelength that corresponds to the maximum in the excitation spectrum as the excitation wavelength The excitation spectrum is measured by monitoring the luminescence intensity at the wavelength of interest (i e the wavelength at which a luminescent device has to operate) By measuring the maximum in the excitation spectrum, one can circumvent the problem encountered by using the maximum in the absorption spectrum A wavelength that corresponds to a maximum in the absorption spectrum is not necessarily a good wavelength for excitation. The maximum in the absorption spectrum can be due to a chromophore that is not able to transfer the excitation energy to the lanthanide ion in general Figure It shows the absorption spectrum of a complex of the invention, but no clear absorption maximum is visible

Examples

The various properties were measured using the following equipment The 'H NMR spectra were recorded on a Bruker Avance 300 spectrometer (300 MHz)Elemental analyses (CHN) were performed on a CE-Instrument EA-l l to elemental analyser The infrared spectra have been measured on a Bruker IFS66 spectrometer, using the KBr pellet method Melting points have been measured by DSC (Mettler-Toledo DSC module 822e) The NIR-luminescence and the luminescence decay curves have been recorded on an Edinburgh Instruments FS-920P spectrofluorimeter equipped with a xenon arc lamp (450 W), a Nd YAG pumped dye-laser, a double excitation monochromator, and a Hamamatsu R5509- 72 NIR-photomultiplier The erbium, neodymium and ytterbium complexes were measured by dispersing microcrystals into KBr pellets Example I Synthesis of tris(bis(nonafluorobutylsulfonyl)imide)( l, l O- phenanthroline)erbium(III), Er(N(SO2C4Fs)2)3 C2HeN2 C4F9_, c'] , The potassium salt of the ligand bis(nonafluorobutylsulfonyl)imide was synthesized by a one- pot synthesis described by Sogabe et al. [6], which involves the reaction of a perfluoroalkylsulfonyl fluoride with trifluoracetamide in the presence of K2CO3 as a base A solution of 0 2 l g (0 54 mmol) ErCl3 6H2O in 20 ml of ethanol was added dropwise to a solution of l g (l 6 mmol) of K(N(SO2C4F9)2) in 50 ml of absolute ethanol After stirring this for 30 minutes the mixture was cooled for one hour and the precipitated KCI was filtered off An equimolar amount of O l l g (0 54 mmol) of l, l O- phenanthroline hydrate (C2HeN2 H20) in 20 ml of ethanol was added to the solution and reflexed for 3 hours After cooling the solution, 50 ml of water were added and the ethanol was distilled off under reduced pressure e 1 8 8 8 8 eta 8 81 1 8 8 8 8 8. 8 . .. e The resulting solid was filtered off, washed with water and n-hexane and recrystallized in a small amount of 2-propanol (yield 75%) The product was dried first 12h under vacuo at 50 C and then for 24h at 105 C The compound is well-soluble e g. in acetone and DMSO CHN-Analysis. Found (calc). C 20 28% (20 71), H 0 24%(0 39), N 3.51% (3 35) IR(KBr) 1342 (m, S=O), 1206, 1243 (s, C-F), 1148 (s, S-O) cm M p. 320 C Example 2 Synthesis oftris(bis(heptadecafluoroocylsulfonyl)imide)(1,10phenanthroline)erbium(III), Er(N(SO2C8F'7)2) C'2H8N2 C8F a The potassium salt of the ligand bis(nonafluorobutylsulfonyl)imide was synthesized by a one pot synthesis described by Sogabe et al. [6] A solution of 0 124 g (0 33 mmol) of ErCI3 6H2O in 20 ml of ethanol was added dropwise to a solution of a mixture of I g (0.98 mmol) of K(N(SO2C8F7)2) in 50 ml of absolute ethanol After stirring this solution for 30 minutes, the mixture was cooled for one hour and the precipitated KCI was filtered off An equimolar amount of 0 0648 g (0 33 mmol) of I,10 phenanthroline hydrate (Cl2H8N2 H20) in 20 ml of ethanol was added to the solution and refluxed for 3 hours After cooling the solution 50 ml of water were added and the ethanol was removed under reduced pressure The resulting solid was filtered off, washed with water and n-hexane and recrystallized in a small amount of 2-propanol (yield 85%) The product was dried first 12h under vacuo at 50 C and then for 24h at 105 C.

