ES2388091B1 - OCTACOORDINATED TERNARY COMPLEXES OF ERBIO (III) OR ITERBIO (III) OPTICALLY ACTIVE AND METHOD OF OBTAINING. - Google Patents
OCTACOORDINATED TERNARY COMPLEXES OF ERBIO (III) OR ITERBIO (III) OPTICALLY ACTIVE AND METHOD OF OBTAINING. Download PDFInfo
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- ES2388091B1 ES2388091B1 ES201130329A ES201130329A ES2388091B1 ES 2388091 B1 ES2388091 B1 ES 2388091B1 ES 201130329 A ES201130329 A ES 201130329A ES 201130329 A ES201130329 A ES 201130329A ES 2388091 B1 ES2388091 B1 ES 2388091B1
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 54
- 239000003446 ligand Substances 0.000 claims abstract description 38
- JHFPQYFEJICGKC-UHFFFAOYSA-N erbium(3+) Chemical compound [Er+3] JHFPQYFEJICGKC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002879 Lewis base Substances 0.000 claims abstract description 23
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 20
- AWSFICBXMUKWSK-UHFFFAOYSA-N ytterbium(3+) Chemical compound [Yb+3] AWSFICBXMUKWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000976 ink Substances 0.000 claims abstract description 15
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 13
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 6
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims abstract description 3
- -1 tris (2,6-dimethyl-3,5-heptanedione) mono (5-nitro-1,10-phenanthroline) erbium Chemical compound 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 35
- 239000007983 Tris buffer Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 13
- 230000003113 alkalizing effect Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 125000005594 diketone group Chemical group 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical group NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- PDDBTWXLNJNICS-UHFFFAOYSA-N 5-nitro-1,10-phenanthroline Chemical compound C1=CC=C2C([N+](=O)[O-])=CC3=CC=CN=C3C2=N1 PDDBTWXLNJNICS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003898 horticulture Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 claims description 2
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 claims description 2
- PKAHQJNJPDVTDP-UHFFFAOYSA-N methyl cyclopropanecarboxylate Chemical compound COC(=O)C1CC1 PKAHQJNJPDVTDP-UHFFFAOYSA-N 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims 2
- 238000005401 electroluminescence Methods 0.000 claims 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims 2
- FDZVJAHIBXZLCP-UHFFFAOYSA-N 1,1,1,5,5,5-hexafluoropentane-2,3-dione Chemical compound FC(F)(F)CC(=O)C(=O)C(F)(F)F FDZVJAHIBXZLCP-UHFFFAOYSA-N 0.000 claims 1
- SUORUQZBFOQDGX-UHFFFAOYSA-N 1,1,1,5,5,6,6,7,7,7-decafluoroheptane-2,4-dione Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)C(F)(F)C(F)(F)F SUORUQZBFOQDGX-UHFFFAOYSA-N 0.000 claims 1
- 241000282693 Cercopithecidae Species 0.000 claims 1
- 150000000917 Erbium Chemical class 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- GLQOFBCJADYRKR-UHFFFAOYSA-K erbium(3+);trifluoromethanesulfonate Chemical compound [Er+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F GLQOFBCJADYRKR-UHFFFAOYSA-K 0.000 claims 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000013307 optical fiber Substances 0.000 claims 1
- 230000005693 optoelectronics Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910021644 lanthanide ion Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 230000005284 excitation Effects 0.000 description 10
- 238000005424 photoluminescence Methods 0.000 description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical group NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000005371 ZBLAN Substances 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000005303 fluorophosphate glass Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000006064 precursor glass Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F1/00—Methods of preparing compounds of the metals beryllium, magnesium, aluminium, calcium, strontium, barium, radium, thorium, or the rare earths, in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Complejos ternarios octacoordinados de erbio(III) o iterbio(III) ópticamente activos y método de obtención.#La presente invención se refiere a un complejo ternario de lantánidos ópticamente activo, donde el ión lantánido se encuentra coordinado a tres ligandos betadicetonato y a un ligando base de Lewis de acuerdo con la siguiente fórmula general:#[Ln({be}-dicetona){sub,3}(N,N-donor)],#donde Ln es Er (erbio) o Yb (iterbio); ({be}-dicetona){sub,3} representa tres ligandos betadicetonato; y (N,N-donor) representa un ligando base de Lewis. También es objeto de la presente invención el método de síntesis de los complejos descritos, así como las múltiples aplicaciones de los mismos en dispositivos ingenieriles de Optoelectrónica y Telecomunicaciones, principalmente como material dopante en NIR-OLEDs, EDFA/YEDFAs, tintas de seguridad, películas transparentes dopadas para invernaderos, pantallas de cristal líquido y reactivos de desplazamiento NMR o células solares, entre otros dispositivos.Octacoordinated ternary complexes of optically active erbium (III) or ytterbium (III) and method of obtaining. # The present invention relates to an optically active lanthanide ternary complex, where the lanthanide ion is coordinated to three betadicetonate ligands and a base ligand Lewis according to the following general formula: # [Ln ({be} -dicetone) {sub, 3} (N, N-donor)], # where Ln is Er (erbium) or Yb (yerbium); ({be} -dicetone) {sub, 3} represents three betadicetonate ligands; and (N, N-donor) represents a Lewis base ligand. The method of synthesis of the described complexes, as well as the multiple applications thereof in engineering devices of Optoelectronics and Telecommunications, mainly as a doping material in NIR-OLEDs, EDFA / YEDFAs, security inks, films, is also object of the present invention. transparent doped for greenhouses, liquid crystal displays and NMR displacement reagents or solar cells, among other devices.
Description
Complejos ternarios octacoordinados de erbio(III) o iterbio(III) ópticamente activos y método de obtención Optically active terbary complexes of erbium (III) or ytterbium (III) and method of obtaining
Campo de la técnica Technical field
La presente invención pertenece al campo de la síntesis de nuevos complejos ternarios de lantánidos(III) que comprenden diferentes ligandos y, concretamente, a complejos octacoordinados de erbio(III) e iterbio(III) ópticamente activos, en los que el ión lantánido se encuentra coordinado con tres ligandos betadicetonato y un ligando base de Lewis; y a su utilización como dopantes de películas, tintas, dispositivos OLED y NIR-OLED, EDFA/ YEDFAs y células solares. 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.
De forma generalizada, se considera que los complejos ternarios de lantánidos(III) con diferentes ligandos son útiles como emisores. También son conocidos los problemas por apagamiento que pueden presentar, debido a hidratación y otras causas, y que conducen a minimizar (o invalidar) su aplicación en dispositivos ingenieriles. Resultados favorables se obtienen cuando se utilizan ligandos betadicetonato fluorados y bases de Lewis. Tales complejos ternarios son muy conocidos en el caso de europio(III) pero no así en los de erbio(III) e iterbio(III), emisores en el infrarrojo (K. Binnemans. Rare earth beta-diketonates. Cap. 25. Handbook on the Physics and Chemistry of Rare Earths. Vol 35, ed K.A. Gschneider, J-C.G. Bünzli y V.K. Pecharsky. 2005 Elsevier B.V.). La causa hay que buscarla en que la caracterización de la emisión en el infrarrojo precisa de equipamiento instrumental no siempre disponible. In general, ternary complexes of lanthanides (III) 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 iterbium (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, JC.G. 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.
