CN115433240B - Iridium metal complex and application thereof in photoelectric device - Google Patents
Iridium metal complex and application thereof in photoelectric device Download PDFInfo
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Abstract
The invention relates to an iridium metal complex and application thereof in photoelectric devices. The iridium metal complex provided by the invention contains a benzisoquinoline group in the structure, and when the iridium metal complex is used as a guest material in a light-emitting layer of an organic electronic device, the light-emitting efficiency of the device can be improved, and the service life of the device can be prolonged.
Description
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to an iridium metal complex and application thereof in photoelectric devices.
Background
Organic Light Emitting Diodes (OLEDs), which are carrier double injection type light emitting devices, are also known as organic electroluminescent devices. At a certain driving voltage, electrons are injected from the cathode, holes are injected from the anode, and then both meet at the organic light emitting layer and recombine to form excitons (i.e., hole-electron pairs). The excitons release energy, return to the ground state in the form of a radiative transition, and fluoresce or phosphorescence. In order to increase the luminous efficiency of organic light emitting diodes, various fluorescent and phosphorescent based luminescent material systems have been developed. The organic light emitting diode using the fluorescent material has high reliability, but the internal electroluminescent quantum efficiency thereof is limited to 25% under the excitation of an electric field. In contrast, since the branching ratio of the singlet excited state and the triplet excited state of excitons is 1:3, the organic light emitting diode using the phosphorescent material can achieve almost 100% internal light emission quantum efficiency. The existing luminescent layer material mostly adopts a host-guest doping mode, and a metal complex is formed by doping heavy metal centers, so that spin orbit coupling can be improved, intersystem crossing is easy to occur under electric field excitation, and triplet excitation is effectively obtained.
Complexes based on iridium (III) are a class of materials widely used in high efficiency OLEDs, with higher efficiency and stability. Baldo et al report the use of fac-tris (2-phenylpyridine) iridium (III) [ Ir (ppy) 3 ]As a phosphorescent light-emitting material, 4'-N, N' -dicarbazole-biphenyl (CBP) is a high quantum efficiency OLED as a host material (appl. Phys. Lett.1999,75,4). Sky blue complex bis [2- (4 ',6' -difluorophenyl) pyridine-N, C2]Iridium (III) picolinate (FIrpic) is another well known phosphorescent dopant material which, when doped into a high triplet energy host, exhibits extremely high photoluminescence quantum efficiencies of about 60% in solution and almost 100% in solid films (appl. Phys. Lett.2001,79,2082). Although iridium (III) systems based on 2-phenylpyridine and its derivatives have been used in large amounts for the preparation of OLEDs, device performance, especially lifetime, still needs to be improved.
Disclosure of Invention
The invention aims to provide a novel iridium metal complex which can be used as a guest material in a light-emitting layer of an organic electronic device, so that the light-emitting efficiency of the device is improved and the service life of the device is prolonged.
In order to achieve the technical scheme of the purpose, the invention provides an iridium metal complex, which is shown as a general formula (I):
Wherein:
R 1 、R 2 、R 3 、R 4 、R 5 each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atomsAlkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, thiocyanate, isothiocyanate, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, substituted or unsubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted aryl having 6 to 50 ring atoms, substituted or unsubstituted heteroaryl having 5 to 50 ring atoms, substituted or unsubstituted aryloxy having 6 to 50 ring atoms, substituted or unsubstituted heteroaryloxy having 5 to 50 ring atoms, or a combination of these groups;
m is selected from 1 or 2;
n1 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; n2 is selected from 0, 1, 2, 3 or 4.
Correspondingly, the invention also provides a luminescent layer guest material which comprises at least one iridium metal complex.
Correspondingly, the invention also provides a mixture which comprises at least one iridium metal complex and at least one other organic functional material, wherein the at least one other organic functional material is selected from a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a luminescent guest material (Emitter), a luminescent Host material (Host) or an organic dye.
Accordingly, the present invention also provides a composition comprising at least one aromatic amine compound or mixture as described above, and at least one organic solvent.
Correspondingly, the invention also provides an organic electronic device, which comprises at least one functional layer, wherein the functional layer comprises at least one iridium metal complex or a mixture or a composition prepared from the iridium metal complex.
Compared with the prior art, the invention has the remarkable advantages that: the iridium metal complex provided by the invention contains a benzisoquinoline group in the structure to improve the charge transmission in an organic electronic device, so that the luminous efficiency of the device is improved, and the service life of the device is prolonged.
Detailed Description
The technical solutions of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the application. In the present application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to upper and lower in the actual use or operational state of the device. In addition, in the description of the present application, the term "comprising" means "including but not limited to," the term "plurality" means "two or more," and the term "and/or" includes any and all combinations of one or more of the associated listed items. Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by a combination of at least two conjunctions selected from the group consisting of "and/or", "and/or", it should be understood that, in the present application, the technical solutions include technical solutions that all use "logical and" connection, and also include technical solutions that all use "logical or" connection. For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).
In the present invention, aromatic groups and aromatic ring systems have the same meaning and can be interchanged.
In the present invention, the heteroaromatic groups, heteroaromatic groups and heteroaromatic ring systems have the same meaning and can be interchanged.
In the present invention, the "heteroatom" is a non-carbon atom, and may be an N atom, an O atom, an S atom, or the like.
In the present invention, "substituted" means that one or more hydrogen atoms in the substituted group are substituted with the substituent.
In the present invention, "monosubstituted" means substituted with one substituent, "disubstituted" means substituted with two substituents, "trisubstituted" means substituted with three substituents, "tetrasubstituted" means substituted with four substituents, "pentasubstituted" means substituted with five substituents.
