Detailed Description
OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically illustrates, without limitation, an organic light-emitting device 100. The drawings are not necessarily to scale, and some of the layer structures in the drawings may be omitted as desired. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the layers described. The nature and function of the various layers and exemplary materials are described in more detail in U.S. patent US7,279,704B2 at columns 6-10, the entire contents of which are incorporated herein by reference.
There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4 -TCNQ at a molar ratio of 50:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1 as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of cathodes are disclosed in U.S. Pat. nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, including composite cathodes having a thin layer of metal, such as Mg: ag, with an overlying transparent, electrically conductive, sputter deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implant layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.
The above-described hierarchical structure is provided by way of non-limiting example. The function of the OLED may be achieved by combining the various layers described above, or some of the layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sublayers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.
In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.
The OLED also requires an encapsulation layer, such as the organic light emitting device 200 shown schematically and without limitation in fig. 2, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to prevent harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film packages are described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.
Devices manufactured according to embodiments of the present invention may be incorporated into a variety of consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, heads-up displays, displays that are fully or partially transparent, flexible displays, smart phones, tablet computers, tablet phones, wearable devices, smart watches, laptops, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and taillights.
The materials and structures described herein may also be used in other organic electronic devices as listed above.
As used herein, "top" means furthest from the substrate and "bottom" means closest to the substrate. In the case where the first layer is described as being "disposed" on "the second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed on" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photosensitive" when it is believed that the ligand directly contributes to the photosensitive properties of the emissive material. When it is believed that the ligand does not contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary," but ancillary ligands may alter the properties of the photosensitive ligand.
It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by spin statistics that delay fluorescence by more than 25%. Delayed fluorescence can be generally classified into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. The P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).
On the other hand, the E-type delayed fluorescence does not depend on the collision of two triplet states, but on the transition between the triplet states and the singlet excited state. Compounds capable of generating E-type delayed fluorescence need to have very small mono-triplet gaps in order for the conversion between the energy states. The thermal energy may activate a transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as Thermally Activated Delayed Fluorescence (TADF). A significant feature of TADF is that the delay component increases with increasing temperature. The fraction of backfill singlet excited states may reach 75% if the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet states. The total singlet fraction may be 100%, well in excess of 25% of the spin statistics of the electrically generated excitons.
Type E delayed fluorescence features can be found in excitation complex systems or in single compounds. Without being bound by theory, it is believed that E-delayed fluorescence requires a luminescent material with a small mono-triplet energy gap (ΔeS-T). Organic non-metal containing donor-acceptor luminescent materials may be able to achieve this. The emission of these materials is typically characterized as donor-acceptor Charge Transfer (CT) type emission. The spatial separation of HOMO from LUMO in these donor-acceptor compounds generally yields a small ΔeS-T. These states may include CT states. Typically, donor-acceptor luminescent materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., an N-containing six-membered aromatic ring).
Definition of terms for substituents
Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.
Alkyl-as used herein, includes straight and branched chain alkyl groups. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. In addition, the alkyl group may be optionally substituted.
Cycloalkyl-as used herein, includes cyclic alkyl. Cycloalkyl groups may be cycloalkyl groups having 3 to 20 ring carbon atoms, preferably 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl are preferred. In addition, cycloalkyl groups may be optionally substituted.
Heteroalkyl-as used herein, a heteroalkyl comprises an alkyl chain in which one or more carbons is replaced by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium, and boron. The heteroalkyl group may be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermylmethyl, trimethylgermylethyl, dimethylethylgermylmethyl, dimethylisopropylgermylmethyl, t-butyldimethylgermylmethyl, triethylgermylmethyl, triethylgermylethyl, triisopropylgermylmethyl, triisopropylgermylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl. In addition, heteroalkyl groups may be optionally substituted.