De hecho, la serie de complejos tris(dicetona)mono(base de Lewis)lantánido(III),[Ln(�-dicetona)3(N,N-donor)], objeto de reivindicación, es enteramente nueva y solo los siguientes antecedentes han aparecido tras exhaustivas búsquedas bibliográficas: In fact, the series of complexes tris (dicetone) mono (Lewis base) lanthanide (III), [Ln (�-diketone) 3 (N, N-donor)], object of claim, is entirely new and only the following antecedents have appeared after exhaustive bibliographic searches:
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- un análogo del complejo tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimetil-3,5-octanodiona) mono(5-nitro-1,1fenantrolina)erbio(III), [Er(Hfod)3(5NO2phen)], que incluye bipiridina en vez de 5NO2phen como ligando donor, publicado por Iftikhar, K; M. Sayeed M; Ahmad, N. en Inorg. Chem., 1982, 21:80, y que no exhibe propiedades luminiscentes; an analogue of the tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione) mono (5-nitro-1,1-phenanthroline) erbium (III) complex, [ Er (Hfod) 3 (5NO2phen)], which includes bipyridine instead of 5NO2phen 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;
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- los análogos de erbio e iterbio del complejo tris(dibenzoilmetano)mono(2,2´-bipiridina)erbio(III), [Er(Hdbm)3(bipy)], que incluyen el ligando batofenantrolina en vez de piridina, informados por Kawamura Y; Wada, Y; Yanagida, S. en Jpn. J. Appl. Phys. 2001, 40:350-356; y the erbium and iterbium analogs of the tris (dibenzoylmethane) mono (2,2'-bipyridine) erbium (III) complex, [Er (Hdbm) 3 (bipy)], which include the batophenanthroline instead of pyridine ligand, reported by Kawamura Y; Wada, Y; Yanagida, S. in Jpn. J. Appl. Phys. 2001, 40: 350-356; Y
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- el complejo Er(Hfac)3bipy, publicado por Van Staveren, D.R.; van Albada, G.A.; Haasnoot, JG; Kooijman, H. et al. en Inorg. Chim. Acta, 2001, 315:163. the Er (Hfac) 3bipy complex, published by Van Staveren, D.R .; van Albada, G.A .; Haasnoot, JG; Kooijman, H. et al. in Inorg. Chim. Acta, 2001, 315: 163.
DESCRIPCIÓN DE LA INVENCIÓN DESCRIPTION OF THE INVENTION
El principal objetivo de esta invención es describir una serie de complejos octacoordinados de erbio e iterbio y aportar algunas de sus estructuras, sus propiedades luminiscentes y sus aplicaciones ingenieriles en Optoeléctrónica, así como divulgar un método general (junto con algunas variantes) de preparación de dichos complejos. Esta invención concierne a nuevos complejos ternarios de lantánidos(III) que comprenden diferentes ligandos, concretamente de complejos de erbio(III) o iterbio(III) ópticamente activos, en los que el ión lantánido se encuentra coordinado con tres ligandos betadicetonato y un ligando base de Lewis. Estos complejos poseen propiedades fotoluminiscentes y de óptica no lineal. La presente invención se refiere asimismo al uso versátil de los complejos descritos como material dopante en muy diversos dispositivos, como OLED y NIR-OLEDs, EDFAs/YEDFAs, células solares y cualquier otro dispositivo que cambie su estado óptico bajo irradiación o aplicación de voltaje. The main objective of this invention is to describe a series of octacoordinated complexes of erbium and iterbium and 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.
Concretamente, la invención corresponde a complejos ternarios octacoordinados de erbio(III) o iterbio(III) ópticamente activos que poseen la fórmula general: Specifically, the invention corresponds to optically active octacoordinated ternary complexes of erbium (III) or iterbium (III) having the general formula:
[Ln(�-dicetona)x(N,N-donor)] [Ln (�-diketone) x (N, N-donor)]
donde Ln es Er (erbio) o Yb (iterbio); (�-dicetona)3 representa tres ligandos betadicetonato; y (N,N-donor) representa un ligando base de Lewis. where Ln is Er (erbium) or Yb (iterbium); (�-diketone) 3 represents three betadicetonate ligands; and (N, N-donor) represents a Lewis base ligand.
Constituye otro objeto principal de la presente invención el método de preparación de los complejos de erbio(III) o iterbio(III) antes descritos. Dicho proceso se caracteriza porque comprende la mezcla, en solución y 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 mixture, in solution and
agitación, de cantidades moleculares de compuestos que aseguren la presencia de erbio o iterbio, dicetona y ligando base de Lewis en proporciones 1:3:1. agitation, of molecular amounts of compounds that ensure the presence of erbium or ytterbium, diketone and Lewis base ligand in 1: 3: 1 ratios.
Descripción detallada Detailed description
En cuanto a la familia de compuestos reivindicada, el ligando �-dicetonato (que, en número de 3 se coordina al ión central) puede ser fluorado o no; y el ligando N,N-donor o base de Lewis es preferiblemente, y de manera indistinta, 5-nitro-1,10-fenantrolina, batofenan-trolina o 2,2-bipiridina. As for the claimed family of compounds, the �-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.
Los complejos de erbio(III) o iterbio(III) más representativos de los aquí divulgados, aunque no los únicos posibles dentro de las combinaciones expuestas, son los tris(dicetona)mono(base de Lewis)lantánido(III): The most representative erbium (III) or ytterbium (III) complexes of those disclosed herein, although not the only ones possible within the combinations presented, are the tris (dicetone) mono (Lewis base) lanthanide (III):
tris(dibenzoilmetano)mono(2,2´-bipiridina)erbio(III), tris (dibenzoylmethane) mono (2,2´-bipyridine) erbium (III),
tris(acetilacetona)mono(batofenantrolina)erbio(III), tris[3-tri fluorometilhidroximetileno)-d-canfor]mono(2,2´bipiridina)erbio(III), tris (acetylacetone) mono (batophenanthroline) erbium (III), tris [3-tri fluoromethylhydroxymethylene) -d-camphor] mono (2,2'bipyridine) erbium (III),
tris[3-heptafluoropropilhidroximetileno)-d-camphor]mono (batofenantrolina)erbio(III), tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (batophenantroline) erbium (III),
tris[3-heptafluoropropilhidroximetileno)-d-canfor]mono (2,2´-bipiridina)erbio(III), tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (2,2'-bipyridine) erbium (III),
tris(1,1,1-trifluoro-2,4-pentanodiona)mono(2,2´-bipiridina)erbio(III), tris (1,1,1-trifluoro-2,4-pentanedione) mono (2,2'-bipyridine) erbium (III),
tris(1,1,1-trifluoro-5,5-dimetil-2,4-hexanodiona)mono(5-nitro-1,10-fenantrolina)erbio(III), tris(1,1,1,5,5,6,6,7,7,7decafluoro-2,4-heptanodiona)mono (5-nitro-1,10-fenantrolina)erbio(III), tris (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione) mono (5-nitro-1,10-phenanthroline) erbium (III), tris (1,1,1,5,5 , 6,6,7,7,7cacafluoro-2,4-heptanedione) mono (5-nitro-1,10-phenanthroline) erbium (III),
tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimetil-3,5-octanodiona)mono(5-nitro-1,10-fenantrolina)erbio(III), tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione) mono (5-nitro-1,10-phenanthroline) erbium (III),
y sus correspondientes complejos de iterbio. and its corresponding iterbium complexes.
Se ha obtenido por difracción de rayos X la elucidación estructural de la mayoría de los complejos ternarios de erbio(III) o iterbio(III) con l-dicetonatos que constituye la serie reivindicada. Ninguna de las estructuras obtenidas responde a la previsión de los poliedros de coordinación propuestos (un dodecaedro con simetría D2d o un antiprisma cuadrado con simetría D4d), porque tales poliedros de coordinación se encuentran tan seriamente distorsionados que no es posible decidir la analogía con uno u otro prototipo. Normalmente, la simetría en torno a un ión de las tierras raras es C1 (sin elementos de simetría). Dos de los complejos pertenecientes a la serie reivindicada presentan las estructuras y empaquetamientos que aparecen en la Figura 1. The structural elucidation of most ternary complexes of erbium (III) or ytterbium (III) with l-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 D2d symmetry or a square antiprism with D4d symmetry), because such coordination polyhedra are so seriously distorted that it is not possible to decide the analogy with one or Another prototype Normally, the symmetry around a rare earth ion is C1 (without symmetry elements). Two of the complexes belonging to the claimed series have the structures and packaging that appear in Figure 1.