In the present invention, the same substituent may be independently selected from different groups when it appears multiple times. If the general formula contains a plurality of R, R can be independently selected from different groups.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, -NR' R ", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and which may be further substituted with substituents acceptable in the art; it is understood that R 'and R "in-NR' R" are each independently selected from, but not limited to: H. deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 20 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 10 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms, silane groups, carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, haloformyl groups, formyl groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, trifluoromethyl groups, and which may be further substituted with substituents acceptable in the art.
In the present invention, the "number of ring atoms" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
"aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removal of one hydrogen atom, which may be a monocyclic aryl group, or a fused ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for a polycyclic species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group having 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthylenyl and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), such as acenaphthene, fluorene, or 9, 9-diaryl fluorene, triarylamine, diaryl ether systems in particular should also be included in the definition of aryl groups.
"heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, which may be an N atom, an O atom, an S atom, or the like. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl is optionally further substituted, suitable examples include, but are not limited to: thienyl, furyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiophenoyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, primary pyridyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.
In the present invention, "alkyl" may denote a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing this term, e.g., "C 1 -C 9 Alkyl "means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be, independently of the other, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and the like.
The term "alkoxy" refers to a structural group of "-O-alkyl"groups, i.e., alkyl groups as defined above, are attached to other groups via oxygen atoms. Phrases containing this term, suitable examples include, but are not limited to: methoxy (-O-CH) 3 or-OMe), ethoxy (-O-CH 2 CH 3 or-OEt) and t-butoxy (-O-C (CH) 3 ) 3 or-OtBu).
In the present invention "×" associated with a single bond represents a linking or fusing site;
in the present invention, when no linking site is specified in the group, an optionally-ligatable site in the group is represented as a linking site;
in the present invention, when the same group contains a plurality of substituents of the same symbol, each substituent may be the same or different from each other, for exampleThe 6R groups on the benzene ring may be the same or different from each other.
In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.gR in (C) is connected with any substitutable site of benzene ring.
As used in the present invention, "a combination thereof", "any combination thereof", "a combination of groups", "a combination", and the like include all suitable combinations of any two or more of the listed groups.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
An iridium metal complex is shown as a general formula (I):
wherein:
R 1 、R 2 、R 3 、R 4 、R 5 each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, amino, -CF 3 -Cl, -Br, -F, -I, substituted or unsubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted aryl having 6 to 50 ring atoms, substituted or unsubstituted heteroaryl having 5 to 50 ring atoms, substituted or unsubstituted aryloxy having 6 to 50 ring atoms, substituted or unsubstituted heteroaryloxy having 5 to 50 ring atoms, or a combination of these groups;
m is selected from 1 or 2;
n1 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; n2 is selected from 0, 1, 2, 3 or 4.
In one embodiment, R 1 、R 2 、R 3 、R 4 、R 5 Each occurrence is independently selected from: -H, -D, straight-chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyanoHydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms, or a combination of these groups.
In one embodiment, R 3 、R 4 、R 5 Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, or a combination of these groups.
In one embodiment, R 5 Selected from H or D.
In one embodiment, R 3 、R 4 Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 6C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, a phenyl group, or a combination of these groups. Preferably, R 3 And R is 4 Selected from the same groups.
More preferably, R 3 、R 4 Each occurrence is independently selected from H, -D, or the following groups:
wherein represents the attachment site.
In one embodiment, R 1 、R 2 Each occurrence is independently selected from: -H, -D, straight chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 10 ring atoms, or a combination of these groups.
Further, R 1 、R 2 Each occurrence is independently selected from H, -D, having 1Straight-chain alkyl of up to 6C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, or the following groups:
Wherein: x is independently selected from CR for each occurrence 6 Or N;
R 6 each occurrence is independently selected from: -H, -D, straight chain alkyl having 1 to 10C atoms, branched or cyclic alkyl having 3 to 10C atoms, silyl, cyano, isocyano, hydroxy, nitro, amino, -CF 3 -Cl, -Br, -F, -I, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms, or a combination of these groups;
* Representing the ligation site.
Specifically, R 1 、R 2 Each occurrence is independently selected from H, -D, or the following groups:
more preferably, R 1 Selected from H.
In one embodiment, the iridium metal complex is selected from the following formulas II-1 to II-8:
iridium metal complexes according to the present application include, but are not limited to, the following structures:
in an embodiment, the iridium metal complex provided by the application can be used as an organic functional material to be applied to a functional layer of an organic electronic device, in particular to a functional layer of an OLED device. The organic functional material may be, but is not limited to, a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting guest material (Gust emission), a light emitting Host material (Host emission), and an organic dye.
In an embodiment, the iridium metal complex of the present application is used in a light-emitting layer, and preferably, the iridium metal complex is used as a guest material of the light-emitting layer in the light-emitting layer.
The present application further provides a mixture comprising at least one iridium metal complex as described above and at least one other organic functional material. The another organic functional material is selected from the group consisting of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting guest material, a light emitting host material, and an organic dye. Wherein the luminophore is selected from singlet luminophores (fluorescent luminophores) or triplet luminophores (phosphorescent luminophores) grade organic thermal excitation delayed fluorescence material (TADF material). Details of various organic functional materials are found in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference. It is understood that the other organic functional material may be a small molecule organic material and a high polymer material.
In an embodiment, the further organic functional material is selected from a host material. Wherein the weight percentage of the iridium metal complex in the mixture is more than 0 and less than or equal to 25wt%, preferably more than 0 and less than or equal to 15wt%, more preferably more than 0 and less than or equal to 5wt%, and further more preferably more than 0 and less than or equal to 2wt%.
The application also relates to a composition comprising at least one iridium metal complex or mixture as described above and at least one organic solvent.
