Organic light emitting device and materials for use in same
11505561 · 2022-11-22
Assignee
Inventors
Cpc classification
H10K85/6574
ELECTRICITY
H10K85/6572
ELECTRICITY
C07D519/00
CHEMISTRY; METALLURGY
C09K11/025
CHEMISTRY; METALLURGY
H05B33/20
ELECTRICITY
International classification
Abstract
Specifically substituted hetero- or carbon-bridged phenylquinazolines of the general formulae (Ia) and (Ib) and a process for their preparation, an electronic device comprising at least one of these compounds, an emitting layer, preferably present in an electronic device, comprising at least one compound of general formulae (Ia) and (Ib) and the use of compounds according to general formulae (Ia) and (Ib) in an electronic device as a host material, a charge transporting material, charge and/or exciton blocking material, preferably as a host material or an electron transporting material.
Claims
1. A compound represented by one of formulae (IV-1), (IV-2), (IV-3), or (IV-4): ##STR00126## wherein X is O, S, NR.sup.10 or CR.sup.11R.sup.12; R.sup.10, R.sup.11 and R.sup.12 are independently H, an unsubstituted or substituted C.sub.6-C.sub.24-aryl group, an unsubstituted or substituted C.sub.1-C.sub.30 heteroaryl group, an unsubstituted or substituted C.sub.1-C.sub.25 alkyl group, an unsubstituted or substituted C.sub.7-C.sub.25aralkyl group, or an unsubstituted or substituted C.sub.5-C.sub.12 cycloalkyl group; and Ar.sup.1 is an unsubstituted or substituted group selected from the group consisting of naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, quinazolinyl, and quionolinyl.
2. The compound of claim 1, wherein Ar.sup.1 is represented by naphthyl, which is unsubstituted or biphenylyl, which is unsubstituted.
3. A process for preparing the compound of claim 1, the process comprising: coupling of a compound of formula ##STR00127## with a compound of formula (a) or (b) below ##STR00128## to obtain a compound of formula (Ia) or (Ib) wherein A is a selected from Cl, Br, I, F, —OSO.sub.2CH.sub.3, .OSO.sub.2CF.sub.3, —OSO.sub.2C.sub.6H.sub.4CH.sub.3 or —CHO; and X is O, S, NR.sup.10 or CR.sup.11R.sup.12; a, c, and e independently represent 0; b is 0; d is 0; R.sup.10, R.sup.11 and R.sup.12 are independently of each other H, an unsubstituted or substituted C.sub.6-C.sub.24aryl group, an unsubstituted or substituted C.sub.1-C.sub.30heteroaryl group, an unsubstituted or substituted C.sub.1-C.sub.25alkyl group, an unsubstituted or substituted C.sub.7-C.sub.25aralkyl group or an unsubstituted or substituted C.sub.5-C.sub.12cycloalkyl group; m and n represent 1; L.sup.1 and L.sup.2 a direct bond: Ar.sup.1 is unsubstituted or substituted group selected from the group consisting of naphthyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, quinazolinyl, and quionolinyl.
4. An electronic device comprising the compound of claim 1.
5. The electronic device of claim 4, comprising: a cathode, an anode, and a plurality of organic thin film layers provided between the cathode and the anode, wherein the organic thin film layers comprises an emitting layer comprising the compound of formula (IV-1) to (IV-4).
6. The electronic device of claim 4, wherein the emitting layer comprises a phosphorescent material, which is an ortho-metallated complex comprising a metal atom selected from the group consisting of iridium, osmium and platinum.
7. An electronic equipment comprising the organic claim 4.
8. An emitting layer comprising the compound of claim 1.
9. A host material, a charge transporting material, charge and/or exciton blocking material in an electronic device comprising the compound of claim 1.
10. A material for an organic electroluminescence device comprising the compound of claim 1.
11. The compound of claim 1, which is represented by formula (IV-1).
12. The compound of claim 1, which is represented by formula (IV-2).
13. The compound of claim 1, which is represented by formula (IV-3).
14. The compound of claim 1, which is represented by formula (IV-4).
Description
(1)
ANODE (A)
(2) The anode is an electrode which provides positive charge carriers. It may be composed, for example, of materials which comprise a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals comprise the metals of groups 11, 4, 5 and 6 of the Periodic Table of the Elements, and also the transition metals of groups 8 to 10. When the anode is to be transparent, mixed metal oxides of groups 12, 13 and 14 of the Periodic Table of the Elements are generally used, for example indium tin oxide (ITO). It is likewise possible that the anode (a) comprises an organic material, for example polyaniline, as described, for example, in Nature, Vol. 357, pages 477 to 479 (Jun. 11, 1992). Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AIZnO), and metals. Anode (and substrate) may be sufficiently transparent to create a bottom-emitting device. A preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate). A reflective anode may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. At least either the anode or the cathode should be at least partly transparent in order to be able to emit the light formed. Other anode materials and structures may be used.
(3) Hole Injection Layer (b) and Hole Transporting Layer (c):
(4) The hole-transporting layer is an organic layer that is formed between the emitting layer and the anode, and has a function of transporting holes from the anode to the emitting layer. If the hole-transporting layer is composed of plural layers, an organic layer that is nearer to the anode may often be defined as the hole-injecting layer. The hole-injecting layer has a function of injecting holes efficiently to the organic layer unit from the anode.
(5) Said hole injection layer is generally used for stabilizing hole injection from anode to hole transporting layer which is generally consist of organic materials.
(6) Organic material having good contact with anode or organic material with p-type doping is preferably used for the hole injection layer.
(7) Acceptor materials, or fused aromatic hydrocarbon materials or fused heterocycles which have high planarity, are preferably used, acceptor materials are more preferably used for the hole injection layer.
(8) Specific examples for acceptor materials are, the quinone derivatives with one or more electron withdrawing groups, such as F.sub.4TCNQ(2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), 1,2,3-Tris[(cyano)(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane, and so on; hexa-azatriphenylene derivatives with one or more electron withdrawing groups, such as hexa-azatriphenylene-hexanitrile; aromatic hydrocarbon derivatives with one or more electron withdrawing groups; aryl boron derivatives with one or more electron withdrawing groups, and so on.