CHN-Analysis Found(calc) C. 21.53%(21.92),H 013%(0.25),N 1.78%(2.13) IR (KBr) 1350 (m, S=O), 1202, 1249 (s, C-F), 1150 (s, S-O) cm M p. 315 C Example 3 Synthesis oftris((heptadecafluoroocylsulfonyl) (nonafluorobutylsulfonyl)imide)(1,10-phenanthroline)erbium(III), Er((so2csF7)N(so2c4Fs))3 C t2HxN2 Cdlr: N,:: The compound Er((SO2CxFl7) N(SO2C4F'))3 Cl2HxN2 was obtained in the same way as example 1, except that 0 80 g (0 98 mmol) of the ligand K(N(SO2C8F7)(SO2C4F')) (synthesized according to the procedure described by Sogabe et al) were used instead of K(N(SO2CsFI7)2) CHN-Analysis Found (calc.) C 21 56% ( 21 45), H. 0 12% (0 30), N 1 79% (2 61) IR(KBr) 1352 (m, S=O), 1249, 1204 (s, C-F), 1150 (s, S-O) cm M p 310 C e C c cat eee.e Example 4 Synthesis oftris((pentafluorophenylsulfonyl)imide) (1,10phenanthroline)erbium(III), ErtN(SO2C6F5)2)3 C 2HaN2 t) \ ] The potassium salt of the ligand bis(nonafluorobutylsulfonyl)imide was synthesized by a one- pot synthesis described by Sogabe et al. (them. Lett (2000), 944 This potassium salt was stirred for 2 hours with a 20% H2SO4 aqueous solution and the mixture was extracted with diethylether The ether was distilled off to give HN(S02C6F5)2.

An amount of 1 g (2 I mmol) of HN(SO2C6F5)2 was dissolved in 50 ml of water and a slight excess of 0 153 g (0 4 mmol) Er2O3 was added The mixture was stirred for 24 hours under reflex The precipitated solids were filtered off and were dissolved in ethanol The unreacted Er2O3 was filtered off and a quantity of 0 069 g (0 35 mmol) of 1,10-phenanthroline hydrate was added to the mixture The system was reflexed for 2 hours. The solid was filtered off and washed with water, ethanol and hexane, the product was then dried first 12h under vacuo at 50 C and then for 24h at 105 C (yield 60%).

CHN -Analysis Found (calc) C 32.63% (32 46), H. 0 28% (0 45), N 3 72% (3 94) IR 1490 (m, C6F5), 1305 (s, S=O), 1249, 1225 (s, C-F); 1120 (s, S-O) cm M p 240 C Example 5 Synthesis of tris(bis(nonafluorobutylsulfonyl)imide)(4,7- diphenyl- 1,10phenanthroline)erbium(III), Er(N(SO2C4F,)2)3 C2H6N2(C6H5)2 N\ |,Er\ 3 C4F9 The compound Er(N(SO2C4F)2)3 C2H6N2(C6H5)2 was obtained in the same way as in example 3, except that 0 11 g (0 33 mmol) of 4,7-diphenyl-1,10phenanthroline was used instead of I,10-phenanthroline.

CHN -Analysis Found (calc) C 25 31% (25 74), H 0 42% (0 72), N 3 53% (3 13) IR (KBr) 1358 (m, S=O); 1265, 1214 (s, C-F); 1140 (s, S-O) cm M P 260 C Example 6 Synthesis oftris(bis(trifluoromethylsulfonyl)imide)(hexa-1,10phenanthroline)erbium(III), [Er(C 2HaN2)6] [(N(S02CF3)2)]3 A solution of 0 44 g (I 16 mmol) of ErCI3 6H2O in 30 ml of absolute ethanol was added dropwise to a stirred solution of 1 g (3 48 mmol) of commercially available Li(N(CF3SO2)2) (Fluke) in 50 ml of ethanol This mixture was stirred for two hours. A slight excess of 0 24 g (1 2 mmol) 1,10-phenanthroline hydrate (C'2HeN2 H20) in 20 ml of absolute ethanol was added to the stirred filtrate This mixture was refluxed for 3 hours and the resulting solid was ces::: cee. :: .e ece.