The organic solvent is at least one selected from aromatic or heteroaromatic based solvents, ester based solvents, aromatic ketone based solvents, aromatic ether based solvents, aliphatic ketones, aliphatic ethers, alicyclic compounds, olefin compounds, boric acid ester compounds and phosphoric acid ester compounds.
In at least one embodiment, the organic solvent is selected from aromatic or heteroaromatic based solvents in the composition.
The aromatic or heteroaromatic based solvent may be selected from, but is not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropylpyridine, 1, 3-dimethylquinoline, 2-dimethylquinoline, and at least one of the ethyl esters of furan.
The ester-based solvent may be selected from, but is not limited to, alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. At least one of octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate is particularly preferable.
The aromatic ketone-based solvent may be selected from, but is not limited to, 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof. Among them, the derivative may be selected from, but not limited to, at least one of 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropophenone, 3-methylpropophenone, and 2-methylpropophenone, as an example.
The aromatic ether-based solvent may be selected from, but is not limited to, at least one of 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran and ethyl-2-naphthyl ether.
The aliphatic ketone-based solvent may be selected from, but is not limited to, 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, di-n-amyl ketone, and the like; or aliphatic ethers such as at least one of amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
It is understood that the organic solvents may be used alone or as a mixed solvent of two or more organic solvents.
In one embodiment, the composition of the present application comprises at least one iridium metal complex or mixture as described above, and at least one organic solvent, and may further comprise another organic solvent.
The other organic solvent may be selected from, but is not limited to, at least one of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide (DMSO), tetrahydronaphthalene, decalin, and indene.
In one embodiment, an organic solvent suitable for the present application is a solvent having Hansen (Hansen) solubility parameters within the following ranges:
δd (dispersion force) is in the range of 17.0MPa1/2 to 23.2MPa1/2, particularly in the range of 18.5MPa1/2 to 21.0MPa 1/2;
δp (polar force) is in the range of 0.2MPa1/2 to 12.5MPa1/2, especially in the range of 2.0MPa1/2 to 6.0MPa 1/2;
δh (hydrogen bonding force) is in the range of 0.9MPa1/2 to 14.2MPa1/2, particularly in the range of 2.0MPa1/2 to 6.0MPa 1/2.
In one embodiment, the organic solvent is selected with consideration of boiling point in the composition according to the present application. In at least some embodiments, the organic solvent has a boiling point of ∈deg.C or greater; preferably not less than 180 ℃; preferably not less than 200 ℃; more preferably not less than 250 ℃; the optimal temperature is more than or equal to 300 ℃. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads.
It is understood that the organic solvent may be evaporated from the solvent system to form a film comprising the organic compound.
In one embodiment, the composition is a solution. In still other embodiments, the composition is a suspension. The solution or suspension may additionally include additives for adjusting viscosity, adjusting film forming properties, improving adhesion, etc. The additive may be selected from at least one of, but not limited to, a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobizing agent, and a binder.
The composition may also be referred to as an ink.
When used in the printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of a suitable ink are suitable for a particular substrate and a particular printing method.
In one embodiment, the ink according to the application has a surface tension at the operating temperature or at 25 ℃ in the range of about 19dyne/cm to 50dyne/cm; more preferably 22dyne/cm to 35dyne/cm; preferably from 25dyne/cm to 33dyne/cm.
In one embodiment, the ink according to the present application has a viscosity in the range of 1cps to 100cps at the working temperature or 25 ℃; preferably 1cps to 50cps; more preferably 1.5cps to 20cps; and preferably from 4.0cps to 20cps.
It will be appreciated that inks having the surface tension and viscosity described above will facilitate inkjet printing.
It will be appreciated that the viscosity of the ink may be adjusted by different methods, such as by appropriate solvent selection and concentration of functional material in the ink. The inks comprising the organic compounds according to the application can be conveniently adjusted to the printing process used in the printing ink in the appropriate range. The compositions according to the application comprise organic compounds or mixtures in a mass percentage of 0.01% to 15% by weight, preferably 0.1% to 10% by weight, more preferably 0.2% to 5% by weight, most preferably 0.25% to 3% by weight.
The application also relates to the use of said composition as a coating or printing ink in the preparation of an organic electronic device. In one embodiment, the composition is used in the preparation of organic electronic devices by a print or coating preparation method. The printing or coating may be prepared by, but is not limited to, ink jet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roller printing, offset printing, flexography, rotary printing, spray coating, brush coating, pad printing, slot die coating, and the like. Preferred are gravure printing, inkjet printing and inkjet printing.
The application also relates to an application of the iridium metal complex, the mixture or the composition in an organic electronic device. In one embodiment, the present application provides an organic electronic device including at least one functional layer. The functional layer comprises at least one iridium metal complex or mixture as described above, or the functional layer is prepared from the composition as described above.
Further, the organic electronic device includes a cathode, an anode, and at least one functional layer. The functional layer comprises at least one iridium metal complex or mixture as described above or is prepared from the composition as described above.
The functional layer may be, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emitting layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), or a hole blocking layer. Preferably, the functional layer is a light emitting layer. The light emitting layer contains at least one iridium metal complex or mixture as described above, or the light emitting layer is prepared from the composition as described above.
In one embodiment, the light emitting layer comprises a light emitting host material and a light emitting guest material, the light emitting guest material being an iridium metal complex or mixture as described above. Further, the light-emitting layer guest material accounts for 25% or more of the host material in mass ratio; further, the light-emitting layer guest material accounts for 15% or more of the host material in mass ratio; further, the light-emitting layer guest material accounts for 5% or more of the host material by mass.
The organic electronic device may be, but is not limited to, an Organic Light Emitting Diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an organic laser, an organic spintronic device, an organic sensor, an organic plasmon emitting diode (Organic Plasmon Emitting Diode), and the like. Organic electroluminescent devices such as OLEDs, oleccs, organic light emitting field effect transistors, etc. are particularly preferred. Further particularly preferred are OLEDs.