(9) p-doping is usually consist of one or more p-dopant materials and one or more matrix materials. Matrix materials preferably have shallower HOMO level and p-dopant preferably have deeper LUMO level to enhance the carrier density of the layer. Aryl or heteroaryl amine derivatives are preferably used as the matrix materials. Specific examples for the matrix material are the same as that for hole transporting layer which is explained at the later part. Specific examples for p-dopant are the above mentioned acceptor materials, preferably the quinone derivatives with one or more electron withdrawing groups, such as F.sub.4TCNQ, 1,2,3-Tris[(cyano)(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane.
(10) The ratio of the p-type dopant is preferably less than 20% of molar ratio, more preferably less than 10%, such as 1%, 3%, 5% and so on.
(11) Hole transporting layer is generally used for injecting and transporting holes efficiently, and aromatic or heterocyclic amine derivatives are preferably used.
(12) Specific examples for hole transporting layer are represented as general formula (H),
(13) ##STR00050##
Ar.sub.1˜Ar.sub.3 each independently represents substituted or unsubstituted aryl group having 5 to 50 carbon atoms or substituted or unsubstituted heterocyclic group having 5 to 50 cyclic atoms, preferably phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, triphenylenyl group, fluorenyl group, spirobifluorenyl group, indenofluorenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazole substituted aryl group, dibenzofuran substituted aryl group or dibenzothiophene substituted aryl group; two or more substituents selected among Ar.sup.1˜Ar.sup.3 may be bonded to each other to form a ring structure, such as carbazole ring structure, acridane ring structure and so on.
(14) According to one embodiment, it is preferable that at least one of Ar.sub.1˜Ar.sub.3 have additional one aryl or heterocyclic amine substituent, more preferably Ar1 have an additional aryl amino substituent, at the case of that it is preferable that Ar1 represents substituted or unsubstituted biphenylene group, substituted or unsubstituted fluorenylene group.
(15) Second hole transporting layer is usually inserted between the first hole transporting layer and the emitting layer to enhance device performance by blocking excess electrons or excitons. Specific examples for second hole transporting layer is the same as the first hole transporting layer. It is preferably that second hole transporting layer have higher triplet energy to block triplet exciton especially for phosphorescent green device, such as bicarbazole derivatives, biphenylamine derivatives, triphenylenyl amine derivatives, fluorenyl amine derivatives, carbazole substituted arylamine derivatives, dibenzofuran substituted arylamine derivatives, dibenzothiophene substituted arylamine derivatives, and so on.
(16) Exciton Blocking Layer (d):
(17) Blocking layers may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. An electron/exciton blocking layer (d) may be disposed between the first emitting layer (e) and the hole transport layer (c), to block electrons from emitting layer (e) in the direction of hole transport layer (c). Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
(18) Suitable metal complexes for use as electron/exciton blocker material are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981, WO2008/000727 and PCT/EP2014/055520. Explicit reference is made here to the disclosure of the WO applications cited, and these disclosures shall be considered to be incorporated into the content of the present application.
(19) According to a preferred embodiment of the present invention, at least one compound of general formula (Ia) or (Ib) is present in the exciton blocking layer of the OLED according to the present invention.
(20) Emitting Layer (e)
(21) The light emitting layer is an organic layer having a light emitting function and is formed from one or more layers, wherein one of the layers comprises a host material (first host material), optionally a second host material, and the light emitting material.
(22) According to a preferred embodiment of the present invention, at least one compound of general formula (Ia) or (Ib) is present in the emitting layer of the OLED according to the present invention, preferably as host material.
(23) When the light emitting layer is composed of two or more layers, the light emitting layer or layers other than that mentioned above contains or contain a host material and a dopant material when a doping system is employed. The major function of the host material is to promote the recombination of electrons and holes and confine excitons in the light emitting layer. The dopant material causes the excitons generated by recombination to emit light efficiently.
(24) In case of a phosphorescent device, the major function of the host material is to confine the excitons generated on the dopant in the light emitting layer.
(25) The light emitting layer may be made into a double dopant layer, in which two or more kinds of dopant materials having high quantum yield are used in combination and each dopant material emits light with its own color. For example, to obtain a yellow emission, a light emitting layer formed by co-depositing a host, a red-emitting dopant and a green-emitting dopant is used.
(26) In a laminate of two or more light emitting layers, electrons and holes are accumulated in the interface between the light emitting layers, and therefore, the recombination region is localized in the interface between the light emitting layers, to improve the quantum efficiency.
(27) The light emitting layer may be different in the hole injection ability and the electron injection ability, and also in the hole transporting ability and the electron transporting ability each being expressed by mobility.
(28) The light emitting layer is formed, for example, by a known method, such as a vapor deposition method, a spin coating method, and LB method. Alternatively, the light emitting layer may be formed by making a solution of a binder, such as resin, and the material for the light emitting layer in a solvent into a thin film by a method such as spin coating.
(29) The light emitting layer is preferably a molecular deposit film. The molecular deposit film is a thin film formed by depositing a vaporized material or a film formed by solidifying a material in the state of solution or liquid. The molecular deposit film can be distinguished from a thin film formed by LB method (molecular build-up film) by the differences in the assembly structures and higher order structures and the functional difference due to the structural differences.
(30) The light-emitting layer (e) comprises at least one fluorescence or phosphorescence emitter, suitable emitter materials being known to those skilled in the art.
(31) The emission wavelength of the phosphorescent dopant used in the light emitting layer is not particularly limited. In a preferred embodiment, at least one of the phosphorescent dopants used in the light emitting layer has the peak of emission wavelength of in general 430 nm or longer and 780 nm or shorter, preferably 490 nm or longer and 700 nm or shorter and more preferably 490 nm or longer and 650 nm or shorter. Most preferred are green emitter materials (490 to 570 nm). In another preferred embodiment, red emitter materials (570 to 680 nm) are preferred.
(32) The phosphorescent dopant (phosphorescent emitter material) is a compound which usually emits light by releasing the energy of excited triplet state.