Si bien en todas las estructuras el poliedro de coordinación está constituido por dos oxígenos l-dicetonato terminales y dos nitrógenos piridilo terminales, la disposición de las especies monoméricas en la red cristalina es muy diferente a lo largo de la serie de complejos estudiados. Estas diferencias son debidas a la variación de la naturaleza y propiedades de los ligandos: rigidez de la molécula N,N-donora (mayor para batofenantrolina que para 2,2´-bipiridina); capacidad electroaceptora del ligando l-dicetonato (más alta en los ligandos fluorados debido al efecto inductivo de los grupos CF3) u otros y que son la causa de la versatilidad de las propiedades físicas (y aplicaciones) mostradas por la serie de complejos reivindicada. Although in all structures the coordination polyhedron consists of two terminal l-diketonate oxygen 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 N molecule, N-donora (greater for batophenantroline than for 2,2'-bipyridine); electro-acceptor capacity of the ligand l-diketonate (higher in the fluorinated ligands due to the inductive effect of the CF3 groups) or others and which are the cause of the versatility of the physical properties (and applications) shown by the claimed complex series.
En lo que respecta al método de síntesis y obtención de esta familia de compuestos, y dado su carácter de complejos ternarios, su consecución puede de manera preferible llevarse a cabo bien a partir de los tres constituyentes básicos (sal de erbio o iterbio, dicetona y base de Lewis) o bien a partir del complejo binario trisbetadicetonato de erbio o iterbio y la especie base de Lewis. La primera de estas posibilidades supone un proceso en dos pasos o etapas mientras la segunda constituye un caso preferido, realizable en un solo paso o etapa. 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.
En la realización preferida en dos etapas, más general, el método de preparación comprende: In the two more preferred preferred embodiment, the preparation method comprises:
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- mezclar en proporción molecular 1:3:3 una disolución de un compuesto binario de erbio(III) o iterbio(III) en un disolvente adecuado, con una disolución de una beta-dicetona en un disolvente adecuado y un alcalinizante en un disolvente adecuado; y 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
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- adicionar a dicha mezcla una disolución de un ligando base de Lewis (seleccionado preferentemente dentro del grupo compuesto por 2,2´-bipiridina, batofenantrolina y 1,10-fenantrolina) en un disolvente adecuado y en proporción molar tal que se obtiene la relación molar sal binaria : dicetona : base de Lewis = 1:3:1, y agitar la mezcla final. 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.
De manera preferida, el compuesto binario de erbio o iterbio a utilizar en la realización inmediatamente descrita es un nitrato o un triflato. También preferentemente, el alcalinizante preferido es un metilato alcalino (por ejemplo sódico o potásico) o un hidróxido alcalino (por ejemplo de cesio). Preferentemente, el disolvente a utilizar para la disolución es un alcohol (por ejemplo, metanol o etanol) o un acetonitrilo. 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.
Cuando se utiliza un nitrato como fuente primaria de erbio o iterbio (por ejemplo, Er(NO3)3.9H2O o Er(NO3)3.9H2O), es preferible asociarlo a una solución alcohólica como disolvente (metanol o etanol) y a un metilato (por ejemplo, sódico o potásico) como medio alcalino ajustador de pH. When a nitrate is used as the primary source of erbium or ytterbium (for example, Er (NO3) 3.9H2O or Er (NO3) 3.9H2O), 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.
Cuando se utiliza un triflato de erbio (Er(CF3SO3)3)o iterbio (Yb(CF3SO3)3) como fuente primaria de erbio o iterbio, respectivamente, es preferible asociarlo a una solución de acetonitrilo y la utilización de hidróxido de cesio como alcalinizante. When an erbium (Er (CF3SO3) 3) or ytterbium (Yb (CF3SO3) 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 cesium hydroxide as alkalizing agent .
Preferiblemente, la cantidad de alcalinizante que se adiciona a la mezcla 1:3 de compuesto binario de erbio o iterbio – betadicetona debe encontrarse en una concentración al 25% en el disolvente adecuado. 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.
En cualquiera de los casos anteriores, las cantidades a utilizar de los reactivos complejo o sal sencilla de erbio o iterbio - betadicetona – ligando base de Lewis, independientemente de si se trabaja a escala micromolar, milimolar, molar o kilomolar, guardan la relación molar 1:3:1 reseñada. 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.
Cuando se trabaja a escala milimolar, las cantidades de disolvente a utilizar para la mezcla 1:3 de compuesto binario de erbio o iterbio–betadicetona están comprendidas entre 10 y 40 mL, incluidos ambos límites, y la cantidad del ligando base de Lewis entre 5 y 15 mL, incluidos ambos límites. Para escalas superior o inferior, las cantidades a utilizar serán múltiplos o submúltiplos de las anteriores. When working on a millimolar scale, the amounts of solvent to be used for the 1: 3 mixture of binary compound of erbium or yerbium-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.
El tiempo de agitación de la mezcla final está comprendido preferiblemente entre 1 y 8 horas, siendo de manera más preferida de 5 horas. The stirring time of the final mixture is preferably between 1 and 8 hours, more preferably 5 hours.
En la realización en un paso, caso preferido por su sencillez y que presupone la disponibilidad del complejo binario trisbetadicetonato, en el que el ión erbio o iterbio está ya unido a la beta-dicetona formando un complejo que presenta una relación 1:3, el método de preparación comprende: In the realization in one step, a preferred case for its simplicity and which presupposes the availability of the binary trisbetadicetonate complex, in which the erbium or iterbium ion is already attached to the beta-diketone forming a complex that has a 1: 3 ratio, the Preparation method comprises:
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- mezclar en cantidades equimoleculares 1:1 una disolución de un complejo trisbetadicetonato de erbio(III) o iterbio(III) en un disolvente y un alcalinizante en un disolvente (que facilita la mezcla y se mezcla con el trisbetadicetonato) con una disolución de un ligando base de Lewis en un disolvente. (Dado que el trisbetadicenato de erbio o iterbio mantiene una relación molar 1:3 entre el complejo de erbio o iterbio y el betadicetonato, en esta realización se alcanza la relación 1:3:1 deseada). mixing 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 (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).
Preferiblemente en ambas disoluciones, tanto de trisbetadicetonato de erbio o iterbio como de base de Lewis, el disolvente es alcohol, y más preferentemente las disoluciones son etanólicas, es decir, el disolvente empleado en ambos casos es etanol. 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.
Debe entenderse del presente texto que el método de preparación de los complejos de erbio o iterbio puede englobar cualquiera de las combinaciones posibles entre todas las alternativas que se ofrecen. 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.
Otro propósito de la presente invención es el de proveer nuevos materiales ópticamente activos (no lineales) para su aplicación en dispositivos ingenieriles de Optoelectrónica y Telecomunicaciones, principalmente NIR-OLEDs, EDFA/YEDFAs. Estos complejos pueden ser utilizados ventajosamente en otras aplicaciones tales como tintas, películas transparentes dopadas para invernaderos, pantallas de cristal líquido y reactivos de desplazamiento NMR. 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.