The substrate may be transparent or opaque. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al, appl. Phys. Lett.1996,68, p2606. The substrate may also be rigid or elastic. In one embodiment, the substrate is plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface, and a substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode is an electrode that injects holes, and the anode can easily inject holes into a hole injection layer, or a hole transport layer, or a light emitting layer. The anode may comprise a conductive metal, conductive metal oxide, or conductive polymer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO aluminum doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present application.
The cathode is an electrode injecting electrons, and the cathode can easily inject electrons into an electron injection layer, or an electron transport layer, or a light emitting layer. The cathode may comprise a conductive metal or conductive metal oxide. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO or conduction band level of the light-emitting body in the light-emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials that can be used as cathodes of the organic electronic devices are possible as cathode materials of the organic electronic devices of the application. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
The OLED may further include other functional layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
The hole injection layer may facilitate injection of holes from the anode to the hole transport layer, thereby reducing the voltage required to inject holes. The hole injection material is a material that can efficiently receive injected holes from the positive electrode, and it is preferable that the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the hole transport layer material. Common hole injection materials include, but are not limited to: metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanitrile hexaazabenzophenanthrene-based organic materials, and the like.
The hole transport layer may be used to smoothly receive holes injected from the anode or the hole injection layer and transfer the holes to the light emitting layer. Common hole transport materials include, but are not limited to: aromatic amine compounds, styrene compounds, butadiene compounds, conductive polymers, block copolymers having both conjugated and non-conjugated moieties, and the like, but are not limited thereto.
The electron blocking layer may be disposed between the hole transport layer and the light emitting layer to block electrons from being transported from the light emitting layer to the hole transport layer, thereby confining holes in the light emitting layer to improve light emitting efficiency. Common electron blocking layer materials include, but are not limited to: triarylamine organic compounds, metazole compounds, or materials known in the art.
The host material for the light-emitting layer includes a condensed ring aromatic ring derivative or a heterocyclic ring-containing compound, or the like. Specifically, examples of the condensed ring aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, benzophenanthrene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocyclic ring-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, triazine derivatives, and the like, but are not limited thereto.
In an embodiment, the host material for the light emitting layer is selected from co-host materials, preferably co-host materials are selected from benzophenanthrene derivatives and triazine derivatives.
The electron transport layer may be used to smoothly transport electrons to the light emitting layer. The electron transport material is selected from materials having high electron mobility, which can efficiently receive electrons injected from the negative electrode or the electron injection layer. Specific examples thereof may include, but are not limited to: at least one of Al complexes of 8-hydroxyquinoline, complexes comprising Alq3, organic radical compounds, hydroxyflavone-metal complexes, lithium 8-hydroxyquinoline (LiQ), ETM and benzimidazole-based compounds.
The electron injection layer can promote electron injection from the negative electrode and reduce the voltage required for electron injection. Specific examples thereof include, but are not limited to: fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, diazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, tmPyPB and the like.
The hole blocking layer may block holes from reaching the electron transport layer, thereby confining electrons in the light emitting layer to improve light emitting efficiency. Specific examples thereof include, but are not limited to, diazole derivatives or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like.
The organic electronic device has a luminescence wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 640 and 650 nm.
In one embodiment, the organic electronic device of the present application is a solution-type organic electronic device, and one or more functional layers thereof are prepared by printing; further, the solution-type organic electronic device is a solution-type OLED.
The application also relates to the use of an organic electronic device according to the application in various electronic devices, which may be, but are not limited to, display devices, lighting devices, light sources, sensors, etc.
The application also relates to an electronic device comprising said electronic device. The electronic device may be, but is not limited to, a display device, a lighting device, a light source, a sensor, and the like.
The present application will now be described in more detail by way of the following examples, which are intended to be illustrative of the application and not limiting thereof. The present application is not limited to the following examples.
The specific embodiment is as follows:
example 1: synthesis of Compound 1
Synthesis of Compound 1-1:
accurately weighing compound A (16.7 g,100 mmol), 2-bromopyridine (15.8 g,100 mmol) tris (dibenzylideneacetone) dipalladium (1.73 g,3 mmol), sodium tert-butoxide (19.2 g,200 mmol) was sequentially added into a 1000mL three-necked flask, anhydrous toluene was added about 450mL, nitrogen was pumped through three times, and then tri-tert-butylphosphine (plastid ratio of 10%12 mL) was added dropwise to the reaction system, followed by heating to 100 ℃ for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, diluting with water, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product with toluene/methanol. About 14.7g of compound 1-1 was obtained in yield: 60.2%. Ms 245.30
Synthesis of Compounds 1-2:
accurately weighing compound 1-1 (14.6 g,60 mmol) and adding into a 500mL three-necked flask, adding iridium trichloride monohydrate (3.8 g 12 mmol), adding 200mL of ethylene glycol diethyl ether, pumping nitrogen gas three times, heating to 120 ℃ for reaction for 12 hours, cooling the reaction solution to room temperature, pumping filtration, leaching the filter cake with petroleum ether several times, and obtaining about 13g of crude product of compound 1-2. Yield: 90% synthesis of compound 1:
accurately weighing compound 1-2 (13 g,9 mmol) and adding into a 250mL three-necked flask, adding sodium carbonate (1.9 g,18 mmol), adding 2, 4-pentanedione (0.9 g,9 mmol) and then adding into dichloromethane 80mL, methanol 40mL, pumping nitrogen gas three times, and heating to 60 ℃ for reaction for 12 hours. After the reaction was completed, the mixture was washed with water, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was distilled off under reduced pressure, followed by column chromatography on silica gel, eluting with PE: dcm=5:1 (volume ratio) to give about 4.6g of compound 1. Yield: 25.6%. Ms 779.92
Example 2: synthesis of Compound 2
Synthesis of Compound 2-1:
accurately weighing a compound A (16.7 g,100 mmol), 2-bromo-4, 6-lutidine (18.6 g,100 mmol), dipalladium tris (dibenzylideneacetone) (1.73 g,3 mmol), sodium tert-butoxide (19.2 g,200 mmol) sequentially added into a 1000mL three-neck flask, adding about 450mL of anhydrous toluene, pumping nitrogen gas three times, dropwise adding tri-tert-butylphosphine (plastid ratio of 10%12 mL) into the reaction system, and then heating to 100 ℃ for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, diluting with water, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product with toluene/methanol. About 18.8g of compound 2-1 was obtained in the yield: 69.0%. Ms 273.35
Synthesis of Compound 2-2:
accurately weighing compound 2-1 (18.8 g,69 mmol) and adding into a 500mL three-necked flask, adding iridium trichloride monohydrate (4.4 g, 13.8 mmol), adding 200mL of ethylene glycol diethyl ether, pumping nitrogen gas three times, heating to 120 ℃ for reaction for 12 hours, cooling the reaction liquid to room temperature, pumping filtration, and leaching a filter cake with petroleum ether for several times to obtain a crude product of compound 2-2 of about 21.5g. Yield: 80.8%.