(33) The compounds according to general formula (Ia) or (Ib) are most preferably used as the matrix (=host material) in the light-emitting layer.
(34) Suitable metal complexes for use in the inventive OLEDs, preferably as emitter material, are described, for example, in documents WO 02/60910 A1, US 2001/0015432 A1, US 2001/0019782 A1, US 2002/0055014 A1, US 2002/0024293 A1, US 2002/0048689 A1, EP 1 191 612 A2, EP 1 191 613 A2, EP 1 211 257 A2, US 2002/0094453 A1, WO 02/02714 A2, WO 00/70655 A2, WO 01/41512 A1, WO 02/15645 A1, WO 2005/019373 A2, WO 2005/113704 A2, WO 2006/115301 A1, WO 2006/067074 A1, WO 2006/056418, WO 2006121811 A1, WO 2007095118 A2, WO 2007/115970, WO 2007/115981, WO 2008/000727, WO2010129323, WO2010056669, WO10086089, US2011/0057559, WO2011/106344, US2011/0233528, WO2012/048266 and WO2012/172482.
(35) Further suitable metal complexes are the commercially available metal complexes tris(2-phenylpyridine)iridium(III), iridium(III) tris(2-(4-tolyl)pyridinato-N,C.sup.2′), bis(2-phenylpyridine)(acetylacetonato)iridium(III), iridium(III) tris(l-phenylisoquinoline), iridium(III) bis(2,2′-benzothienyl)pyridinato-N,C.sup.3′)(acetylacetonate), tris(2-phenylquinoline)iridium(III), iridium(III) bis(2-(4,6-difluorophenyl)pyridinato-N,C.sup.2)picolinate, iridium(III) bis(1-phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acetylacetonato)iridium(III), iridium(III) bis(di-benzo[f,h]quinoxaline)(acetylacetonate), iridium(III) bis(2-methyldi-benzo[f,h]quinoxaline)(acetylacetonate) and tris(3-methyl-1-phenyl-4-trimethylacetyl-5-pyrazolino)terbium(III), bis[l-(9,9-dimethyl-9H-fluoren-2-yl)isoquinoline](acetyl-acetonato)iridium(III), bis(2-phenylbenzothiazolato)(acetylacetonato)iridium(III), bis(2-(9,9-dihexylfluorenyl)-1-pyridine)(acetylacetonato)iridium(III), bis(2-benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III).
(36) In addition, the following commercially available materials are suitable: tris(dibenzoylacetonato)mono(phenanthroline)europium(III), tris(dibenzoylmethane)-mono(phenanthroline)europium(III), tris(dibenzoylmethane)mono(5-aminophenanthroline)-europium(Ill), tris(di-2-naphthoylmethane)mono(phenanthroline)europium(III), tris(4-bromobenzoylmethane)mono(phenanthroline)europium(III), tris(di(biphenyl)methane)-mono(phenanthroline)europium(III), tris(dibenzoylmethane)mono(4,7-diphenyl-phenanthroline)europium(III), tris(dibenzoylmethane)mono(4,7-di-methyl-phenanthroline)europium(III), tris(dibenzoylmethane)mono(4,7-dimethylphenanthrolinedisulfonic acid)europium(Ill) disodium salt, tris[di(4-(2-(2-ethoxyethoxy)ethoxy)benzoylmethane)]mono-(phenanthroline)europium(III) and tris[di[4-(2-(2-ethoxyethoxy)ethoxy)benzoylmethane)]mono(5-aminophenanthroline)europium(III), osmium(II) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1,2,4-triazolato)diphenylmethylphosphine, osmium(II) bis(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4-triazole)dimethylphenylphosphine, osmium(II) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1,2,4-triazolato)dimethylphenylphosphine, osmium(II) bis(3-(trifluoromethyl)-5-(2-pyridyl)-pyrazolato)dimethylphenylphosphine, tris[4,4′-di-tert-butyl(2,2′)-bipyridine]ruthenium(III), osmium(II) bis(2-(9,9-dibutylfluorenyl)-1-isoquinoline(acetylacetonate).
(37) Particularly suitable metal complexes are described in US2014048784, US2012223295, US2014367667, US2013234119, US2014001446, US2014231794, US2014008633, WO2012108388 and WO2012108389. The emitters mentioned in US2013234119, paragraph [0222], are exemplified. Selected emitters, especially red emitters, of said emitters mentioned in US2013234119 paragraph [0222], are:
(38) ##STR00051## ##STR00052##
(39) Further suitable Emitters are mentioned in: Mrs Bulletin, 2007, 32, 694:
(40) ##STR00053##
(41) Further suitable Emitters are mentioned in: WO2009100991:
(42) ##STR00054##
(43) Further suitable Emitters are mentioned in: WO2008101842:
(44) ##STR00055##
(45) Further suitable Emitters are mentioned in: US 20140048784, especially in paragraph [0159]:
(46) ##STR00056## ##STR00057## ##STR00058## ##STR00059##
(47) Further suitable red emitters are shown in WO 2008/109824. Preferred red emitters according to this document are the following compounds:
(48) ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064##
(49) The emitter materials (dopants), preferably the phosphorescent emitter materials, may be used alone or in combination of two or more.
(50) Further red emitters that may be used in the OLEDs according to the present invention are disclosed in US 2013/0299795 and are shown in the following:
(51) ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077##
(52) Further red emitters that may be used in the OLEDs according to the present invention are disclosed in US 2013/0146848 and are shown in the following:
(53) ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089##
(54) Further suitable red emitters are shown in US 2015/0001472. Preferred red emitters according to this document are the following compounds:
(55) ##STR00090## ##STR00091## ##STR00092## ##STR00093##
(56) Further suitable red emitters are shown in US 2016/0093808. Preferred red emitters according to this document are the following compounds:
(57) ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105##
(58) According to a further embodiment of the OLED according to the present invention, the light emitting layer may comprise at least one fluorescent, preferably blue, emitter. Examples of preferred blue dopants that may be present in the light emitting layer of the OLED according to the present invention are polycyclic amine derivatives as mentioned in EP 2924029. Particularly preferred aromatic amine derivatives are selected from compounds according to the following formula (20):
(59) ##STR00106##
(60) In the formula (20), Y is a substituted or unsubstituted fused aromatic hydrocarbon group including 10 to 50 ring carbon atoms.