Alkenyl-as used herein, covers straight chain, branched chain, and cyclic alkylene groups. Alkenyl groups may be alkenyl groups containing 2 to 20 carbon atoms, preferably alkenyl groups having 2 to 10 carbon atoms. Examples of alkenyl groups include ethenyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, 1-methylvinyl, styryl, 2-diphenylvinyl, 1-methallyl, 1-dimethylallyl, 2-methallyl, 1-phenylallyl, 2-phenylallyl, 3-diphenylallyl, 1, 2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl and norbornenyl. In addition, alkenyl groups may be optionally substituted.
Alkynyl-as used herein, straight chain alkynyl is contemplated. The alkynyl group may be an alkynyl group containing 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl and the like. Among the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl and phenylethynyl. In addition, alkynyl groups may be optionally substituted.
Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. The aryl group may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methylbiphenyl-4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-tetrabiphenyl. In addition, aryl groups may be optionally substituted.
Heterocyclyl or heterocycle-as used herein, non-aromatic cyclic groups are contemplated. The non-aromatic heterocyclic group includes a saturated heterocyclic group having 3 to 20 ring atoms and an unsaturated non-aromatic heterocyclic group having 3 to 20 ring atoms, at least one of which is selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom and boron atom, and preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms including at least one hetero atom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxacycloheptatrienyl, thietaneyl, azepanyl and tetrahydrosilol. In addition, the heterocyclic group may be optionally substituted.
Heteroaryl-as used herein, non-fused and fused heteroaromatic groups that may contain 1 to 5 heteroatoms, at least one of which is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms. Heteroaryl also refers to heteroaryl. The heteroaryl group may be a heteroaryl group having 3 to 30 carbon atoms, preferably a heteroaryl group having 3 to 20 carbon atoms, more preferably a heteroaryl group having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, furodipyridine, benzothiophene, thienodipyridine, benzoselenophene, selenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-aza-boron, 1, 3-aza-boron, 1-aza-boron-4-aza, boron-doped compounds, and the like. In addition, heteroaryl groups may be optionally substituted.
Alkoxy-as used herein, is represented by-O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or-O-heterocyclyl. Examples and preferred examples of the alkyl group, cycloalkyl group, heteroalkyl group and heterocyclic group are the same as described above. The alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. In addition, the alkoxy group may be optionally substituted.
Aryloxy-as used herein, is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. The aryloxy group may be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenoxy. In addition, the aryloxy group may be optionally substituted.
Aralkyl-as used herein, encompasses aryl-substituted alkyl. The aralkyl group may be an aralkyl group having 7 to 30 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 13 carbon atoms. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthyl-ethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthyl-ethyl, 2- β -naphthyl-ethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, cyano, o-cyanobenzyl, o-chlorobenzyl, 1-chlorophenyl and 1-isopropyl. Among the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl. In addition, aralkyl groups may be optionally substituted.
Alkyl-as used herein, alkyl-substituted silicon groups are contemplated. The silyl group may be a silyl group having 3 to 20 carbon atoms, preferably a silyl group having 3 to 10 carbon atoms. Examples of the alkyl silicon group include trimethyl silicon group, triethyl silicon group, methyldiethyl silicon group, ethyldimethyl silicon group, tripropyl silicon group, tributyl silicon group, triisopropyl silicon group, methyldiisopropyl silicon group, dimethylisopropyl silicon group, tri-t-butyl silicon group, triisobutyl silicon group, dimethyl-t-butyl silicon group, and methyldi-t-butyl silicon group. In addition, the alkyl silicon group may be optionally substituted.
Arylsilane-as used herein, encompasses at least one aryl-substituted silicon group. The arylsilane group may be an arylsilane group having 6 to 30 carbon atoms, preferably an arylsilane group having 8 to 20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenyl silyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyltert-butylsilyl. In addition, arylsilane groups may be optionally substituted.
Alkyl germanium group-as used herein, alkyl substituted germanium groups are contemplated. The alkylgermanium group may be an alkylgermanium group having 3 to 20 carbon atoms, preferably an alkylgermanium group having 3 to 10 carbon atoms. Examples of alkyl germanium groups include trimethyl germanium group, triethyl germanium group, methyl diethyl germanium group, ethyl dimethyl germanium group, tripropyl germanium group, tributyl germanium group, triisopropyl germanium group, methyl diisopropyl germanium group, dimethyl isopropyl germanium group, tri-t-butyl germanium group, triisobutyl germanium group, dimethyl-t-butyl germanium group, methyl-di-t-butyl germanium group. In addition, alkyl germanium groups may be optionally substituted.