Synthesis of Compound 2:
compound 2-2 (21.5 g,13.9 mmol) was accurately weighed into a 500mL three-necked flask, sodium carbonate (2.9 g,27.8 mmol) was added, 2, 4-pentanedione (1.4 g,13.9 mmol) was then added, 150mL of methylene chloride was added, 50mL of methanol was added, and after purging nitrogen three times, the temperature was raised to 60℃for reaction for 12 hours. After the reaction, washing with water, extracting with dichloromethane, mixing organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and carrying out silica gel column chromatography, wherein the eluting agent is PE (polyethylene) with DCM=5:1 (volume ratio) to obtain about 5.6g of compound 2. Yield: 24.1%. Ms:836.03.
example 3: synthesis of Compound 7
Synthesis of Compound 3-1:
accurately weighing a compound A (16.7 g,100 mmol), 2-bromo-4-phenylpyridine (23.4 g,100 mmol), dipalladium tris (dibenzylideneacetone) (1.73 g,3 mmol), sodium tert-butoxide (19.2 g,200 mmol) sequentially added into a 1000mL three-neck flask, adding anhydrous toluene about 450mL, pumping nitrogen gas three times, then dropwise adding tri-tert-butylphosphine (plastid ratio 10%12 mL) into the reaction system, and then heating to 100 ℃ for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, diluting with water, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product with toluene/methanol. About 21.5g of compound 3-1 was obtained in yield: 67.1%. Ms 321.40.
Synthesis of Compound 3-2:
accurately weighing compound 3-1 (21.5 g,67 mmol) and adding into a 500mL three-necked flask, adding iridium trichloride monohydrate (4.2 g,13.4 mmol), adding 200mL of ethylene glycol diethyl ether, pumping nitrogen gas three times, heating to 120 ℃ for reaction for 12 hours, cooling the reaction liquid to room temperature, pumping filtration, and leaching a filter cake with petroleum ether for several times to obtain a crude product of compound 3-2 of about 23.2g. Yield: 79.8%.
Synthesis of Compound 7:
accurately weighing compound 3-2 (23.2 g,13.4 mmol) and adding sodium carbonate (2.8 g,26.8 mmol) and 2, 4-pentanedione (1.3 g,13.4 mmol) into a 500mL three-necked flask, adding 200mL of dichloromethane and 80mL of methanol, pumping nitrogen gas three times, and heating to 60 ℃ for reaction for 12 hours. After the reaction, washing with water, extracting with dichloromethane, mixing the organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and carrying out column chromatography on silica gel, wherein the eluting agent is PE (polyethylene) with DCM=5:1 (volume ratio) to obtain about 5.1g of compound 7. Yield: 20.4%. Ms 931.12.
Example 4: synthesis of Compound 20:
synthesis of Compound 4-1:
2, 5-dibromopyridine (23.7 g,100 mmol), 3, 5-dimethylbenzeneboronic acid (15 g,100 mmol), tetraphenylphosphine palladium (3.5 g,3 mmol), potassium carbonate (27.6 g,200 mmol) were weighed accurately, sequentially added to a 1000mL three-necked flask, toluene was added in an amount of about 400mL, water was added in an amount of 100mL, and after three times of nitrogen filling was performed, the temperature was raised to 90℃for reaction overnight. After the raw materials are completely reacted, cooling to room temperature, separating liquid, extracting with ethyl acetate for three times, combining organic phases, and carrying out silica gel sample mixing column chromatography. Eluent was pe:ea=5:1 (volume ratio) yielding compound 4-1 about 20.5g, yield: 78.2%. Ms 263.15.
Synthesis of Compound 4-2:
accurately weighing compound 4-1 (20.5 g,78 mmol), compound A (13 g,78 mmol) of tris (dibenzylideneacetone) dipalladium (1.34 g,2.3 mmol), sodium tert-butoxide (14.9 g,156 mmol) were sequentially added into a 1000mL three-neck flask, anhydrous toluene was added about 450mL, nitrogen was pumped through three, and then tri-tert-butylphosphine (plastid ratio 10%9.4 mL) was added dropwise into the reaction system, followed by heating to 100 ℃ for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, diluting with water, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product with toluene/methanol. About 23.6g of compound 4-2 was obtained in yield: 86.8%. Ms 349.45.