(61) Ar.sub.101, and Ar.sub.02 are independently a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic ring group including 5 to 50 ring atoms.
(62) Specific examples of Y include the above-mentioned fused aryl group. Y is preferably a substituted or unsubstituted anthryl group, a substituted or unsubstituted pyrenyl group or a substituted or unsubstituted chrysenyl group.
(63) n is an integer of 1 to 4. It is preferred that n be an integer of 1 to 2.
(64) The above-mentioned formula (20) is preferably one represented by the following formulas (21) to (24).
(65) ##STR00107## ##STR00108## ##STR00109## ##STR00110##
(66) In the formulae (21) to (24), R.sub.e, R.sub.f and R.sub.g are independently a substituted or unsubstituted alkyl group including 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group including 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group including 2 to 50 carbon atoms, a substituted or unsubstituted aralykyl group including 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 20 ring carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 20 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkyl germanium group including 1 to 50 carbon atoms or a substituted or unsubstituted aryl germanium group including 6 to 50 ring carbon atoms. R.sub.e, R.sub.f and R.sub.g may independently be bonded to any of the bonding positions of the benzene rings that constitutes the fused polycyclic skeleton.
(67) As preferable examples of R.sub.e, R.sub.f and R.sub.g, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms can be given. More preferably, R.sub.e, R.sub.f and R.sub.g are a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or the like.
(68) t is an integer of 0 to 10. u is an integer of 0 to 8. m is an integer of 0 to 10. Ar.sub.201 to Ar.sub.218 are independently an aryl group including 6 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic group including 5 to 50 ring atoms.
(69) Preferred examples of Ar.sub.201 to Ar.sub.218 include a substituted or unsubstituted phenyl group, a substituted or unsubstituted dibenzofuranyl group or the like. As preferable examples of the substituent of Ar.sub.201 to Ar.sub.218, an alkyl group, a cyano group and a substituted or unsubstituted silyl group can be given.
(70) In the formulae (21) to (24), as examples of the alkyl group, the alkoxy group, the aryl group, the aryloxy group and the heterocyclic group, those exemplified above can be given.
(71) As the alkenyl group including 2 to 50, preferably 2 to 30, more preferably 2 to 20, and particularly preferably 2 to 10, carbon atoms, a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butanedienyl group, a 1-methylvinyl group, a styryl group, a 2,2-diphenylvinyl group, a 1,2-diphenylvinyl group, a 1-methylallyl group, a 1,1-dimethylallyl group, a 2-methylallyl group, a 1-phenylallyl group, a 2-phenylallyl group, a 3-phenylallyl group, a 3,3-diphenylallyl group, a 1,2-dimethylallyl group, a 1-phenyl-1-butenyl group, a 3-phenyl-1-butenyl group or the like can be given. Preferred are a styryl group, a 2,2-diphenylvinyl group, a 1,2-diphenylvinyl group or the like.
(72) As the alkynyl group including 2 to 50 (preferably 2 to 30, more preferably 2 to 20, particularly preferably 2 to 10) carbon atoms, a propargyl group, a 3-pentynyl group or the like can be given.
(73) As the alkyl germanium group, a methylhydrogermyl group, a trimethylgermyl group, a triethylgermyl group, a tripropylgermyl group, a dimethyl-t-butylgermyl group or the like can be given.
(74) As the aryl germanium group, a phenyldihydrogermyl group, a diphenylhydrogermyl group, a triphenylgermyl group, a tritolylgermyl group, a trinaphthylgermyl group or the like can be given.
(75) As the styrylamine compound and the styryldiamine compound, those represented by the following formulas (17) and (18) are preferable.
(76) ##STR00111##
(77) In the formula (17), Ar.sub.301 is a k-valent group; a k-valent group corresponding to a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a stilbene group, a styrylaryl group and a distyrylaryl group. Ar.sub.302 and Ar.sub.303 are independently an aryl group including 6 to 20 ring carbon atoms, and Ar.sub.301, Ar.sub.302 and Ar.sub.303 may be substituted.
(78) k is an integer of 1 to 4, with an integer of 1 and 2 being preferable. Any one of Ar.sub.302 to Ar.sub.303 is a group including a styryl group. It is further preferred that at least one of Ar.sub.302 and Ar.sub.303 be substituted by a styryl group.
(79) As for the aryl group including 6 to 20 ring carbon atoms, the above-mentioned aryl group can be specifically given. Preferable examples include a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a terphenyl group or the like.
(80) In the formula (18), Ar.sub.304 to Ar.sub.306 are a v-valent substituted or unsubstituted aryl group including 6 to 40 ring carbon atoms. v is an integer of 1 to 4, with an integer of 1 and 2 being preferable.
(81) Here, as the aryl group including 6 to 40 ring carbon atoms in the formula (18), the above-mentioned aryl group can be specifically given. A naphthyl group, an anthranyl group, a chrysenyl group, a pyrenyl group or an aryl group represented by the formula (20) is preferable.
(82) As preferable substituents that substitute on the aryl group, an alkyl group including 1 to 6 carbon atoms, an alkoxy group including 1 to 6 carbon atoms, an aryl group including 6 to 40 ring carbon atoms, an amino group substituted by an aryl group including 6 to 40 ring carbon atoms, an ester group including an aryl group that includes 5 to 40 ring carbon atoms, an ester group including an alkyl group that includes 1 to 6 carbon atoms, a cyano group, a nitro group, a halogen atom or the like can be given.
(83) The content of the emitter materials (dopants), preferably the phosphorescent emitter materials, in the light emitting layer is not particularly limited and selected according to the use of the device, and preferably 0.1 to 70% by mass, and more preferably 1 to 30% by mass. If being 0.1% by mass or more, the amount of light emission is sufficient. If being 70% by mass or less, the concentration quenching can be avoided. The further component in the emitting layer is usually one or more host material, which is preferably present in an amount of 30 to 99.9% by mass, more preferably 70 to 99% by mass, wherein the sum of the emitter material(s) and the host material(s) is 100% by mass.