Debido a que en la mayor parte de los complejos estudiados la no-simetría aparece preservada a lo largo de las dimensiones físicas de la estructura global, se reivindica aquí para toda la serie de compuestos su potencial y uso como materiales ópticos no lineales (materiales NLO) y sus aplicaciones como tales en áreas como la Optoelectrónica y la Fotónica. En relación con la respuesta de segundo-orden y en aspectos de condiciones operativas, se reivindica la favorable influencia de los vapores de cloroformo en la generación del segundo armónico. Respecto a la respuesta NLA de tercer orden, se reivindica su aplicación como soporte para la propagación de solitones ópticos espaciales. Because in most of the complexes studied, non-symmetry is preserved throughout the physical dimensions of the overall structure, its potential and use as non-linear optical materials (NLO materials) are claimed here for the entire series of compounds. ) and its 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.
La presente invención engloba asimismo el uso versátil de los complejos descritos como elementos dopantes, preferiblemente en muy diversos dispositivos como películas, tintas de seguridad, diodos orgánicos emisores de luz (OLEDs) y que emiten en el NIR (NIR-OLEDs), EDFAs/YEDFAs, células solares y cualquier otro dispositivo que cambie su estado óptico bajo irradiación o aplicación de voltaje. También se refiere la presente invención al uso en horticultura de los complejos reivindicados; la mezcla de varios de estos complejos, unos emisores en el azul y otros emisores en el rojo y el infrarrojo cercano, puede ser utilizada como dopante en plásticos para invernaderos debido a que producen un aumento de su vida de servicio media y un uso más eficiente de su energía solar. 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.
Obviamente, también es objeto de protección de la presente solicitud cualquiera de los dispositivos reseñados que comprenden cualquiera de los complejos de erbio o iterbio descritos; una célula solar, una tinta de seguridad, un dispositivo NIR-OLEDs, un dispositivo EDFA/YEDFAs, una película como las transparentes dopadas que se usan para invernaderos, pantallas de cristal líquido y reactivos de desplazamiento NMR, etc. 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.
FIGURA 1. Estructura y empaquetamiento de dos complejos de erbio e iterbio obtenidos en el Ejemplo 1: [Er(Hacac)3bath] (gráfico izquierda) y [Yb(Hfhd)3(5NO2phen)] (gráfico derecha). FIGURE 1. Structure and packaging of two complexes of erbium and ytterbium obtained in Example 1: [Er (Hacac) 3bath] (left graph) and [Yb (Hfhd) 3 (5NO2phen)] (right graph).
FIGURA 2. Espectros de emisión en metanol tras excitación a 522 nm para los compuestos [Er(Hhfc)3(bath)](gráfico izquierda) y [Er(Hfhd)3(5NO2phen)],[Er(Htpm)3(5NO2phen)] y [Er(Hfod)3(5NO2phen)] (gráfico derecha). FIGURE 2. Methanol emission spectra after excitation at 522 nm for the compounds [Er (Hhfc) 3 (bath)] (left graph) and [Er (Hfhd) 3 (5NO2phen)], [Er (Htpm) 3 (5NO2phen )] and [Er (Hfod) 3 (5NO2phen)] (right graph).
FIGURA 3. Evaluación de la fotoluminiscencia de las muestras en la región NIR tras excitación a 350 nm y 522 nm. para los complejos [Er(Hacac)3(bath)] (gráfico izquierda) y [Er(Hfhd)3(5NO2phen)] (gráfico derecha). 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)] (left graph) and [Er (Hfhd) 3 (5NO2phen)] (right graph).
A continuación se describe, a modo de ejemplo y con carácter no limitante, una realización concreta de la invención, donde se muestra la preparación preferida de algunos de los complejos reivindicados, y se analizan tanto sus propiedades luminiscentes como sus potenciales aplicaciones ingenieriles en Optoelectrónica. 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.
Ejemplo 1. Preparación de complejos octacoordinados de erbio(III) o iterbio(III) óptimamente activos de acuerdo con la presente invención. Example 1. Preparation of octacoordinated complexes of erbium (III) or ytterbium (III) optimally active in accordance with the present invention.
Se han preparado diversos complejos octacoordinados de erbio(III) e iterbio(III) ópticamente activos a partir del siguiente procedimiento: Various optically active octabordinate complexes of erbium (III) and ytterbium (III) have been prepared from the following procedure:
Se mezcla Er(NO3)3.9H2O -o su correspondiente nitrato de iterbio-(0.451 g, 1 mmol) con una �-dicetona (3 mmol) en metanol (20 mL) y una cantidad equimolecular de solución de metilato potásico (0.841 g, 3 mmol) al 25% en metanol y la adición subsiguiente, a la mezcla anterior (25 mL), de 10 mL de una solución en metanol de 2,2´bipiridina, batofenantrolina o 1,10-fenantrolina (1 mmol). Esta mezcla de reacción se agita a reflujo durante 5 horas. Si un precipitado blanco (nitrato potásico) aparece durante la agitación, decantar repetidamente. La solución clara así obtenida proporciona microcristales rosa-amarillentos. Er (NO3) 3.9H2O - or its corresponding iterbium nitrate - (0.451 g, 1 mmol) is mixed with a �-diketone (3 mmol) in methanol (20 mL) and an equimolecular amount of potassium methylate solution (0.841 g , 3 mmol) to 25% in methanol and the subsequent addition, to the previous mixture (25 mL), of 10 mL of a methanol solution of 2,2'bipyridine, batophenantroline or 1,10-phenanthroline (1 mmol). This reaction mixture is stirred at reflux for 5 hours. If a white precipitate (potassium nitrate) appears during stirring, decant repeatedly. The clear solution thus obtained provides pinkish-yellow microcrystals.
Los complejos obtenidos son los siguientes: tris(acetilacetona)mono(batofenantrolina)erbio(III), [Er(Hacac)3(bath)]; tris(2,4-hexanediona)mono (batofenantrolina)erbio(III), [Er(h)3(bath)]; tris(2,2,6,6,-tetrametil-3,5-heptanodiona)mono(bato-fenantrolina)erbio(III), [Er(Hthd)3(bath)]; tris(2,6-dimethyl-3,5-heptanodiona)mono(batofenantrolina) erbio(III), [Er(Hdmh)3(bath)]; tris(2,6-dimetil-3,5-heptanodiona)mono(5-nitro-1,10-fenantrolina)erbio(III), [Er(Hdmh)3(5NO2phen)]; tris(2,6-dimetil-3,5-heptanodiona)mono(2,2-bipiridina) erbio(III), [Er(Hdmh)3(bipy)]; tris(2,4-hexanodiona)mono(2,2-bipiridina)erbio(III), [Er(hd)3(bipy)]; tris(3,5-heptanodiona)mono(2,2-bipiridina)erbio(III), [Er(hpd)3(bipy)]; tris(octanodiona)mono(2,2-bipiridina)erbio(III), [Er(od)3(bipy)]; tris(nonanodiona)mono(2,2-bipiridina)erbio(III), [Er(nd)3(bipy)]; tris(metil-2-oxociclopentanocarboxilato)mono(2,2-bipiridina)erbio(III), [Er(MCPC)3(bipy)]; tris(ethil-2-oxociclohexanocarboxilato)mono(2,2-bipiridina)erbio(III) [Er(ECHC)3(bipy)]; The complexes obtained are the following: tris (acetylacetone) mono (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-1,10-phenanthroline) erbium (III), [Er (Hdmh) 3 (5NO2phen)]; 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(dibenzoilmetano)mono(2,2´-bipiridina)erbio(III), [Er(Hdbm)3(bipy)]; tris[3-trifluorometilhidroximetileno)-d-canfor]mono(2,2´-bipiridina)erbio(III),[Er(Hfacam)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-heptafluoropropilhidroximetileno)-d-canfor]mono (batofenantrolina)erbio(III), [Er(Hhfc)3(bath)]; tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (batophenantroline) erbium (III), [Er (Hhfc) 3 (bath)];
tris[3-heptafluoropropylhydroximetileno)-d-canfor]mono(2,2´-bipiridina)erbio(III), [Er(Hhfc)3(bipy)]; tris(1,1,1-trifluoro-2,4-pentanodiona)mono(2,2´-bipiridina)erbio(III), [Er(Htfac)3(bipy)]; tris [3-heptafluoropropylhydroxymethylene) -d-camphor] mono (2,2'-bipyridine) erbium (III), [Er (Hhfc) 3 (bipy)]; tris (1,1,1-trifluoro-2,4-pentanedione) mono (2,2'-bipyridine) erbium (III), [Er (Htfac) 3 (bipy)];
tris(1,1,1-trifluoro-5,5-dimetil-2,4-hexanodiona)mono(5-nitro-1,10-fenantrolina)erbio(III), [Er(Htpm)3(5NO2phen)]; tris(1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanodiona)mono (5-nitro-1,10-fenantrolina)erbio(III), [Er(Hfhd)3(5NO2phen)]; tris (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione) mono (5-nitro-1,10-phenanthroline) erbium (III), [Er (Htpm) 3 (5NO2phen)]; tris (1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione) mono (5-nitro-1,10-phenanthroline) erbium (III), [Er ( Hfhd) 3 (5NO2phen)];
tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimetil-3,5-octanodiona) mono(5-nitro-1,1-fenantrolina)erbio(III), [Er(Hfod)3(5NO2phen)]; 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 (5NO2phen)];
y sus correspondientes complejos de iterbio. and its corresponding iterbium complexes.