Arylgermanium group-as used herein, encompasses at least one aryl or heteroaryl substituted germanium group. The arylgermanium group may be an arylgermanium group having 6-30 carbon atoms, preferably an arylgermanium group having 8 to 20 carbon atoms. Examples of aryl germanium groups include triphenylgermanium group, phenylbiphenyl germanium group, diphenylbiphenyl germanium group, phenyldiethyl germanium group, diphenylethyl germanium group, phenyldimethyl germanium group, diphenylmethyl germanium group, phenyldiisopropylgermanium group, diphenylisopropylgermanium group, diphenylbutylgermanium group, diphenylisobutylglycol group, and diphenyltert-butylgermanium group. In addition, the arylgermanium group may be optionally substituted.
The term "aza" in azadibenzofurans, azadibenzothiophenes and the like means that one or more C-H groups in the corresponding aromatic fragment are replaced by a nitrogen atom. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives will be readily apparent to those of ordinary skill in the art, and all such analogs are intended to be included in the terms described herein.
In the present disclosure, when any one of the terms from the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermanium, substituted arylgermanium, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, alkyl, cycloalkyl, heteroalkyl, heterocyclyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups, which may be substituted with one or more groups selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted cycloalkyl having 1 to 20 carbon atoms, unsubstituted alkenyl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, unsubstituted arylgermanium groups having 6 to 20 carbon atoms, unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphine groups, and combinations thereof.
It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered equivalent.
In the compounds mentioned in this disclosure, the hydrogen atoms may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred because of their enhanced efficiency and stability of the device.
In the compounds mentioned in this disclosure, polysubstituted means inclusive of disubstituted up to the maximum available substitution range. When a substituent in a compound mentioned in this disclosure means multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), it means that the substituent may be present at a plurality of available substitution positions on its linking structure, and the substituent present at each of the plurality of available substitution positions may be of the same structure or of different structures.
In the compounds mentioned in this disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless explicitly defined, for example, adjacent substituents can optionally be linked to form a ring. In the compounds mentioned in this disclosure, adjacent substituents can optionally be linked to form a ring, both in the case where adjacent substituents can be linked to form a ring and in the case where adjacent substituents are not linked to form a ring. Where adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic (including spiro, bridged, fused, etc.), as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to further distant carbon atoms. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.
The expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
the expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
the expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that the two substituents bound to further distant carbon atoms are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
Furthermore, the expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that, in the case where one of the adjacent two substituents represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:
according to one embodiment of the present invention, a compound having formula 1 is disclosed:
Wherein,
X1 to X4,X9 to X12 are, identically or differently, selected from CRx or N;
x5 to X8 are selected identically or differently from C, CRx or N;
Y1 to Y3,Y12 to Y15 are, identically or differently, selected from CRy or N for each occurrence;
Y4 to Y11 are, identically or differently, selected from C, CRy or N;
Z is selected from O, S or Se;
Rx,Ry is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
ar is selected from the group consisting of substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, and combinations thereof.
According to an embodiment of the present invention, wherein the compound has a structure represented by any one of formulas 1 to 8:
Wherein,
X1 to X5,X7 to X12 are selected identically or differently for each occurrence from CRx or N in formula 1-1, formula 1-2, formula 1-5 and formula 1-6, and X1 to X4,X6 to X12 are selected identically or differently for each occurrence from CRx or N in formula 1-3, formula 1-4, formula 1-7 and formula-8;
Y1 to Y15 are, identically or differently, selected from CRy or N for each occurrence;
Z is selected from O, S or Se;
Rx,Ry is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
ar is selected from the group consisting of substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, and combinations thereof.
According to an embodiment of the present invention, the compound has a structure represented by formula 1-1, formula 1-2, formula 1-3 or formula 1-5.