(84) Further possible fluorescent blue emitters that may be present in the emitting layer of the OLED according to the present invention are mentioned in US2012112169.
(85) Host (Matrix) Materials
(86) The compound of formula (Ia) or (Ib) is preferably employed as host material, more preferably as phosphorescent host material.
(87) The light-emitting layer may comprise further components in addition to the emitter material. For example, a fluorescent dye may be present in the light-emitting layer in order to alter the emission color of the emitter material. In addition—in a preferred embodiment—a matrix material can be used. This matrix material may be a polymer, for example poly(N-vinylcarbazole) or polysilane. The matrix material may, however, be a small molecule, for example 4,4′-N,N′-dicarbazolebiphenyl (CDP=CBP) or tertiary aromatic amines, for example TCTA.
(88) In the case that one or more phosphorescent emitter materials are used in the light emitting layer, one or more phosphorescent hosts are usually employed as host material. The phosphorescent host is a compound which confines the triplet energy of the phosphorescent dopant efficiently in the light emitting layer to cause the phosphorescent dopant to emit light efficiently.
(89) In a preferred embodiment, the light-emitting layer is formed of at least one emitter material and of at least one of the matrix materials (hosts) mentioned in this application. According to a preferred embodiment, the electronic device according to the present invention, preferably the OLED according to the present invention, comprises at least one compound according to general formula (Ia) or (Ib) as matrix (host) material.
(90) According to one embodiment, the light-emitting layer comprises at least one emitter material and at least two matrix materials (co-host system), wherein one of the matrix materials is a compound according to general formula (Ia) or (Ib) and the other matrix material(s) is/are used as co-host(s). Suitable other host materials than the compounds of general formula (Ia) or (Ib) (co-hosts) are known by a person skilled in the art. “Further host materials” means in the sense of the present application, host materials different from the compounds of general formula (Ia) or (Ib). However, it is also possible to use two or more different compounds of general formula (Ia) and/or (Ib) as host material in the light-emitting layer in an OLED of the present application. This embodiment is preferably realized with emitter materials that emit red light.
(91) According to another embodiment, the light-emitting layer comprises at least one emitter material and a compound according to general formula (Ia) or (Ib) as a single matrix material. Examples of preferred compounds of general formula (Ia) or (Ib) useful as single host material are shown above. This embodiment is preferably realized with emitter materials that emit red light.
(92) In a more preferred embodiment, the light-emitting layer is formed from 0.1 to 70% by weight, preferably 1 to 30% by weight, of at least one of the aforementioned emitter materials and 30 to 99.9% by weight, preferably 70 to 99% by weight, of at least one of the matrix materials mentioned in the specification—in one preferred embodiment at least one compound according to general formula (Ia) or (Ib)—where the sum total of the emitter material and of the matrix material adds up to 100% by weight.
(93) Suitable host materials that may be used in the electronic device according to the present invention as host materials, if the compounds according to the present invention are not used as host material, but for example as charge transporting material, i.e. as electron transporting material or hole transporting material, are also known by a person skilled in the art.
(94) According to the present invention, the compounds according to general formula (Ia) or (Ib) are preferably be used as host material in the light emitting layer of the electronic device, preferably in a OLED, according to the present invention. The compounds according to general formula (Ia) or (Ib) can be used (a) as single host materials or can be used (b) in combination with any compounds suitable as host materials as mentioned above.
(95) Electron Transport Layer (g) and Electron Injecting Layer (h):
(96) The electron-transporting layer is an organic layer that is formed between the emitting layer and the cathode and has a function of transporting electrons from the cathode to the emitting layer. When the electron-transporting layer is formed of plural layers, an organic layer that is nearer to the cathode is often defined as the electron-injecting layer. The electron-injecting layer has a function of injecting electrons from the cathode efficiently to the organic layer unit.
(97) According to one embodiment, it is preferred that ET layer further comprising the other one or more layer(s) than electron injection layer to enhance efficiency and lifetime of the device, preferably between an electron injection layer and an emitting layer as a hole blocking layer, a exciton blocking layer or a triplet blocking layer.
(98) A compound of the formula (1) is also preferable as all the use of the electron transporting layer, such as an electron transporting layer, an electron-injecting layer, a hole blocking layer, a exciton blocking layer or a triplet blocking layer.
(99) According to one embodiment, it is preferred that an electron-donating dopant be contained in the interfacial region between the cathode and the emitting unit. Due to such a configuration, the organic EL device can have an increased luminance or a long life. Here, the electron-donating dopant means one having a metal with a work function of 3.8 eV or less. As specific examples thereof, at least one selected from an alkali metal, an alkali metal complex, an alkali metal compound, an alkaline earth metal, an alkaline earth metal complex, an alkaline earth metal compound, a rare earth metal, a rare earth metal complex and a rare earth metal compound or the like can be mentioned.
(100) As the alkali metal, Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV) and the like can be given. One having a work function of 2.9 eV or less is particularly preferable. Among them, K, Rb and Cs are preferable. Rb or Cs is further preferable. Cs is most preferable. As the alkaline earth metal, Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV) and the like can be given.
(101) One having a work function of 2.9 eV or less is particularly preferable. As the rare-earth metal, Sc, Y, Ce, Tb, Yb and the like can be given. One having a work function of 2.9 eV or less is particularly preferable.
(102) Examples of the alkali metal compound include an alkali oxide such as Li2O, Cs2O or K2O, and an alkali halide such as LiF, NaF, CsF and KF. Among them, LiF, Li2O and NaF are preferable.
(103) Examples of the alkaline earth metal compound include BaO, SrO, CaO, and mixtures thereof such as BaxSr1-xO (0<x<1) and BaxCa1-xO (0<x<1). Among them, BaO, SrO and CaO are preferable. Examples of the rare earth metal compound include YbF3, ScF3, ScO3, Y2O3, Ce2O3, GdF3 and TbF3. Among these, YbF3, ScF3 and TbF3 are preferable.