Ejemplo 2. Descripción de propiedades y aplicaciones de los complejos de erbio e iterbio del Ejemplo 1. Example 2. Description of properties and applications of the erbium and iterbium complexes of Example 1.
En solución, la naturaleza lábil de los complejos, su proclividad a la asociación y su susceptibilidad a la formación de aductos con moléculas de disolvente no favorecen la presencia de especies monoméricas. La extensión de la autoasociación tiene la siguiente dependencia del disolvente: n-hexano > tetracloruro de carbono > benceno > cloroformo = metanol. En consecuencia, es preciso recurrir a la disolución en los disolventes más polares, cloroformo o metanol, donde los complejos reivindicados se encuentran preferentemente en forma monomérica, para llevar a cabo el estudio de propiedades deseado. De este modo, la información sobre propiedades físicas obtenida tanto en estado sólido como en disolución puede ser relacionada. 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 dependence on the solvent: n-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.
Se ha podido comprobar que en la mayor parte de los complejos estudiados, la no-simetría aparece preservada a lo largo de las dimensiones físicas de la estructura global, demostrando su potencial como materiales ópticos no lineales (materiales NLO) y sus aplicaciones como tales en áreas como la Optoelectrónica y la Fotónica. En relación con la respuesta de segundo-orden y en aspectos de condiciones operativas, se reivindica la favorable influencia de los vapores de cloroformo en la generación del segundo armónico. Respecto a la respuesta NLA de tercer orden, se reivindica su aplicación como soporte para la propagación de solitones ópticos espaciales. 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 is claimed. Regarding the third-order NLA response, its application is claimed as a support for the propagation of spatial optical solitons.
El estudio de los espectros de excitación y emisión en cloroformo para los complejos [Er(Hacac)3bath] y [Er(Hthd)3bath], muestra down-conversion: después de excitación a 350 nm se observa emisión en el intervalo 365600 nm con máximos en el violeta azulado a 398 nm y 420 nm, respectivamente. Aquí se reivindica este hallazgo y su aplicación en horticultura debido a que ambas radiaciones, roja y azul, son esenciales para el crecimiento de las plantas durante todas sus etapas de desarrollo. La mezcla de los dos complejos citados (emisores en el azul) con cualquiera del resto de complejos de la serie (emisores en el rojo y el infrarrojo cercano) puede ser utilizada como dopante en plásticos para invernaderos debido a que producen un aumento de su vida de servicio media y un uso más eficiente de su energía solar. El mayor crecimiento y desarrollo de las plantas bajo tales películas plásticas es conocido como efecto Polysvetan. Actualmente, compuestos conteniendo europio(III) para su dispersión en películas poliméricas están siendo comercializados con la denominación Ksanta por Ranita (Regensburg, Germany) y las películas poliméricas que incorporan el aditivo Ksanta se encuentran disponibles en el mercado con el nombre de Redlight. The study of the excitation and emission spectra in chloroform for the [Er (Hacac) 3bath] and [Er (Hthd) 3bath] complexes shows down-conversion: after excitation at 350 nm, emission is observed in the 365600 nm range with highs 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.
La característica anteriormente descrita puede también ser aplicada en tintas de seguridad. Estas tintas son utilizadas como contramedidas a la falsificación para la protección de billetes, cheques, tarjetas y documentos de valor. Las tintas de seguridad son invisibles pero destellan en diferentes colores (pueden hacerlo en el rojo, el azul y en el infrarrojo en el caso del Er3+) bajo irradiación con luz ultravioleta. Los billetes de euro muestran, bajo irradiación ultravioleta, fibras y diagramas emisores en el rojo, el azul y el verde y si bien la composición exacta de estas tintas de seguridad se mantiene en secreto por razones obvias, resulta muy probable que el color rojo sea debido a la emisión de un complejo l-dicetonato de europio(III). Se reivindica por tanto la serie de complejos como una alternativa a los complejos de Eu3+ en tintas de seguridad. 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 Er3 +) under irradiation with ultraviolet light. Euro bills show, under ultraviolet irradiation, fibers and emitting 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 color red is due to the emission of a l-diketonate complex of europium (III). The complex series is therefore claimed as an alternative to the Eu3 + complexes in security inks.
El estudio del espectro de emisión en metanol después de excitación a 522 nm (Figura 2) ha ayudado a establecer las vidas medias de emisión (T) de los complejos estudiados y con ellas, la siguiente secuencia: The study of the emission spectrum in methanol after excitation at 522 nm (Figure 2) has helped establish the emission half-lives (T) of the complexes studied and with them, the following sequence:
[Er(Hdbm)3(bipy)](5.4 fs) > [Er(Hhfc)3(bath)](3 fs) > [Er(Hfhd)3(5NO2phen)](1.45 fs) > [Er (Hdbm) 3 (bipy)] (5.4 fs)> [Er (Hhfc) 3 (bath)] (3 fs)> [Er (Hfhd) 3 (5NO2phen)] (1.45 fs)>
[Er(Htpm)3(5NO2phen)](1.4 fs)=[Er(Hfod)3(5NO2phen)](1.4 fs) [Er (Htpm) 3 (5NO2phen)] (1.4 fs) = [Er (Hfod) 3 (5NO2phen)] (1.4 fs)
= [Er(Htfac)3(bipy)](1.4 fs) > [Er(Hthd)3(bath)](1.3 fs) > [Er(acac)3(bath)] (1 fs) = [Er (Htfac) 3 (bipy)] (1.4 fs)> [Er (Hthd) 3 (bath)] (1.3 fs)> [Er (acac) 3 (bath)] (1 fs)
La fotoluminiscencia (PL) de los complejos ha sido medida en la región del infrarrojo cercano (NIR) después de excitación a longitudes de onda de 350 (fuente UV-vis) y 522 nm (laser Argón). En un estudio sobre el efecto de la excitación de las anteriores longitudes de onda sobre la intensidad de la luminiscencia para los complejos [Er(Hacac)3(bath)] (muestra 1; gráfico izquierda) y [Er(Hfhd)3(5NO2phen)] (muestra 2, gráfico derecha), hemos observado (Figura 3) que tras excitación a 522 nm la intensidad de la PL es la mitad o un tercio de la conseguida tras excitación a 350 nm. Se reivindica este hallazgo para su aplicación a dispositivos en los que anfitriones de naturaleza polimérica o vítrea sean dopados con complejos ternarios l-dicetonatos para obtener emisión en la región de 1532 nm region, la llamada tercera ventana de telecomunicaciones. The photoluminescence (PL) of the complexes has been measured in the near infrared (NIR) region 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; left graph) and [Er (Hfhd) 3 (5NO2phen )] (sample 2, right 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 application to devices in which hosts of polymeric or vitreous nature are doped with ternary complexes l-diketonates to obtain emission in the region of 1532 nm region, the so-called third telecommunications window.