According to one embodiment of the invention, wherein said Rx,Ry is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein said Rx,Ry is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, phenyl, pyridyl, vinyl, naphthyl, biphenyl, phenanthryl, triphenylene, dibenzofuranyl, dibenzothienyl, t-butyl, trifluoromethyl, carbazolyl, 9-dimethylfluorenyl, and combinations thereof.
According to one embodiment of the present invention, wherein Ar is selected from the group consisting of substituted or unsubstituted aryl groups having from 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 18 carbon atoms, and combinations thereof.
According to one embodiment of the present invention, wherein Ar is selected from the group consisting of substituted or unsubstituted aryl groups having from 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 15 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein said Ar is selected identically or differently on each occurrence from the group consisting of: phenyl, pyridyl, naphthyl, biphenyl, phenanthryl, terphenyl, triphenylene, dibenzofuranyl, dibenzothienyl, benzoxazolyl, benzothiazolyl,A base, and combinations thereof.
According to an embodiment of the invention, wherein the compound is selected from the group consisting of compound a-1 to compound a-213, wherein the specific structure of the compound a-1 to compound a-213 is seen in claim 5.
According to one embodiment of the invention, the hydrogen energy in the structures of compounds a-1 to a-213 is partially or completely replaced by deuterium.
According to another embodiment of the present invention, there is also disclosed an organic electroluminescent device including:
An anode is provided with a cathode,
A cathode electrode, which is arranged on the surface of the cathode,
And an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound having the structure of formula 1, the specific structure of the compound being as described in any of the previous embodiments.
According to one embodiment of the present invention, in the organic electroluminescent device, the organic layer is a light emitting layer, and the compound is a host material.
According to an embodiment of the present invention, in the organic electroluminescent device, the organic layer is a light emitting layer, and the organic layer includes a second compound selected from structures represented by any one of formulas 2-1 to 2-3:
Wherein,
In formulas 2-1 to 2-3, ar31 to Ar35 are, identically or differently, selected for each occurrence from substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms;
L31 to L35 are, identically or differently, selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
x is selected identically or differently on each occurrence from O, S, CR21R22 or NR23;
R31 to R37, which are identical or different for each occurrence, represent mono-, poly-or unsubstituted;
R31 to R37,R21 to R23 are, identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents R31 to R37 can optionally be linked to form a ring.
Herein, "adjacent substituents R31 to R37 can optionally be linked to form a ring" is intended to mean that any one or more of these substituent groups can be linked to form a ring between adjacent substituents R31, between adjacent substituents R32, between adjacent substituents R33, between adjacent substituents R34, between adjacent substituents R35, between adjacent substituents R36, between adjacent substituents R37. Obviously, none of these adjacent groups of substituents may be linked to form a ring.
According to one embodiment of the invention, wherein each occurrence of said Ar31 to Ar35,R21 to R23 is identically or differently selected from the group consisting of: substituted or unsubstituted aryl groups having from 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 18 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein each occurrence of said Ar31 to Ar35,R21 to R23 is identically or differently selected from the group consisting of: phenyl, deuterated phenyl, methylphenyl, fluorophenyl, t-butylphenyl, trideutero methylphenyl, biphenyl, naphthyl, deuterated naphthyl, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, carbazolyl, pyridinyl, pyrimidinyl, 4-cyanophenyl, 3-cyanophenyl, triphenylene, and combinations thereof. According to an embodiment of the present invention, in the organic electroluminescent device, the organic layer is a light-emitting layer, and the second compound is a host material.
According to an embodiment of the present invention, in the organic electroluminescent device, wherein the second compound has a structure represented by any one of formulae 2 to 4 to 2 to 14:
in formulas 2-4 to 2-14,
Ar31,Ar32,Ar34 and Ar35 are, identically or differently, selected for each occurrence from substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms;
L31 to L35 are, identically or differently, selected from a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
x is selected identically or differently on each occurrence from O, S, CR21R22 or NR23;
R31 to R38, which are identical or different for each occurrence, represent mono-, poly-or unsubstituted;
R31 to R38,R21 to R23 are, identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents R31 to R38 can optionally be linked to form a ring.