c. . . . first washed with hot acetonitrile, filtered and washed with ethanol and hexane The obtained compound was recrystallized in isopropanol and dried in vacuo at 60 C (yield 90%) The compound is well soluble in DMSO and DMF. Though we tried to get a stoichiometry according to "Er(N(SO2CF)2)3.C2HxN2", the composition ofthe precipitated solid was found to be [Er(C'2HxN2)6][(N(SO2cFl)2)]3 CHN -Analysis Found (calc) C 44 11% (43 72), H 2 67% (2 54), N 9 15% (9 80) IR(KBr) 1349 (m, S=O), 1202, 1229 (s, C-F), 1150 (s, S-O) cm M p decomposition starts at 310 C Example 7 Synthesis of tris(bis(nonafluorobutylsulfonyl)imide)( l,10phenanthroline)neodymium(III), Nd(N(SO2CF,)2)3 C2HxN2

V

The compound Nd(N(SO2C4F')2)3 C'2HxN2 was obtained in the same way as in example 1, except that 0 194 g (0 54mmol) of NdCI3 6H20 was used instead of ErCI3 6H2O CHN-Analysis Found (calc) C 20.34% (cal 20.94), H 0 61%(0 40), N 3 31% (3 39) IR(KBr) 1345 (m, S=O), 1202, 1245 (s, C-F), 1149 (s, S-O) cm M p 320 C Example 8 Luminescence measurements on tris(bis(heptadecafluorooctylsulfonyl)imide)(1,10-phenanthroline) erbium(III) A KBr pellet containing about 20 mg of tris(bis(heptadecafluoroocylsulfonyl)imide)(l,10phenanthroline)erbium(IIl) and 180 mg of IR-grade KBr was prepared The pellet was then introduced in the sample compartment of the Edinburgh Instruments FS-920P spectrofluorimeter With equal settings of the fluorimeter (emission slits 0 55 mm, spectral resolution 3 nary), two photoluminescence spectra were recorded (1) excitation at 520 nm, in the 2H,,/2 level, emission recorded between 1350 and 1700 nm (figure 1); (2) excitation at 333 nm, corresponding to the phenanthroline n * band, emission recorded between 1350 and 1700 nm (figure 2) A third photoluminescence spectrum was recorded, monitoring the emission at 1509 nm, varying the excitation wavelength between 250 and 650 nm (figure 4) Example 9 general example With bis(sulfonyl)imide lanthanide complexes Lewis base adducts of the tris complexes were formed with l,10-phenanthroline, in analogy with the 1,10- phenanthroline adducts of the tris(,8-diketonato)lanthanide(lII) complexes The lanthanide ion of choice was the trivalent erbium The function of 1,10-phenanthroline is to saturate the coordination sphere of the erbium(lII) ion and to harvest excitation light that can be transferred to the excited states of the Er3t ion The erbium complexes can be formed by addition of one equivalent of erbium(IlI) chloride hexahydrate to three equivalents of the potassium salt of a disulfonylamide, in the presence of one equivalent of l,10-phenanthroline, and with absolute ethanol as the solvent Compounds of disulfonylimides were made with CF3, CF', CxF and C'6F33 chains The complexes were characterised by elemental analysis, IR-spectroscopy and by '3C NMR spectroscopy. The stoichiometry of the complexes (except for the ligand with CF3 groups) is such that for each erbium(III) ion, three bis(perfluoroalkylsulfonyl)imide c: ce. : .' :e::: c. . . . ligands and one 1,10-phenanthroline ligand are present The coordination number of erbium is therefore eight The analytical results of the complex with the bis(trifluoromethylsulfonyl) imide ligand indicate that six 1,10-phenanthroline ligands and three bis(trifluoromethylsulfonyl)imide are present for each erbium ion Repetition of the synthesis gave compounds with similar monomeric analysis results The luminescence intensity of the erbium complexes was found to be a function of the chain length of the perfluoroalkyl group, in the sense that the intensity increases with increasing chain length The intensity increase between the C4F, and the Cafe is more pronounced than between the CAFE, and the C6F33 chain On the other hand, the solubility of the compounds decreases drastically with increasing chain length The compound with the perfluorooctyl chain gives a good compromise between luminescence intensity and solubility.