(104) The alkali metal complexes, the alkaline earth metal complexes and the rare earth metal complexes are not particularly limited as long as they contain, as a metal ion, at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions. Meanwhile, preferred examples of the ligand include, but are not limited to, quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, hydroxyfluborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, azomethines, and derivatives thereof.
(105) Regarding the addition form of the electron-donating dopant, it is preferred that the electron-donating dopant be formed in a shape of a layer or an island in the interfacial region. A preferred method for the formation is a method in which an organic compound (a light emitting material or an electron-injecting material) for forming the interfacial region is deposited simultaneously with deposition of the electron-donating dopant by a resistant heating deposition method, thereby dispersing the electron-donating dopant in the organic compound. The dispersion concentration of the organic compound: the electron-donating dopant (molar ratio) is 100:1 to 1:100, preferably 5:1 to 1:5.
(106) In a case where the electron-donating dopant is formed into the shape of a layer, the light-emitting material or electron-injecting material which serves as an organic layer in the interface is formed into the shape of a layer. After that, a reductive dopant is solely deposited by the resistant heating deposition method to form a layer preferably having a thickness of from 0.1 nm to 15 nm. In a case where the electron-donating dopant is formed into the shape of an island, the emitting material or the electron-injecting material which serves as an organic layer in the interface is formed into the shape of an island. After that, the electron-donating dopant is solely deposited by the resistant heating deposition method to form an island preferably having a thickness of from 0.05 nm to 1 nm.
(107) The ratio of the main component and the electron-donating dopant in the organic EL device according to the invention is main component: electron-donating dopant=5:1 to 1:5 in terms of molar ratio, more preferably 2:1 to 1:2.
(108) As the electron-transporting material used in the electron-transporting layer other than a compound of the formula (1), an aromatic heterocyclic compound having one or more hetero atoms in the molecule may preferably be used. In particular, a nitrogen containing heterocyclic derivative is preferable.
(109) According to one embodiment, it is preferable that ET layer comprises a nitrogen containing heterocyclics metal chelate, such as 8-hydroxyquinolinolato aluminum, which is generally called as Alq.sub.3.
(110) According to the other embodiment, it is preferable that ET layer comprising substituted or unsubstituted nitrogen containing heterocyclic derivative.
(111) Specific examples of the preferable heterocyclic derivative for ET layer are, 6-membered azine derivatives; such as pyridine derivatives, pyrimidine derivatives, triazine derivatives, pyrazine derivatives, preferably pyrimidine derivatives or triazine derivatives; 6-membered fused azine derivatives, such as quinolone derivatives, isoquinoline derivatives, quinoxaline derivatives, quinazoline derivatives, phenanthroline derivatives, benzoquinoline derivatives, benzoisoquinoline derivatives, dibenzoquinoxaline derivatives, preferably quinolone derivatives, isoquinoline derivatives, phenanthroline derivatives; 5-membered heterocyclic derivatives, such as imidazole derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, thiazole derivatives, thiadiazole derivatives; fused imidazole derivatives, such as benzimidazole derivatives, imidazopyridine derivatives, naphthoimidazole derivatives, benzimidazophenanthridine derivatives, benzimidzobenzimidazole derivatives, preferably benzimidazole derivatives, imidazopyridine derivatives or benzimidazophenanthridine derivatives.
(112) According to the other embodiment, it is preferable ET layer comprises phosphine oxide derivative represented as Ar.sub.p1Ar.sub.p2Ar.sub.P3P═O.
(113) Ar.sub.p1˜Ar.sub.p3 are the substituents of phosphor atom and each independently represent substituted or unsubstituted above mentioned aryl group or substituted or unsubstituted above mentioned heterocyclic group.
(114) According to the other embodiment, it is preferable that ET layer comprises aromatic hydrocarbon derivatives.
(115) Specific examples of the preferable aromatic hydrocarbon derivatives for ET layer are, oligo-phenylene derivatives, naphthalene derivatives, fluorene derivatives, fluoranthenyl group, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, triphenylene derivatives, benzanthracene derivatives, chrysene derivatives, benzphenanthrene derivatives, naphthacene derivatives, benzochrysene derivatives, and so on, preferably anthracene derivatives, pyrene derivatives and fluoranthene derivatives.
(116) Cathode (i):
(117) The cathode (i) is an electrode which serves to introduce electrons or negative charge carriers. The cathode may be any metal or nonmetal which has a lower work function than the anode. Suitable materials for the cathode are selected from the group consisting of alkali metals of group 1, for example Li, Cs, alkaline earth metals of group 2, metals of group 12 of the Periodic Table of the Elements, comprising the rare earth metals and the lanthanides and actinides. In addition, metals such as aluminum, indium, calcium, barium, samarium and magnesium, and combinations thereof, may be used.
(118) In general, the different layers, if present, have the following thicknesses:
(119) anode (a): 500 to 5000 Å (Angstrom), preferably 1000 to 2000 Å;
(120) hole injection layer (b): 50 to 1000 Å, preferably 200 to 800 Å,
(121) hole-transport layer (c): 50 to 1000 Å, preferably 100 to 800 Å,
(122) exciton blocking layer (d): 10 to 500 Å, preferably 50 to 100 Å,
(123) light-emitting layer (e): 10 to 1000 Å, preferably 50 to 600 Å,
(124) hole/exciton blocking layer (f): 10 to 500 Å, preferably 50 to 100 Å,
(125) electron-transport layer (g): 50 to 1000 Å, preferably 200 to 800 Å,
(126) electron injection layer (h): 10 to 500 Å, preferably 20 to 100 Å,
(127) cathode (i): 200 to 10 000 Å, preferably 300 to 5000 Å.
(128) The person skilled in the art is aware (for example on the basis of electrochemical studies) of how suitable materials have to be selected. Suitable materials for the individual layers are known to those skilled in the art and are disclosed, for example, in WO 00/70655.
(129) In addition, it is possible that some of the layers used in the inventive OLED have been surface-treated in order to increase the efficiency of charge carrier transport. The selection of the materials for each of the layers mentioned is preferably determined by obtaining an OLED with a high efficiency and lifetime.