El estudio de eficiencia PL en solución solo ha sido llevado a cabo, hasta la fecha, para tris(dibenzoilmetano) mono(2,2´-bipiridina)erbium(III), [Er(Hdbm)3(bipy)], que ha mostrado la clásica banda estrecha debida a las transiciones f–f transitions en la región NIR a 980 y 1532 nm, con un resultado de <PL = 7.2×10-5. The PL efficiency study in solution has only been carried out, to date, for tris (dibenzoylmethane) mono (2,2´-bipyridine) erbium (III), [Er (Hdbm) 3 (bipy)], which has showed the classic narrow band due to the f-f transitions in the NIR region at 980 and 1532 nm, with a result of <PL = 7.2 × 10-5.
Por otro lado, la mayor parte de los complejos de la serie reivindicada han sido utilizados como componentes activos en diodos orgánicos emisores de luz (OLEDs) que emiten en el NIR (NIR-OLEDs). Aquí, los NIR-OLEDs han sido fabricados con la configuración ITO/PEDOT:PSS (50 nm)/capa activa /Ca (20 nm)/Al. Las características de dispositivo corriente(J)-voltaje(V) han sido medidas utilizando un analizador de parámetros semiconductores Agilent 4155C y un generador de pulsos SMU Agilent 41501B. Las curvas J-V con más alta pendiente son las obtenidas para dispositivos con [Er(Hhfc)3(bath)] y [Er(Hdbm)3(bipy)] en sus capas emisoras. Estos dispositivos tienen potencial en tecnología laser, sensores ópticos y telecomunicaciones. 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 current device (J) -voltage (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.
El fenómeno de up-conversion ha sido mostrado en muchos sistemas pero, preferentemente, en los constituidos por iones activos de los lantánidos en un material anfitrión. Para células solares de silicio, el erbio(III) es una buena elección como ión activo debido a que absorbe a longitudes de onda más bajas que la longitud de onda que corresponde a la band gap del silicio (1.1 !m) y emite dentro del intervalo de absorción del silicio. Se reivindica un material vítreo transparente dopado con complejos lantánido l-dicetonato que exhibe eficiencias de upconversion dos órdenes de magnitud mejor que sus vidrios precursores. Procesos de absorción bi- y tri-fotónicos dan lugar a tres bandas de emisión en este material centradas a 550, 650 and 980 nm bajo excitación infrarroja a 1480 nm. Este material podría ser utilizado para fabricar células solares de silicio de alta eficiencia. 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, the erbium (III) is a good choice as an active ion because it absorbs at wavelengths lower than the wavelength corresponding to the silicon band gap (1.1 µm) and emits within the silicon absorption interval. A transparent vitreous material doped with lanthanide l-diketonate complexes is claimed that exhibits upconversion 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.
Se ha dopado, indistintamente, vidrio de sílice mesoporosa, vidrio fluorado tipo ZBLAN y vidrio fluorofosfato con los complejos de la serie reivindicada y demostrado su aplicación para la fabricación de dispositivos EDFA y YEDFA. Basados en los resultados, se reivindica la adición de los nuevos complejos con ligandos fluorados a vidrios fosfato-fluorado como un recurso para la optimización de EDFAs y YEDFAs. 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 (32)
- 2.2.
- Un complejo según la reivindicación 1, caracterizado por que el �-dicetonato se encuentra fluorado. A complex according to claim 1, characterized in that the �-diketonate is fluorinated.
- 3.3.
- Un complejo según una cualquiera de las reivindicaciones 1 o 2, caracterizado por que el ligando N,Ndonor es seleccionado dentro del grupo compuesto por: 5-nitro-1,10-fenantrolina, batofenantrolina y 2,2bipiridina. A complex according to any one of claims 1 or 2, characterized in that the N, Ndonor ligand is selected from the group consisting of: 5-nitro-1,10-phenanthroline, batophenantroline and 2,2-dipyridine.
- 4.Four.
- Un complejo según una cualquiera de las reivindicaciones anteriores, caracterizado por que está seleccionado entre: tris(acetilacetona)mono(batofenantrolina)erbio(III), [Er(Hacac)3(bath)]; tris(2,4-hexanedione)mono (batofenantrolina)erbio(III), [Er(h)3(bath)]; tris(2,2,6,6,-tetrametil-3,5-heptanodiona)mono (batofenantrolina)erbio(III), [Er(Hthd)3(bath)]; tris(2,6-dimethyl-3,5-heptanodiona)mono(batofenantrolina) erbio(III), [Er(Hdmh)3(bath)]; tris(2,6-dimetil-3,5-heptanodiona)mono(5-nitro-1,10-fenantrolina)erbio(III), [Er(Hdmh)3(5NO2phen)]; tris(2,6-dimetil-3,5-heptanodiona)mono(2,2-bipiridine)erbio(III), [Er(Hdmh)3(bipy)]; tris(2,4-hexanodiona)mono(2,2-bipiridina)erbio(III), [Er(hd)3(bipy)]; tris(3,5-heptanodiona)mono(2,2-bipiridina)erbio(III), [Er(hpd)3(bipy)]; tris(octanodiona)mono(2,2-bipiridina)erbio(III), [Er(od)3(bipy)]; tris(nonanodiona)mono(2,2-bipiridina)erbio(III), [Er(nd)3(bipy)]; A complex according to any one of the preceding claims, characterized in that it is selected from: 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 (batophenantroline) 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-1,10-phenanthroline) erbium (III), [Er (Hdmh) 3 (5NO2phen)]; 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)];
- 5. 5.
- Método de obtención de un complejo de erbio(III) o iterbio(III) descrito en una cualquiera de las reivindicaciones anteriores, caracterizado por que comprende mezclar y agitar, en solución, cantidades moleculares de compuestos que aseguren la presencia de erbio o iterbio, dicetona y ligando base de Lewis en proporciones 1:3:1. 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 iterbium, diketone and Lewis base ligand in 1: 3: 1 ratios.
- 6.6.
- Método de acuerdo con la reivindicación anterior, caracterizado por que comprende: Method according to the preceding claim, characterized in that it comprises:
- --
- mezclar en proporción molecular 1:3:3 una disolución de un compuesto binario de erbio(III) o iterbio(III) en un disolvente con una disolución de una beta-dicetona en un disolvente y un alcalinizante en un disolvente, y 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
- --
- adicionar a dicha mezcla una disolución de un ligando base de Lewis en un disolvente en proporción molar tal que se obtiene la relación molar 1:3:1, y agitar la mezcla final. 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 stirring the final mixture.
- 7.7.
- Método de acuerdo con la reivindicación 6, caracterizado por que el compuesto de erbio o iterbio es un nitrato o un triflato de erbio o iterbio. Method according to claim 6, characterized in that the compound of erbium or iterbium is a nitrate or a triflate of erbium or iterbium.