Synthesis of Compound 4-3:
accurately weighing compound 4-2 (23.5 g,67 mmol) and adding into a 500mL three-necked flask, adding iridium trichloride monohydrate (4.2 g, 13.4 mmol), adding 200mL of ethylene glycol diethyl ether, pumping nitrogen gas three times, heating to 120 ℃ for reaction for 12 hours, cooling the reaction liquid to room temperature, pumping filtration, and leaching a filter cake with petroleum ether for several times to obtain a crude product of compound 4-3 of about 20.5g. Yield: 66.3%.
Synthesis of Compound 20:
accurately weighing compound 4-3 (20.5 g,11.1 mmol) and adding into a 500mL three-necked flask, adding sodium carbonate (2.4 g,22.2 mmol), 2, 4-pentanedione (1.1 g,11.1 mmol), then adding into 200mL of dichloromethane and 80mL of methanol, pumping nitrogen gas for three times, and heating to 60 ℃ for reaction for 12 hours. After the reaction, washing with water, extracting with dichloromethane, mixing the organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and performing silica gel column chromatography, wherein the eluting agent is PE (polyethylene) with DCM=5:1 (volume ratio) to obtain about 4.3g of compound 8. Yield: 19.6%. Ms 988.23.
Example 5: synthesis of Compound 35
Synthesis of Compound 5-1:
accurately weighing a compound A (16.7 g,100 mmol), 2-bromo-5-methylpyridine (18.6 g,100 mmol), dipalladium tris (dibenzylideneacetone) (1.73 g,3 mmol), sodium tert-butoxide (19.2 g,200 mmol) sequentially added into a 1000mL three-neck flask, adding about 450mL anhydrous toluene, pumping nitrogen gas three times, dropwise adding tri-tert-butylphosphine (plastid ratio 10%12 mL) into the reaction system, and then heating to 100 ℃ for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, diluting with water, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product with toluene/methanol. About 20.8g of compound 5-1 was obtained in yield: 80.5%. Ms 259.32.
Synthesis of Compound 5-2:
accurately weighing compound 5-1 (20.8 g,80 mmol) and adding into a 500mL three-necked flask, adding iridium trichloride monohydrate (5.1 g, 16 mmol), adding 200mL of ethylene glycol diethyl ether, pumping nitrogen gas three times, heating to 120 ℃ for reaction for 12 hours, cooling the reaction solution to room temperature, pumping filtration, leaching the filter cake with petroleum ether several times, and obtaining a crude product of compound 5-2 of about 22.3g. Yield: 75%.
Synthesis of Compound 5-3:
Accurately weighing compound 5-2 (22.3 g,15 mmol) and adding into a 500mL three-necked flask, adding sodium carbonate (3.2 g,30 mmol), adding 2, 4-pentanedione (1.5 g,15 mmol) and then adding 150mL of dichloromethane, 50mL of methanol, pumping nitrogen gas three times, and heating to 60 ℃ for reaction for 12 hours. After the reaction, washing with water, extracting with dichloromethane, mixing organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and performing silica gel column chromatography, wherein the eluting agent is PE (polyethylene) DCM=5:1 (volume ratio) to obtain 5-3 about 6.6g of compound. Yield: 27%. Ms:807.97.
synthesis of Compound 35:
accurately weighing 5-3 (6.6 g,8 mmol) sodium carbonate (1.7 g,16 mmol) and sequentially adding the compound into a 250mL three-necked flask, adding 50mL of ethylene glycol diethyl ether and 10mL of heavy water, pumping nitrogen three times, and heating to 100 ℃ for reaction for 12 hours. After the reaction was completed, the excess solvent was distilled off under reduced pressure, and the mixture was subjected to column chromatography on silica gel, wherein the eluent was about 5.4g of compound 35 from PE: EA=5:1 (volume ratio). Yield: 81.8%. Ms 808.97.
Example 6: synthesis of Compound 42
Synthesis of Compound 42:
accurately weighing compound 20 (4 g,4 mmol), sequentially adding sodium carbonate (0.85 g,8 mmol) into a 100mL three-neck flask, adding 30mL of ethylene glycol diethyl ether and 5mL of heavy water, pumping nitrogen gas three times, and heating to 100 ℃ for reaction for 12 hours. After the reaction was completed, the excess solvent was distilled off under reduced pressure, and the mixture was subjected to column chromatography on silica gel, wherein the eluent was about 3.3g of compound 42 per unit volume (PE: ea=5:1). Yield: 82.5%. Ms 989.23.
Example 7: synthesis of Compound 53
Synthesis of Compound 7-1:
2, 4-dibromopyridine (23.7 g,100 mmol), phenylboronic acid (12.2 g,100 mmol), tetraphenylphosphine palladium (3.5 g,3 mmol) and potassium carbonate (27.6 g,200 mmol) were weighed accurately, sequentially added into a 1000mL three-necked flask, toluene of about 400mL and water of 100mL were added, and after pumping in nitrogen three times, the temperature was raised to 90 ℃ for reaction overnight. After the raw materials are completely reacted, cooling to room temperature, separating liquid, extracting with ethyl acetate for three times, combining organic phases, and carrying out silica gel sample mixing column chromatography. Eluent was pe:ea=5:1 to give compound 7-1 about 18.5g, yield: 78.7%. Ms 235.10.
Synthesis of Compound 7-2:
accurately weighing compound 7-1 (18.3 g,78 mmol), compound A (13 g,78 mmol) of tris (dibenzylideneacetone) dipalladium (1.34 g,2.3 mmol), sodium tert-butoxide (14.9 g,156 mmol) were sequentially added into a 1000mL three-neck flask, anhydrous toluene was added about 450mL, nitrogen was pumped through three, and then tri-tert-butylphosphine (plastid ratio 10%9.4 mL) was added dropwise into the reaction system, followed by heating to 100℃for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, diluting with water, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product with toluene/methanol. About 21.5g of compound 7-2 was obtained in yield: 86%. Ms 321.40.