The photoluminescence of erbium complex with perfluoroalkyl chains was evaluated at room temperature by dispersing the powdered compound into a KBr pellet Upon direct excitation of the erbium(III) ion in the 4f manifold at 520 nm (population of the 2H' '/2 level), a weak nearinfrared photoluminescence signal centred around 1520 nm was observed (Figure 1) This signals corresponds to the transition of the first excited state (4I'3/2) to the ground state ( 15/2) When we changed the excitation wavelength to 333 nm, the intensity of the photoluminescence signal increased dramatically by a factor of more than 20 (Figure 2-3) This excitation wavelength corresponds to the absorption maximum of the 1, 10phenanthroline ligand and this absorption maximum was determined by measuring the excitation spectrum (Figure 4). The fine structure in the emission spectrum is due to transitions between the crystal-field levels of the 4I3/2 and 4I5/2 manifolds The presence of crystal-field fine structure is an indication that the Er34 ion occupies well-defined crystallographic sites in compound 1. To enable a wide gain bandwidth for optical amplification, a broad emission band is desirable The full width at half maximum (FWHM) of the 4I3/2 415/2 transition in compound l is 100 rim This is an exceptional broad emission band for an erbium-doped material. For instance, in erbium-implanted silicium dioxide the FWHM of the emission band is only 11 nm This value increases to 19 nm in sodalime glass, to 55 nm in alumina, and to 64 nm in a fluorohafnate glass Slooffet al observed a FWHM of nm for a terphenyl-based acyclic erbium complex Therefore, it is shown that a dramatic increase of the erbium- centered near-infrared luminescence intensity can be achieved by using 1, 10-phenanthroline as the light-harvesting moiety in complexes with inorganic chelate rings These rings, consisting of bis(perfluoroalkylsulfonyl)imides, contain no C-H bonds which could be efficient quenchers of the near-infrared luminescence, resulting in low loss of the absorbed energy. By using l,l0-phenanthroline, the amount of light that can be absorbed is several orders of magnitude higher than when exciting directly into the f-levels of the erbium ion Example 10 Luminescence measurements on tris(bis(heptadecafluoroocylsulfonyl)imide) (1,10-phenanthroline)neodymium(III).

A KBr pellet containing about 20 mg of tris(bis(heptadecafluoroocylsulfonyl)imide)( l, l 0phenanthroline)neodymium(III) and 180 mg of IR-grade KBr was prepared The pellet was then introduced in the sample compartment of the Edinburgh Instruments FS-920P spectrofluorimeter With equal settings of the fluorimeter (emission slits 0.55 mm, spectral resolution 3 nary), two photoluminescence spectra were recorded (l) excitation at 586 nm, in the 4G5/2 level, emission recorded between 750 and 1450 nm (figure 5), (2) excitation at 334 nm, corresponding to the phenanthroline n it* band, emission recorded between 750 and a c a a , a c a. a as a a. a a 1450 rim (figure 6) A third photoluminescence spectrum was recorded, monitoring the emission at 1055 nm, varying the excitation wavelength between 270 and 600 nm (figure 8) Figure 5 shows that neodymium-centered luminescence can be observed upon direct excitation in the 4G5/2 level However, the intensity is rather low Figure 6 shows the neodymium- centered luminescence upon excitation in the phenanthroline moiety at 334 nm The integrated emission is over lO times more intense than that in figure 5 Figure 7 shows the combined spectra, clearly indicating the dramatic increase of the neodymium-centered luminescence when excitation occurs in the phenanthroline unit Figure 8 shows the excitation spectrum, indicating a much higher luminescence intensity upon excitation in the UV Example 11 Luminescence measurements on tris(bis(heptadecafluoroocylsulfonyl)imide)( 1,1 0-phenanthroline) ytterbium(III) A KBr pellet containing about 20 mg of tris(bis(heptadecafluorooctylsulfonyl)imide)( l, 10phenanthroline)ytterbium(lII) and 180 mg of IR-grade KBr was prepared The pellet was then introduced in the sample compartment of the Edinburgh Instruments FS-920P spectrofluorimeter.