Herein, "adjacent substituents R31 to R38 can optionally be linked to form a ring" is intended to mean that any one or more of these substituent groups can be linked to form a ring between adjacent substituents R31, between adjacent substituents R32, between adjacent substituents R33, between adjacent substituents R34, between adjacent substituents R35, between adjacent substituents R36, between adjacent substituents R37, between adjacent substituents R38. Obviously, none of these adjacent groups of substituents may be linked to form a ring.
According to one embodiment of the invention, wherein said X is chosen, identically or differently, for each occurrence, from O, S or NR23.
According to one embodiment of the invention, wherein said X is chosen, identically or differently, for each occurrence, from NR23.
According to one embodiment of the invention, wherein said R31 to R38 are, identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, cyano, hydroxy, mercapto, substituted or unsubstituted alkyl having 1to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein said R31 to R38 are, identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, cyano, hydroxy, mercapto, methyl, tridentate methyl, vinyl, phenyl, biphenyl, naphthyl, 4-cyanophenyl, dibenzofuranyl, dibenzothienyl, triphenylene, carbazolyl, 9-phenylcarbazolyl, 9-dimethylfluorenyl, pyridinyl, phenylpyridinyl, and combinations thereof.
According to one embodiment of the invention, wherein the L31 to L35 are, identically or differently, selected from the group consisting of: single bond, substituted or unsubstituted arylene of 6 to 18 carbon atoms, substituted or unsubstituted heteroarylene of 3 to 18 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein the L31 to L35 are, identically or differently, selected from the group consisting of: single bonds, phenylene, naphthylene, biphenylene, terphenylene, triphenylene, pyridylene, thienylene, dibenzofuranylene, dibenzothienyl, and combinations thereof.
According to one embodiment of the invention, wherein each occurrence of said Ar31 to Ar35,R21 to R23 is identically or differently selected from the group consisting of: substituted or unsubstituted aryl groups having from 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 18 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein each occurrence of said Ar31 to Ar35,R21 to R23 is identically or differently selected from the group consisting of: phenyl, deuterated phenyl, methylphenyl, fluorophenyl, t-butylphenyl, trideutero methylphenyl, biphenyl, naphthyl, deuterated naphthyl, dibenzofuranyl, dibenzothienyl, 9-dimethylfluorenyl, carbazolyl, pyridinyl, pyrimidinyl, 4-cyanophenyl, 3-cyanophenyl, triphenylene, and combinations thereof.
According to one embodiment of the invention, wherein the second compound is selected from the group consisting of:
According to an embodiment of the present invention, in the production of a device, when a light-emitting layer is formed by co-evaporation of the compound of the present invention and the second host compound with a light-emitting material, the light-emitting layer may be formed by co-evaporation of the compound of the present invention and the second compound in separate evaporation sources, or the light-emitting layer may be formed by evaporation of a mixture of the compound of the present invention and the second compound mixed in advance in one evaporation source.
According to one embodiment of the invention, wherein in the organic electroluminescent device, the organic layer is a light emitting layer comprising at least one phosphorescent light emitting material.