Synthesis of Compound 7-3:
accurately weighing compound 7-2 (21.5 g,67 mmol) and adding into a 500mL three-necked flask, adding iridium trichloride monohydrate (4.2 g, 13.4 mmol), adding 200mL of ethylene glycol diethyl ether, pumping nitrogen gas three times, heating to 120 ℃ for reaction for 12 hours, cooling the reaction liquid to room temperature, pumping filtration, and leaching a filter cake with petroleum ether for several times to obtain a crude product of compound 7-3 of about 20.5g. Yield: 70.5%.
Synthesis of Compound 53:
accurately weighing compound 7-3 (20.5 g,11.8 mmol) and adding sodium carbonate (2.5 g,23.6 mmol) into a 500mL three-necked flask, adding compound B (2.5 g,11.8 mmol) and then adding 200mL of dichloromethane and 80mL of methanol, pumping nitrogen gas three times, and heating to 60 ℃ for reaction for 12 hours. After the reaction was completed, the mixture was washed with water, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was distilled off under reduced pressure, followed by column chromatography on silica gel, eluting with PE: dcm=5:1 (volume ratio) to give about 4.6g of compound 53. Yield: 37.5%. Ms 1040.31.
Example 8: synthesis of Compound 62
Synthesis of Compound 8-1:
2, 4-dibromopyridine (23.7 g,100 mmol), 3, 5-dimethylbenzeneboronic acid (15 g,100 mmol), tetrakis triphenylphosphine palladium (3.5 g,3 mmol), potassium carbonate (27.6 g,200 mmol) were weighed accurately, sequentially added to a 1000mL three-necked flask, toluene was added to about 400mL, water was added to 100mL, nitrogen was pumped in three times, and the temperature was raised to 90℃for reaction overnight. After the raw materials are completely reacted, cooling to room temperature, separating liquid, extracting with ethyl acetate for three times, combining organic phases, and carrying out silica gel sample mixing column chromatography. Eluent was pe:ea=5:1 (volume ratio) yielding compound 8-1 about 20.5g, yield: 78.2%. Ms 263.15.
Synthesis of Compound 8-2:
accurately weighing compound 8-1 (20.5 g,78 mmol), compound A (13 g,78 mmol) of tris (dibenzylideneacetone) dipalladium (1.34 g,2.3 mmol), sodium tert-butoxide (14.9 g,156 mmol) were sequentially added into a 1000mL three-neck flask, anhydrous toluene was added about 450mL, nitrogen was pumped through three, and then tri-tert-butylphosphine (plastid ratio 10%9.4 mL) was added dropwise into the reaction system, followed by heating to 100 ℃ for reaction for 6 hours. After the raw materials are completely reacted, cooling to room temperature, diluting with water, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, and recrystallizing the crude product with toluene/methanol. About 23.6g of compound 8-2 was obtained in yield: 86.8%. Ms 349.45.
Synthesis of Compound 8-3:
accurately weighing compound 8-2 (23.5 g,67 mmol) and adding into a 500mL three-necked flask, adding iridium trichloride monohydrate (4.2 g, 13.4 mmol), adding 200mL of ethylene glycol diethyl ether, pumping nitrogen gas three times, heating to 120 ℃ for reaction for 12 hours, cooling the reaction liquid to room temperature, pumping filtration, and leaching a filter cake with petroleum ether for several times to obtain a crude product of compound 8-3 of about 20.5g. Yield: 66.3%.
Synthesis of Compound 62:
accurately weighing compound 8-3 (20.5 g,11.1 mmol) and adding sodium carbonate (2.4 g,22.2 mmol) and compound C (2.6 g,11.1 mmol) into a 500mL three-necked flask, adding 200mL of dichloromethane and 80mL of methanol, pumping nitrogen gas three times, and heating to 60 ℃ for reaction for 12 hours. After the reaction was completed, the mixture was washed with water, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was distilled off under reduced pressure, followed by column chromatography on silica gel, eluting with PE: dcm=5:1 (volume ratio) to give about 5.1g of compound 62. Yield: 40.9%. Ms 1124.46.
Preparing a device:
the structure of the device is as follows: ITO/HIL (30 nm)/HTL (60 nm)/EBL (10 nm)/EML (40 nm)/ETL (30 nm)/EIL (1 nm)/cathode (100 nm).
Wherein the EML consists of H-Host, E-Host and guest material metal complex, the mass ratio of the H-Host to the E-Host is 6:4, and the doping amount of the metal complex is 10% (w/w) of the total mass of the H-Host and the E-Host. The iridium metal complex (1) or (2) or (7) or (20) or (35) or (42) or (53) or (62) or REF) prepared by the embodiment of the invention is used as the light emitting layer guest material. ETL consists of LiQ (8-hydroxyquinoline-lithium) doped with 40% (w/w) ETM.
The OLED device used the following material structure:
REF synthesis refers to patent CN110229192a.
Preparation of OLED device
1) The ITO conductive glass anode layer was cleaned, then ultrasonically cleaned with deionized water, acetone, isopropanol for 15 minutes, and then treated in a plasma cleaner for 5 minutes to increase the work function of the electrode.
2) On the ITO anode layer, a hole injection layer material HIM is evaporated by a vacuum evaporation method, and the thickness is 30nm.
3) On the hole injection layer, a hole transport material HTM was vapor deposited by vacuum vapor deposition to a thickness of 60nm.
4) On the hole transport layer, an electron blocking material EBM was vapor deposited by vacuum vapor deposition to a thickness of 10nm.
5) And evaporating a luminescent layer material on the electron blocking layer by a vacuum evaporation mode, wherein the thickness of the luminescent layer material is 40nm.