(130) The inventive electronic device, preferably OLED, can be produced by methods known to those skilled in the art. In general, the inventive OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass, inorganic semiconductors or polymer films. For vapor deposition, it is possible to use customary techniques, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others. In an alternative process, the organic layers of the OLED can be applied from solutions or dispersions in suitable solvents, employing coating techniques known to those skilled in the art.
(131) Use of the compounds according to general formula (Ia) or (Ib) in at least one layer of the OLED, preferably in the light-emitting layer, preferably as a host material, a charge transporting material, particularly preferably as a host material and hole or electron transporting material, makes it possible to obtain OLEDs, with high efficiency and with low use and operating voltage. Frequently, the OLEDs obtained by the use of the compounds according to general formula (Ia) or (Ib) additionally have long lifetime. The efficiency of the electronic devices, preferably OLEDs can additionally be improved by optimizing the other layers of the OLEDs. For example, high-efficiency cathodes such as Ca or Ba, if appropriate in combination with an intermediate layer of LiF, can be used. Moreover, additional layers may be present in the OLEDs in order to adjust the energy level of the different layers and to facilitate electroluminescence.
(132) The OLEDs may further comprise at least one second light-emitting layer. The overall emission of the OLEDs may be composed of the emission of the at least two light-emitting layers and may also comprise white light.
(133) The OLEDs can be used in all apparatus in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units and illumination units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Further devices in which the inventive OLEDs can be used are, for example, keyboards; items of clothing; furniture; wallpaper. In addition, the present invention relates to a device selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising at least one inventive organic light-emitting diode or at least one inventive light-emitting layer.
(134) The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.
EXAMPLES
(135) Compounds Synthesized
(136) Compound 1
(137) Intermediate 1-1
(138) ##STR00112##
(139) (9H-Carbazole-1-yl)boronic acid (26.38 g, 90.0 mmol) and 1-bromo-2-nitrobenzene (20.20 g, 100.0 mmol) were dissolved in 700 ml of dimethylacetamide. The reaction mixture was evacuated and purged with Argon gas three times. Then, PdCl.sub.2(dppf)-CH.sub.2Cl.sub.2 (4.08 g, 5.00 mmol) and potassium acetate (29.44 g, 300.0 mmol) were added to the mixture, and the reaction mixture was stirred at 135° C. for 21 h. The solid was removed by filtration, and the filtrate was concentrated. The solid was washed with toluene, and the toluene solution was concentrated. The crude product was purified by column chromatography on silica gel eluting with a mixed solvent of toluene and heptane to yield 13.61 g (55%) of 1-1 as a brown solid.
(140) Without further purification, it was used for the next reaction.
(141) Intermediate 1-2
(142) ##STR00113##
(143) 1-1 (2.50 g, 8.67 mmol), 2-bromonaphthalene (2.33 g, 11.27 mmol), and sodium-tert-butoxide (1.17 g, 12.14 mol) were suspended in 58 ml of xylene. The mixture was evacuated and purged with Argon gas three times. Then, tBu.sub.3P—HBF.sub.4 (0.20 g, 0.695 mmol) and Pd.sub.2(dba).sub.3 (0.159 g, 0.173 mmol) were added there, and the mixture was stirred at 100° C. overnight. The reaction mixture was filtered off, and then washed with toluene, ethanol, and water. After the solid was dried in vacuum oven, 1-2 was obtained as a grey solid in a yield of 70% (2.50 g). Without further purification, it was used for the next reaction.
(144) LC-MS: 414 [M+H]
(145) Intermediate 1-3
(146) ##STR00114##
(147) 1-2 (1.45 g, 3.50 mmol) and triphenylphosphine (2.75 g, 10.5 mmol) were added in 3 ml of 1,2-dichlorobenzene. The mixture was stirred at 180° C. for 21 h under nitrogen flow. After the solvent was evaporated, the crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and toluene to yield 1.13 g (84%) of 1-3 as a white solid.
(148) LC-MS: 382 [M+H]
(149) Compound 1
(150) ##STR00115##
(151) 1-3 (1.75 g, 4.58 mmol), 2-chloromeno[4,3,2-de]quinazoline (1.22 g, 4.80 mmol), which was prepared according to the procedure disclosed in WO2017/109727, and potassium carbonate (1.26 g, 9.15 mmol) were added to 30 ml of dimethylacetamide. The reaction mixture was stirred at 120° C. overnight. After the reaction mixture was cooled at room temperature, the solid was collected by filtration, and washed with ethanol and water. The solid was recrystallized with 1,2-dichlorobenzene to yield 2.38 g (87%) of Compound 1 as a yellow solid.
(152) LC-MS: 601 [M+H]
(153) Compound 2
(154) Intermediate 2-1
(155) ##STR00116##
(156) 1-1 (1.70 g, 5.90 mmol), 4-bromo-1,1′-biphenyl (1.44 g, 6.19 mmol), and sodium-tert-butoxide (793 mg, 8.26 mol) were suspended in 30 ml of xylene. The mixture was evacuated and purged with Argon gas three times. Then, tBu.sub.3P—HBF.sub.4 (137 mg, 0.472 mmol) and Pd.sub.2(dba).sub.3 (108 mg, 0.118 mmol) were added there, and the mixture was stirred at 130° C. for 2 h. The reaction mixture was filtered off, and washed with ethanol, and water. The solid was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and toluene to yield 1.80 g (69%) of 2-1 as a white solid.
(157) LC-MS: 440 [M+H]
(158) Intermediate 2-2
(159) ##STR00117##
(160) 2-1 (1.79 g, 4.06 mmol) and triphenylphosphine (3.41 g, 13.0 mmol) were added in 4 ml of 1,2-dichlorobenzene. The mixture was stirred at 180° C. overnight under nitrogen flow. After the solvent was evaporated, the crude product was purified by column chromatography on silica gel eluting with a mixed solvent of heptane and toluene to yield 1.20 g (72%) of 2-2 as a beige solid.