According to one embodiment of the invention, wherein the phosphorescent material is a metal complex having the general formula M (La)m(Lb)n(Lc)q;
m is selected from metals with a relative atomic mass greater than 40;
La,Lb and Lc are a first ligand, a second ligand, and a third ligand, respectively, that coordinate to the M; la,Lb and Lc can optionally be linked to form a multidentate ligand;
La,Lb and Lc may be the same or different; m is 1,2 or 3; n is 0,1 or 2; q is 0,1 or 2; the sum of M, n, q is equal to the oxidation state of M; when m is 2 or more, the plurality of La may be the same or different; when n is 2, two Lb may be the same or different; when q is 2, two Lc may be the same or different;
La is selected identically or differently from the structures shown in formula 3 for each occurrence:
Wherein,
Ring D is selected from a 5 membered heteroaryl ring or a 6 membered heteroaryl ring;
Ring E is selected from a 5 membered unsaturated carbocycle, a benzene ring, a 5 membered heteroaromatic ring or a 6 membered heteroaromatic ring;
Ring D and ring E are fused via Ua and Ub;
Ua and Ub are, identically or differently, selected from C or N at each occurrence;
Rd and Re, which are identical or different for each occurrence, represent mono-substituted, polysubstituted or unsubstituted;
V1 to V4 are selected identically or differently from CRv or N at each occurrence;
Rd,Re and Rv are selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
Adjacent substituents Rd,Re and Rv can optionally be linked to form a ring;
Lb and Lc are, identically or differently, selected at each occurrence from any one of the following structures:
Wherein,
Ra,Rb and Rc, which are identical or different at each occurrence, represent monosubstituted, polysubstituted or unsubstituted;
Xb is selected identically or differently on each occurrence from the group consisting of: o, S, se, NRN1 and CRC1RC2;
Xc and Xd are selected identically or differently on each occurrence from the group consisting of: o, S, se and NRN2;
Ra,Rb,Rc,RN1,RN2,RC1 and RC2 are selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;
In the structure of the ligand Lb,Lc, adjacent substituents Ra,Rb,Rc,RN1,RN2,RC1 and RC2 can optionally be linked to form a ring.
Herein, adjacent substituents Rd,Re,Rv can optionally be linked to form a ring, intended to mean that when substituents Rd, Re, Rv are present, wherein any one or more of the adjacent groups of substituents, such as between adjacent substituents Rd, between adjacent substituents Re, between adjacent substituents Rv, between adjacent substituents Rd and Re, between adjacent substituents Rd and Rv, and between adjacent substituents Re and Rv, can be linked to form a ring. Obviously, when substituents Rd, Re and Rv are present, none of these groups of substituents may be linked to form a ring.
Herein, adjacent substituents Ra,Rb,Rc,RN1,RN2,RC1 and RC2 can optionally be linked to form a ring, intended to mean groups of substituents wherein adjacent substituents are, for example, between two substituents Ra, between two substituents Rb, between two substituents Rc, between substituents Ra and Rb, between substituents Ra and Rc, between substituents Rb and Rc, between substituents Ra and RN1, between substituents Rb and RN1, between substituents Ra and RC1, between substituents Ra and RC2, between substituents Rb and RC1, between substituents Rb and RC2, between substituents Ra and RN2, between substituents Rb and RN2, and between RC1 and RC2, any one or more of these substituent groups may be linked to form a ring. For example, the number of the cells to be processed,Optionally, adjacent substituents Ra,Rb can be joined to form a ring, which can form one or more of the following structures including, but not limited to: /(I)
Wherein W is selected from O, S, se, NRw or CRwRw; wherein the definition of Rw,Ra',Rb' is the same as Ra. Obviously, these substituents may not all be linked to form a ring.
According to one embodiment of the invention, wherein in formula 3, two Re are linked in a ring.
According to one embodiment of the invention, wherein in formula 3, two Re are linked to form a 5-membered unsaturated carbocycle, a 5-membered heteroaromatic ring or a 6-membered aromatic ring.
According to one embodiment of the invention, wherein in formula 3, ring D is a 6 membered heteroaryl ring and ring E is a benzene ring or a 6 membered heteroaryl ring.
According to one embodiment of the invention, wherein in formula 3, ring D is a 6 membered heteroaryl ring and ring E is a 5 membered heteroaryl ring or a 5 membered unsaturated carbocycle.
According to one embodiment of the invention, wherein in formula 3, ring D is a 6 membered heteroaryl ring, ring E is a benzene ring or a 6 membered heteroaryl ring, and two Re are linked into a 6 membered aryl ring or a 6 membered heteroaryl ring.
According to one embodiment of the invention, wherein in formula 3, ring D is a 6 membered heteroaryl ring, ring E is a5 membered heteroaryl ring or a5 membered unsaturated carbocycle, and two Re are linked to form a 6 membered aryl ring or a 6 membered heteroaryl ring.