6) An electron transport material was deposited on the light-emitting layer by vacuum deposition to a thickness of 30nm.
7) And vacuum evaporating an electron injection layer Liq on the electron transport layer, wherein the thickness of the electron injection layer Liq is 1nm.
8) And vacuum evaporating a cathode Al layer with the thickness of 100nm on the electron injection layer.
9) Encapsulation the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.
Wherein: the evaporation rates of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer are as followsAnd/s, the evaporation rate of the cathode layer is +.>And/s. High vacuum of 1X 10 -6 And millibars.
Characterization of OLED devices
The current-voltage-luminance (JVL) characteristics of the OLED devices 1 to 8 and OLED-REF are characterized by a characterization apparatus while recording important parameters such as external quantum efficiency and device lifetime. Lt95@1000nits is the time at constant current at which the luminance drops from an initial luminance of 1000nits to 95% of the initial luminance. The relative parameters of the OLED device are shown in the following table:
device relative data made of different dopants
As can be seen from the above table data, compared with the device made of REF metal complex, the external quantum efficiency and the device lifetime of the OLED device are both significantly improved by using the iridium metal complex material of the present invention as the doping material of the EML (light-emitting layer). The reason for the beneficial effect is inferred to be that the iridium metal complex provided by the invention contains a benzisoquinoline group to replace, so that charge transmission in the device is assisted, and the charge can be effectively used, thereby improving the luminous efficiency of the device, reducing the starting voltage and prolonging the service life of the device.
If the invention is further optimized, such as optimizing the structure of the device and optimizing the combination of the HTM, the ETM and the main material, the performance, particularly the efficiency, the driving voltage and the service life of the device are further improved.
The technical features of the above-described embodiments and examples may be combined in any suitable manner, and for brevity of description, all of the possible combinations of the technical features of the above-described embodiments and examples are not described, however, as long as there is no contradiction between the combinations of the technical features, they should be considered to be within the scope described in the present specification.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. An iridium metal complex is characterized by being shown in a general formula (I):
wherein:
R 1 、R 2 each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 10C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, an aromatic group having 6 to 10 ring atoms, a heteroaromatic group having 6 ring atoms, or a combination of these groups;
R 3 、R 4 Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 6C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, or a combination of these groups;
R 5 selected from H or D;
m is selected from 2;
n1 is selected from 0, 1, 2, 3, 4, 5, 6 or 7;
n2 is selected from 0, 1, 2, 3 or 4.
2. The iridium metal complex as claimed in claim 1, wherein R 3 、R 4 Each occurrence is independently selected from-H, -D, or the following groups:
-*
3. the iridium metal complex as claimed in claim 1, wherein R 1 、R 2 Each independently selected from H, -D, a straight chain alkyl group having 1 to 6C atoms, a branched or cyclic alkyl group having 3 to 10C atoms, or the following groups:
wherein each occurrence of X is independently selected from CR 6 Or N;
R 6 each time go outNow, independently selected from-H, -D, straight chain alkyl groups having 1 to 10C atoms, branched or cyclic alkyl groups having 3 to 10C atoms, or combinations of these groups;
* Representing the ligation site.
4. The iridium metal complex as claimed in claim 1, wherein the iridium metal complex has the following structure: r is R 1 、R 2 Each occurrence is independently selected from H, -D, or the following groups:
-*
wherein, represents the site of attachment.
5. The iridium metal complex according to claim 1, wherein the iridium metal complex is selected from the group consisting of:
6. a mixture comprising at least one iridium metal complex of any one of claims 1-5 and at least one other organic functional material, wherein the at least one other organic functional material is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting guest material, a light-emitting host material, or an organic dye.
7. A composition comprising the iridium metal complex as in any one of claims 1-5 or the mixture as in claim 6 and at least one organic solvent.
8. An organic electronic device comprising at least one functional layer, wherein the functional layer comprises an iridium metal complex as claimed in any one of claims 1 to 5 or a mixture as claimed in claim 6, or wherein the functional layer is prepared from the composition as claimed in claim 7.
9. An organic electronic device as claimed in claim 8, wherein: the organic electronic device is selected from an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic laser, an organic spintronic device, an organic sensor and an organic plasmon emitting diode.
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| CN107200754A (en) * | 2017-05-25 | 2017-09-26 | 吉林奥来德光电材料股份有限公司 | Metal iridium complex class luminous organic material and preparation method thereof and organic electroluminescence device |
| CN109705166A (en) * | 2019-01-24 | 2019-05-03 | 北京诚志永华显示科技有限公司 | Metal complex, electroluminescent organic material, organic electroluminescent device, electronic equipment |
| CN111892631A (en) * | 2020-07-15 | 2020-11-06 | 奥来德(上海)光电材料科技有限公司 | Iridium-matched electroluminescent material and preparation method and application thereof |
| CN114891042A (en) * | 2022-05-18 | 2022-08-12 | 吉林奥来德光电材料股份有限公司 | Organic metal compound and application thereof, luminescent device and luminescent device |
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| CN107200754A (en) * | 2017-05-25 | 2017-09-26 | 吉林奥来德光电材料股份有限公司 | Metal iridium complex class luminous organic material and preparation method thereof and organic electroluminescence device |
| CN109705166A (en) * | 2019-01-24 | 2019-05-03 | 北京诚志永华显示科技有限公司 | Metal complex, electroluminescent organic material, organic electroluminescent device, electronic equipment |
| CN111892631A (en) * | 2020-07-15 | 2020-11-06 | 奥来德(上海)光电材料科技有限公司 | Iridium-matched electroluminescent material and preparation method and application thereof |
| CN114891042A (en) * | 2022-05-18 | 2022-08-12 | 吉林奥来德光电材料股份有限公司 | Organic metal compound and application thereof, luminescent device and luminescent device |
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