Because Yb3+ has only got one excited 4f level, direct excitation of the Yb3+ ion with common techniques is not obvious. However, the excitation spectrum, monitored at 976 rim indicates that here also, excitation in the phenanthroline moiety gives best results Figure 9 shows the emission spectrum of the tris(bis(heptadecafluoroocylsulfonyl)imide)( 1, 10phenanthroline)ytterbium(III), excited at 340 nm, corresponding to the phenanthroline n it* band The emission was recorded between 850 and 1150 rim In figure 1O, the excitation spectrum is given Example 12 preparation The lanthanide complexes are well soluble in coordinating solvents, e.g acetone and dimethylsulfoxide (DMSO), but these solvents can remove the bis(sulfonyl)imide ligands from the first coordination sphere This results in a loss of luminescence intensity Therefore after processing these complexes with coordinating solvents, a drying step is necessary in order to remove these coordinating solvents from the first coordination sphere and to bring the bis(sulfonyl)imide back to the first coordination sphere of the lanthanide ion This drying step is typically performed at temperatures between 100 and 200 C (but well below the decomposition temperature of the complexes), in a hot-air oven, or in a vacuum-oven c: ce. .e: : .e c:. .e ë:e .

REFERENCES TO THIS APPLICATION

[1] L H Slooff, A Polman, M P Oude Wolbers, F.C J M. van Veggel, D N Reinhoudt, J.W Hofstraat, "Optical properties of erbium-doped organic polydentate cage complexes", J. Appl.

Phys. 83 (1998) 497 [2] R J Curry and W P Gillin, "I 54 1lm electroluminescence from erbium III-tris-8 hydroxyquinoline - ErQ-based organic light-emitting diodes," Appl. Phys. I'ett. 75 (1999) [3] Y Hasegawa, T. Ohkubo, K Sogabe, Y Kawamura, Y Wada, N Nakashima and S Yanagida, "Luminescence of Novel Neodymium Sulfonylaminate Complexes in Organic Media", Angew. (.,hem. 112 (2000) 365 [4] M Ryo, Y Wada, T Okubo, T Nakazawa, Y Hasagawa and S Yanagida, "Spectroscopic study on strongly luminescent Nd(III) exchanged zeolite TMAi-containing FAU type zeolite as a suitable host for ship-in-bottle synthesis", J Mater Chem 12 (2002) [5] J W Hofstraat, M P Oude Wolbers, F C J M Veggel, D N. Reinhoudt, M H V Werts and J.W Verhoeven, "Near lR-Luminescent Rare Earth Ion-Sensitizer Complexes", Journal of Fluorescence, 8, 4, (1998) 301 [6] K Sogabe, Y Hasegawa, Y. Wada, T. Kitamura, S Yanagida, Chem Lett., (2000) 944 [7] Y. Hasegawa et al, J Lumin, 101 (2003) 235