(161) LC-MS: 408 [M+H]
(162) Compound 2
(163) ##STR00118##
(164) 2-2 (1.20 g, 2.94 mmol), 2-chloromeno[4,3,2-de]quinazoline (786 mg, 3.08 mmol), and potassium carbonate (812 mg, 5.88 mmol) were added to 20 ml of dimethylacetamide. The reaction mixture was stirred at 140° C. overnight. After the reaction mixture was cooled at room temperature, the solid was collected by filtration, and washed with ethanol and water. The solid was recrystallized with 1,2-dichlorobenzene to yield 1.35 g (73%) of Compound 2 as a yellow solid.
(165) LC-MS: 627 [M+H]
(166) Compound 3
(167) Intermediate 3-1
(168) ##STR00119##
(169) 1-1 (1.20 g, 4.16 mmol), 2-chloroquinoline (0.82 g, 4.99 mmol), and sodium-tert-butoxide (560 mg, 5.83 mol) were suspended in 28 ml of xylene. The mixture was evacuated and purged with Argon gas three times. Then, tBu.sub.3P—HBF.sub.4 (97 mg, 0.33 mmol) and Pd.sub.2(dba).sub.3 (76 mg, 0.08 mmol) were added there, and the mixture was stirred at 145° C. overnight. After the reaction mixture was cooled at room temperature, filtered off, and washed with ethanol and water. The solid was dried in vacuum oven. 1.80 g (69%) of 3-1 was obtained as a white solid.
(170) This product was used for the next reaction without further purification.
(171) Intermediate 3-2
(172) ##STR00120##
(173) 3-1 (1.17 g, 2.82 mmol) and triphenylphosphine (3.69 g, 14.1 mmol) were added in 6 ml of 1,2-dichlorobenzene. The mixture was stirred at 180° C. overnight under nitrogen flow. After the solvent was evaporated, the crude product was purified by column chromatography on silica gel eluting with a mixed solvent of dichloromethane and toluene to yield 0.81 g (75%) of 3-2 as a beige solid. This product was used for the next reaction without further purification.
(174) Compound 3
(175) ##STR00121##
(176) 3-2 (1.30 g, 3.39 mmol), 2-chloromeno[4,3,2-de]quinazoline (907 mg, 3.56 mmol), and potassium carbonate (937 mg, 6.78 mmol) were added to 23 ml of dimethylacetamide. The reaction mixture was stirred at 120° C. overnight. After the reaction mixture was cooled at room temperature, the solid was collected by filtration, and washed with ethanol and water. The solid was recrystallized with 1,2-dichlorobenzene to yield 1.85 g (91%) of Compound 3 as a yellow solid.
(177) LC-MS: 602 [M+H]
(178) Compound 4
(179) ##STR00122##
(180) 4-1 (1.14 g, 3.00 mmol), which was prepared according to the procedure disclosed in WO2010113755, 2-chloromeno[4,3,2-de]quinazoline (779 mg, 3.06 mmol), and sodium tert-butoxide (404 mg, 4.20 mmol) were added to 20 ml of toluene. .sup.tBu.sub.3P—HBF.sub.4 (73 mg, 0.252 mmol) and Pd.sub.2(dba).sub.3 (55 mg, 0.06 mmol) were added to the solution, and then the mixture was evacuated and purged with Argon gas three times. The reaction mixture was stirred at 100° C. overnight. After the reaction mixture was cooled at room temperature, water was added there, and the aqueous layer was extracted. The organic layer was dried with MgSO.sub.4, filtered and concentrated. The crude product was purified by column chromatography eluting with CHCl.sub.3 to yield 1.22 g (68%) of Compound 4 as a yellow solid.
(181) LC-MS: 600 [M+H]
Application Example 1
(182) A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode was first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate was exposed to an ultraviolet light and ozone for further 30 min. This treatment also improved the hole injection properties of the ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below were applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 Å/sec at about 10.sup.−6-10.sup.−8 mbar. As the first layer, 5 nm-thick of electron accepting Compound A was vapor-deposited. Then 210 nm-thick of aromatic amine Compound B was applied as a hole transporting layer and 10 nm-thick of Compound C. Then, a mixture of 2% by weight of an emitter compound (compound D), 98% by weight of a host (Compound 1) was applied to form a 40 nm-thick phosphorescent-emitting layer. On the emitting layer, a mixture of 50% by weight of an electron transporting compound (Compound E), 50% by weight of Liq (8-hydroxyquinolate lithium) was applied to form a 30 nm-thick as an electron transport layer. Finally, 1 nm-thick LiF is deposited as an electron injection layer and 80 nm-thick Al was then deposited as a cathode to complete the device. The device was sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen.
(183) ##STR00123## ##STR00124##
Application Examples 2 and 3
(184) According to the process of Application Example 1, Application Examples 2 and 3 were repeated except that the host (Compound 1) was replaced by Compound 2 and Compound 3. The device results were shown in Table 1.
Comparative Application Examples 1 and 2
(185) According to the process of Application Example 1, Comparative Application Examples 1 and 2 were repeated except that the host (Compound 1) was replaced by comparative compounds (Comparative 1 and 2). The device results were shown at Table 1.
(186) ##STR00125##
OLED Characterization
(187) To characterize the OLED, electroluminescence spectra are recorded at various currents and voltages. In addition, the current-voltage characteristic is measured in combination with the luminance to determine luminous efficiency. Driving voltage (Voltage) and Commission Interna-tionale de l'Éclairage (CIE) coordinate are given at 10 mA/cm.sup.2 except otherwise stated.
(188) TABLE-US-00001 TABLE 1 Appl. Ex. Host Voltage (V) CIE x, y Appl. Ex. 1 Compound 1 4.34 0.66, 0.34 Appl. Ex. 2 Compound 2 4.62 0.66, 0.34 Appl. Ex. 3 Compound 3 4.74 0.66, 0.34 Comp. Appl. Ex. 1 Comparative 1 5.21 0.66, 0.34 Comp. Appl. Ex. 2 Comparative 2 5.09 0.66, 0.34
(189) The results are shown in Table 1. The CIE values show that the electroluminescence is origi-nated from the red emitter compound (Compound D). The Compounds 1, 2 and 3 show lower driving voltage than the comparative compounds (Comparative 1 and 2).