- 8.8.
- Método de acuerdo con una cualquiera de las reivindicaciones 6 o 7, caracterizado por que el disolvente es seleccionado entre un alcohol y acetonitrilo. Method according to any one of claims 6 or 7, characterized in that the solvent is selected from an alcohol and acetonitrile.
- 9.9.
- Método de acuerdo con la reivindicación 8, caracterizado por que el alcohol es metanol o etanol. Method according to claim 8, characterized in that the alcohol is methanol or ethanol.
- 10.10.
- Método de acuerdo con una cualquiera de las reivindicaciones 6 a 9, caracterizado por que el alcalinizante es seleccionado entre metilato alcalino y un hidróxido alcalino. 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.eleven.
- Método de acuerdo con la reivindicación 10, caracterizado por que el metilato es sódico o potásico y el hidróxido es de cesio. Method according to claim 10, characterized in that the methylate is sodium or potassium and the hydroxide is cesium.
- 12.12.
- Método de acuerdo con una cualquiera de las reivindicaciones 7 a 11, caracterizado por que cuando el compuesto de erbio o iterbio es un nitrato, el disolvente es metanol o etanol y el alcalinizante es metilato sódico o potásico. 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. 13.
- Método de acuerdo con una cualquiera de las reivindicaciones 7 a 11, caracterizado por que cuando el compuesto de erbio o iterbio es un triflato, el disolvente es acetonitrilo y el alcalinizante es hidróxido de cesio. 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.
- 14.14.
- Método de acuerdo con una cualquiera de las reivindicaciones 6 a 13, caracterizado por que la concentración de alcalinizante en el disolvente es al 25%. Method according to any one of claims 6 to 13, characterized in that the concentration of alkalizing agent in the solvent is 25%.
- 15.fifteen.
- Método de acuerdo con una cualquiera de las reivindicaciones 5 o 6, caracterizado por que el compuesto de erbio o iterbio es trisbetadicetonato de erbio o iterbio, donde el complejo de erbio o iterbio está unido a la betadicetona en una proporción 1:3. 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.
- 16.16.
- Método de acuerdo con la reivindicación 15, caracterizado por que comprende: Method according to claim 15, characterized in that it comprises:
- --
- mezclar en cantidades equimoleculares 1:1 una disolución de un complejo trisbetadicetonato de erbio(III) o iterbio(III) en un disolvente y un alcalinizante en un disolvente con una disolución de un ligando base de Lewis en un disolvente. 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.
- 17.17.
- Método de acuerdo con la reivindicación 16, caracterizado por que el disolvente en las dos disoluciones es etanol. Method according to claim 16, characterized in that the solvent in the two solutions is ethanol.
- 18.18.
- Método de acuerdo con una cualquiera de las reivindicaciones 6 a 17, caracterizado por que, cuando se trabaja a escala milimolar, la cantidad de disolvente a utilizar para la mezcla que contiene los iones de erbio o iterbio y betadicetonato está comprendida entre 10 y 40 mL, incluidos ambos límites, y la que contiene el ligando base de Lewis entre 5 y 15 mL, incluidos ambos límites. Method according to any one of claims 6 to 17, characterized in that, when working on a millimolar scale, the amount of solvent to be used for the mixture containing the erbium or iterbium and betadicetonate ions is between 10 and 40 mL. , including both limits, and the one containing the Lewis base ligand between 5 and 15 mL, including both limits.
- 19.19.
- Método de acuerdo con una cualquiera de las reivindicaciones 6 a 18, caracterizado por que el tiempo de agitación de la mezcla final está comprendido entre 1 y 8 horas. 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. twenty.
- Uso de un complejo de erbio(III) o iterbio(III) como el descrito en una cualquiera de las reivindicaciones 1 a 4 como material óptico no lineal. 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.twenty-one.
- Uso de un complejo de erbio(III) o iterbio(III) como el descrito en una cualquiera de las reivindicaciones 1 a 4 como soporte para la propagación de solitones ópticos espaciales. 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.
- 22.22
- Uso de un complejo de erbio(III) o iterbio(III) como el descrito en una cualquiera de las reivindicaciones 1 a 4 como material dopante. Use of a complex of erbium (III) or ytterbium (III) as described in any one of claims 1 to 4 as a doping material.
- 23.2. 3.
- Uso según la reivindicación 22, caracterizado por que el complejo de erbio(III) o iterbio(III) se usa como material dopante en uno de los dispositivos seleccionados dentro del grupo compuesto por: 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:
- 25.25.
- Uso según la reivindicación 24 en Horticultura. Use according to claim 24 in Horticulture.
- 26.26.
- Tinta de seguridad caracterizada por que comprende el complejo de erbio(III) o iterbio(III) descrito según una cualquiera de las reivindicaciones 1 a 4. Security ink characterized in that it comprises the erbium (III) or iterbium (III) complex described according to any one of claims 1 to 4.
- 27. 27.
- Diodo orgánico emisor de luz, OLED, caracterizado por que comprende el complejo de erbio(III) o 10 iterbio(III) descrito según una cualquiera de las reivindicaciones 1 a 4. Organic light emitting diode, OLED, characterized in that it comprises the complex of erbium (III) or 10 iterbium (III) described according to any one of claims 1 to 4.
- 28.28.
- Diodo según la reivindicación 27, caracterizado por que es un diodo que emite en el NIR. Diode according to claim 27, characterized in that it is a diode emitting in the NIR.
- 29. 29.
- Amplificador de fibra óptica caracterizado por que comprende el complejo de erbio(III) o iterbio(III) descrito según una cualquiera de las reivindicaciones 1 a 4. 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.
- 30.30
- Célula solar caracterizada por que comprende el complejo de erbio(III) o iterbio(III) descrito según 15 una cualquiera de las reivindicaciones 1 a 4. 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.
- Categoría Category
- 56 Documentos citados Reivindicaciones afectadas 56 Documents cited Claims Affected
- X X
- COYA, C. et al. “Novel Er-doped organic complexes for application in 1.5 mm emitting solution 1-12, 14-20, 22, COYA, C. et al. “Novel Er-doped organic complexes for application in 1.5 mm emitting solution 1-12, 14-20, 22,
- processed organic light emitting diodes (OLEDs)”. Material Research Society Symposium Proceedings, 2011, Vol. 1286.Ver Resumen; Experimental, párrafo 1; página41, párrafo 3; Conclusiones. processed organic light emitting diodes (OLEDs) ”. Material Research Society Symposium Proceedings, 2011, Vol. 1286. See Summary; Experimental, paragraph 1; page41, paragraph 3; Conclusions
- 23, 27, 28, 30 y 31 23, 27, 28, 30 and 31
- Y Y
- 21, 26 21, 26
- Y Y
- US 5195160 A (BYRON KEVIN C ) 16/03/1993. Ver reivindicaciones 1 y 6. 21 US 5195160 A (BYRON KEVIN C) 03/16/1993. See claims 1 and 6. twenty-one
- Y Y
- US 5837042 A (LENT BRUCE A et al.) 17/11/1998. Ver reivindicaciones 1 y 5. 26 US 5837042 A (LENT BRUCE A et al.) 11/17/1998. See claims 1 and 5. 26
- X X
- HONG, Z. et al. “Infrared light emitting devices based on organic erbium complexes”. Faguang 1-4, 20, 22, 23 y HONG, Z. et al. "Infrared light emitting devices based on organic erbium complexes". Faguang 1-4, 20, 22, 23 and
- Xuebao, 2000, Vol. 21, N. 3, páginas269-272. Resumen recuperado de base de datos HCAPLUS, STN [recuperado el 03/05/2012]. Xuebao, 2000, Vol. 21, N. 3, pages 269-272. Summary retrieved from HCAPLUS database, STN [retrieved on 05/03/2012].