Claims (2)

se :: ce. :: .ë e e e CLAIMS

1 A lanthanide organic ternary complex according to following formula I, wherein R Y S o No \L B R2 X ISl O n the dotted lines represent one double bond, which is dispersed over several bonds, n is any integer from 1, 2, 3 or 4, each X and Y is independently selected from the group consisting of a single bond or a dialect, saturated or unsaturated, substituted or unsubstituted Cl-Co hydrocarbon group optionally including one or more heteroatoms in or at the ends of the carbon atom chain, said heteroatoms being selected from the group consisting of 0, S. and N (provided that said heteroatom is not linked to the S of the sulfonyl), such as C-6 alkylene, C2.6 alkenylene, C2 6 alkynylene, -O(CH2) 5-, -(CH2)4-O-(CH2)4-, -S-(CH2)5-, - (CH2)4-S- (CH2)4-, -NR''-(CH2)-5-' -(cH2)-4-NR-(cH2)-4-and C30 cycloalkylidene, each of said C-C,o hydrocarbon group is optionally substituted with one or more R9, each R' and R2 can independently be perfluorinated, partially or not fluorinated and is independently selected from C2 24 alkyl, C3 0 cycloalkyl, C2 24 alkenyl, C3,0 cycloalkenyl, C2 24 alkynyl; C3 0 cycloalkynyl, each of said C2 24 alkyl, C3t, cycloalkyl, C2 24 alkenyl, C3 0 cycloalkenyl, C2 24 alkynyl, C3 '0 cycloalkynyl optionally includes one or more heteroatoms in the carbon-atom chain or at the ends of said chain, said heteroatoms being selected from the groups consisting of 0, S and N. aryl, arylalkyl, heterocyclic ring, and each of said C2 24 alkyl, C o cycloalkyl, C2 24 alkenyl, C3 0 cycloalkenyl, C224 alkynyl, C3 0 cycloalkynyl, aryl, arylalkyl, heterocyclic ring s optionally substituted with one or more R3, Each R3, Rx and R9 can independently be perfluorinated, partially or not fluorinated and are independently selected from the group consisting of hydrogen, halogen, C 24 alkyl, C2 24 alkenyl, C2 24 alkynyl, C3 0 cycloalkyl, C3' cycloalkenyl, C3, cycloalkynyl, each of said C 24 alkyl, C3 o cycloalkyl, C2 24 alkenyl, C3 0 cycloalkenyl, C2 24 alkynyl, C3 o cycloalkynyl optionally includes one or more heteroatoms in the carbon-atom chain or at the ends of said chain, said heteroatoms being selected from the groups consisting of 0, S and N. oR4, SR4 CN, isocyano, thiocyano, isothiocyano, nitroso, NO2, NR5R6, sulfonate, haloalkyl, c(=o)R7' C(=S)R7, aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy (optionally a oxybenzyl), arylalkylthio (optionally a benzylthio), heterocyclic ring, oxyheterocyclic ring, thioheterocyclic ring, alkyl-heterocyclic ring, oxyalkyl- heterocyclic ring, thoalkylheterocyclic ring, Each R4, R5, and R can independently be perfluorinated, partially or not fluorinated and are independently selected from the group consisting of H. OH, Ct 24 alkyl, C' 24 alkenyl, aryl, C3 0 cycloalkyl, C4 0 cycloalkenyl, 5-6 membered heterocyclic ring, e. :: :e c:: . c. cece.

:e:. :. - Each R7 can independently be perfluorinated, partially or not fluorinated and is independently selected from the group consisting of H. OH, C'-8 alkyl, Cat 24 alkenyl, Cal 24 alkoxy, Cat 24 alkylthio, C3 0 cycloalkyl, C4 0 cycloalkenyl; aryl, 5-6 membered heterocyclic ring, - L is selected from the group of lanthanides; - B is selected from neutral bidentate and tridentate heterocyclic rings, optionally with the proviso that at least one of Rut R2, X or Y contains hydrogen.

2 Use of a lanthanide organic ternary complex according to formula II, as luminescence emitting complexes in advanced optically amplifying material for data communications and telecommunications applications wherein _ -\ N\ /L B O n