- 27-31 27-31
- X X
- VAN STAVEREN, D. et al.”Increase in coordination number of lanthanide complexes with 2,2'-bipyridine and 1,10-phenanthrolineby using �-diketonates with electron-withdrawing groups”. Inorganica Chimica Acta, 2001, Volumen315, Issue 2, páginas 163–171. Ver Resumen. 1-3, 5-11, 13 y 15 VAN STAVEREN, D. et al. ”Increase in coordination number of lanthanide complexes with 2,2'-bipyridine and 1,10-phenanthrolineby using �-diketonates with electron-withdrawing groups”. Inorganica Chimica Acta, 2001, Volume315, Issue 2, pages 163–171. See Summary. 1-3, 5-11, 13 and 15
- Categoría de los documentos citados X: de particular relevancia Y: de particular relevancia combinado con otro/s de la misma categoría A: refleja el estado de la técnica O: referido a divulgación no escrita P: publicado entre la fecha de prioridad y la de presentación de la solicitud E: documento anterior, pero publicado después de la fecha de presentación de la solicitud Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application
- El presente informe ha sido realizado • para todas las reivindicaciones • para las reivindicaciones nº: This report has been prepared • for all claims • for claims no:
- Fecha de realización del informe 31.05.2012 Date of realization of the report 31.05.2012
- Examinador N. Martín Laso Página 1/6 Examiner N. Martín Laso Page 1/6
- Categoría Category
- 56 Documentos citados Reivindicaciones afectadas 56 Documents cited Claims Affected
- X X
- MARTÍN-RAMOS, P. et al. “Diodos emisores de luz para la irradiación de plantas”[en línea] 24/11/2010[recuperado el 03/05/2012].Recuperado de Internet: <URL: http://oa.upm.es/7044/2/INVE_MEM_2010_76665.pdf>.Ver resumen, Figura 13. 1-3 y 22-25 MARTÍN-RAMOS, P. et al. “Light emitting diodes for plant irradiation” [online] 11/24/2010 [retrieved on 05/03/2012]. Recovered from the Internet: <URL: http://oa.upm.es/7044/2 /INVE_MEM_2010_76665.pdf>. See summary, Figure 13. 1-3 and 22-25
- X X
- KAWAMURA, Y. et al. “Near-Infrared Photoluminiscence And electroluminescence of 1,3, 20, 22, 23 y KAWAMURA, Y. et al. “Near-Infrared Photoluminiscence And electroluminescence of 1,3, 20, 22, 23 and
- neodymium(III),Erbium(III) and Ytterbium(III) Complexes”. Japanese Journal of Applied Physics, 2001, Vol. 40, páginas 350-356. Ver Resumen, Introducción; Experimental, párrafo 1; Figura 1. neodymium (III), Erbium (III) and Ytterbium (III) Complexes ”. Japanese Journal of Applied Physics, 2001, Vol. 40, pages 350-356. See Summary, Introduction; Experimental, paragraph 1; Figure 1.
- 27-29 27-29
- Categoría de los documentos citados X: de particular relevancia Y: de particular relevancia combinado con otro/s de la misma categoría A: refleja el estado de la técnica O: referido a divulgación no escrita P: publicado entre la fecha de prioridad y la de presentación de la solicitud E: documento anterior, pero publicado después de la fecha de presentación de la solicitud Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application
- El presente informe ha sido realizado • para todas las reivindicaciones • para las reivindicaciones nº: This report has been prepared • for all claims • for claims no:
- Fecha de realización del informe 31.05.2012 Date of realization of the report 31.05.2012
- Examinador N. Martín Laso Página 2/6 Examiner N. Martín Laso Page 2/6
- Novedad (Art. 6.1 LP 11/1986) Novelty (Art. 6.1 LP 11/1986)
- Reivindicaciones Reivindicaciones 21, 26 1-20, 22-25 y 27-31 SI NO Claims Claims 21, 26 1-20, 22-25 and 27-31 IF NOT
- Actividad inventiva (Art. 8.1 LP11/1986) Inventive activity (Art. 8.1 LP11 / 1986)
- Reivindicaciones Reivindicaciones 1-31 SI NO Claims Claims 1-31 IF NOT
- Documento Document
- Número Publicación o Identificación Fecha Publicación Publication or Identification Number publication date
- D01 D01
- COYA, C. et al. “Novel Er-doped organic complexes for application in 1.5 mm emitting solution-processed organic light emitting diodes (OLEDs)”. Material Research Society Symposium Proceedings, 2011, Vol. 1286. 14.01.2011 COYA, C. et al. “Novel Er-doped organic complexes for application in 1.5 mm emitting solution-processed organic light emitting diodes (OLEDs)”. Material Research Society Symposium Proceedings, 2011, Vol. 1286. 01/14/2011
- D02 D02
- HONG, Z. et al. “Infrared lightemittingdevices based on organic erbium complexes”. Faguang Xuebao, 2000, Vol. 21, N. 3, páginas269-272. Resumen recuperado de base de datos HCAPLUS, STN [recuperado el 03/05/2012]. 2000 HONG, Z. et al. “Infrared lightemittingdevices based on organic erbium complexes”. Faguang Xuebao, 2000, Vol. 21, N. 3, pages 269-272. Summary retrieved from HCAPLUS database, STN [retrieved on 05/03/2012]. 2000
- D03 D03
- VAN STAVEREN, D. et al.”Increasein coordination number of lanthanide complexes with 2,2'-bipyridine and 1,10phenanthrolineby using -diketonates with electron-withdrawing groups”. Inorganica Chimica Acta, 2001, Volumen315, Issue 2, pages 163–171. 27.04.2001 VAN STAVEREN, D. et al. ”Increasein coordination number of lanthanide complexes with 2,2'-bipyridine and 1,10phenanthrolineby using -diketonates with electron-withdrawing groups”. Inorganica Chimica Acta, 2001, Volume315, Issue 2, pages 163–171. 27.04.2001
- D04 D04
- MARTÍN-RAMOS, P. et al. “Diodos emisores de luz para la irradiación de plantas”[en línea] 24/11/2010[recuperado el 03/05/2012].Recuperado de Internet: <URL: http://oa.upm.es/7044/2/INVE_MEM_2010_76665.pdf>. 24.11.2010 MARTÍN-RAMOS, P. et al. “Light emitting diodes for plant irradiation” [online] 11/24/2010 [retrieved on 05/03/2012]. Recovered from the Internet: <URL: http://oa.upm.es/7044/2 /INVE_MEM_2010_76665.pdf>. 11/24/2010
- D05 D05
- KAWAMURA, Y. et al. “Near-Infrared Photoluminiscence and electroluminescence of neodymium(III),Erbium(III) and Ytterbium(III) Complexes”. Japanese Journal of Applied Physics, 2001, Vol. 40, páginas 350-356. 2001 KAWAMURA, Y. et al. "Near-Infrared Photoluminiscence and electroluminescence of neodymium (III), Erbium (III) and Ytterbium (III) Complexes." Japanese Journal of Applied Physics, 2001, Vol. 40, pages 350-356. 2001
- D06 D06
- US 5837042 A 16.03.1993 US 5837042 A 16.03.1993
- D07 D07
- US 5837042 A 17.11.1998 US 5837042 A 17.11.1998
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| PCT/ES2012/070143 WO2012120175A1 (en) | 2011-03-10 | 2012-03-07 | Optically active octacoordinated ternary complexes of erbium (iii) or ytterbium (iii) and production method |
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