II

- the dotted lines represent one double bond, which is dispersed over several bonds, - n is any integer from 1, 2, 3 or 4, - each X and Y is independently selected from the group consisting of a single bond or a divalent, saturated or unsaturated, substituted or unsubstituted C-C0 hydrocarbon group optionally including one or more heteroatoms in or at the ends of the carbon atom chain, said heteroatoms being selected from the group consisting of O. S. and N (provided that said heteroatom is not linked to the S of the sulfonyl), such as C'-6 alkylene, C26 alkenylene, C2 6 alkynylene, -O(CH2) 5-, -(CH2) 4-O-(CH2) 4-, -S-(CH2), 5- , -(CH2) 4-S- (CH2) 4-, -NR''-(CH2)' 5-, -(CH2) 4-NR -(CH2) 4-and C3 0 cycloalkylidene, each of said C-Co hydrocarbon group is optionally substituted with one or more R9, - each R' and R2 can independently be perfluorinated, partially or not fluorinated and is independently selected from C2 24 alkyl, C3 0 cycloalkyl, C2 24 alkenyl, Cal 0 cycloalkenyl, C2 24 alkynyl, C3 0 cycloalkynyl, each of said C2 24 alkyl, C3 0 cycloalkyl, C2 24 alkenyl, Cal,0 cycloalkenyl, C2 24 alkynyl, C3,0 cycloalkynyl optionally includes one or more heteroatoms in the carbon-atom chain or at the ends of said chain, said heteroatoms being selected from the groups consisting of O. S and N. aryl; arylalkyl; heterocyclic ring, and each of said C2 24 alkyl, C3 0 cycloalkyl, C2 2s alkenyl, C3 0 cycloalkenyl, C2 24 alkynyl, C3 0 cycloalkynyl, aryl, arylalkyl, heterocyclic ring is optionally substituted with one or more R3; - Each R3, R8 and R9 can independently be perfluorinated, partially or not fluorinated and are independently selected from the group consisting of hydrogen, halogen, Cat 24 alkyl, C2 24 alkenyl, C2 24 alkynyl, C3 0 cycloalkyl, C3 0 cycloalkenyl, C3 0 cycloalkynyl, each of said Cal 24 alkyl, C3 0 cycloalkyl, C2 24 alkenyl, C3 0 cycloalkenyl, C2 24 alkynyl, C3 0 cycloalkynyl optionally includes one or more heteroatoms in the carbon-atom chain or at e. :: ë:: I. see.. ee.

the ends of said chain, said heteroatoms being selected from the groups consisting of O. S and N. oR4, SR4 CN, isocyano, thiocyano, isothiocyano, nitroso, NO2, NR5R6, sulfonate, haloalkyl, C(=o)R7, C(=S)R7, aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy (optionally a oxybenzyl), arylalkylthio (optionally a benzylthio), heterocyclic ring, oxyheterocyclic ring, thioheterocyclic ring, alkyl-heterocyclic ring, oxyalkyl- heterocyclic ring, thioalkyl- heterocyclic ring, Each R4, R5, and R6 can independently be perfluorinated, partially or not fluorinated and are independently selected from the group consisting of H. OH, C 24 alkyl, C 24 alkenyl, aryl, C3 0 cycloalkyl, C4 0 cycloalkenyl, 5-6 membered heterocyclic ring, Each R can independently be perfluorinated, partially or not fluorinated and is independently selected from the group consisting of H. OH, C x alkyl, C' 24 alkenyl, C' 24 alkoxy; C 24 alkylthio, C3 0 cycloalkyl, C4 0 cycloalkenyl, aryl, 5-6 membered heterocyclic ring, L is selected from the group of lanthanides, B is selected from neutral bidentate and tridentate heterocyclic rings, optionally 3 The use according to claim 2, wherein L is erbium 4 The use according to claim 2 and 3, wherein the luminescence output is obtained by indirect excitation of L The use according to claim 3, wherein the luminescence is obtained by using an excitation wavelength of between 300 nm and 350 nm 6 A method for obtaining an intense luminescence, said method comprising the steps of preparing a complex comprising a lanthanide, I or more bis(sulfonyl)imide ligands and I or more bidentate or tridentate heterocyclic rings and irradiating the complex with a wavelength in the range of 25 nm above or under the maximum of the excitation spectrum of said complex measured in the range of the luminescence wavelength of the lanthanide, hereby excluding the direct excitation in the lanthanide of said complexes 7 A method as in claim 6, wherein the complex is according to formula I