According to one embodiment of the invention, wherein in formula 3, at least one or two adjacent groups of substituents in Rd,Re,Rv are linked to form a ring. For example, two substituents Rd are linked to form a ring, or two substituents Re are linked to form a ring, or two substituents Rv are linked to form a ring, or a substituent Rd is linked to a substituent Re, or a substituent Rd is linked to a substituent Rv, or a substituent Re is linked to a substituent Rv to form a ring, or two substituents Rd are linked to form a ring while two substituents Re are linked to form a ring, or two substituents Rd are linked together to form a ring while two substituents Rv are linked together to form a ring, or two substituents Re are linked together to form a ring while two substituents Rv are linked together to form a ring, substituent Re is linked together with substituent Rv to form a ring while 2 substituents Rv are linked together to form a ring, or substituent Rd is linked together with substituent Rv to form a ring while 2 substituents Rv are linked together to form a ring; similar situation exists when more groups of adjacent substituents in Rd、Re、Rv are linked to form a ring.
According to one embodiment of the present invention, in the organic electroluminescent device, wherein the phosphorescent light emitting material is a metal complex having the general formula of M (La)m(Lb)n;
m is selected from metals with a relative atomic mass greater than 40;
la,Lb is a first ligand and a second ligand, respectively, that coordinate to the M; la,Lb can optionally be linked to form a multidentate ligand;
m is 1, 2 or 3; n is 0, 1 or 2; the sum of M and n is equal to the oxidation state of M; when m is 2 or more, the plurality of La may be the same or different; when n is 2, two Lb may be the same or different;
La is selected identically or differently from the structures shown in formula 3 for each occurrence:
Wherein,
Ring D is selected from a 5 membered heteroaryl ring or a 6 membered heteroaryl ring;
Ring E is selected from a 5 membered unsaturated carbocycle, a benzene ring, a 5 membered heteroaromatic ring or a 6 membered heteroaromatic ring;
Ring D and ring E are fused via Ua and Ub;
Ua and Ub are, identically or differently, selected from C or N at each occurrence;
Rd and Re, which are identical or different for each occurrence, represent mono-substituted, polysubstituted or unsubstituted;
V1 to V4 are selected identically or differently from CRv or N at each occurrence;
Rd,Re and Rv are selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
Adjacent substituents Rd,Re and Rv can optionally be linked to form a ring;
Wherein the ligand Lb is selected identically or differently on each occurrence from the following structures:
Wherein R1 to R7 are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 ring carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted germanium having 6 to 20 carbon atoms, substituted or unsubstituted carbonyl having 0 carbon atoms, cyano, sulfonyl, cyano, carbonyl, sulfonyl, cyano, or the like.
According to one embodiment of the invention, in the organic electroluminescent device, the ligand Lb is selected identically or differently for each occurrence from the following structures:
Wherein at least one of R1 to R3 is selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, or combinations thereof; and/or at least one of R4 to R6 is selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, or combinations thereof.
According to one embodiment of the invention, in the organic electroluminescent device, the ligand Lb is selected identically or differently for each occurrence from the following structures:
Wherein at least two of R1 to R3 are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, or combinations thereof; and/or at least two of R4 to R6 are, identically or differently, selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, or combinations thereof.
According to one embodiment of the invention, in the organic electroluminescent device, the ligand Lb is selected identically or differently for each occurrence from the following structures:
Wherein at least two of R1 to R3 are, identically or differently, selected from the group consisting of substituted or unsubstituted alkyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 2 to 20 carbon atoms, or combinations thereof; and/or at least two of R4 to R6 are, identically or differently, selected from substituted or unsubstituted alkyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having from 2 to 20 carbon atoms, or combinations thereof.
According to one embodiment of the present invention, in the organic electroluminescent device, the phosphorescent light emitting material is an Ir complex, a Pt complex or an Os complex.
According to one embodiment of the present invention, in the organic electroluminescent device, the phosphorescent light emitting material is an Ir complex and has a structure shown in either Ir(La)(Lb)(Lc)、Ir(La)2(Lb)、Ir(La)(Lb)2、Ir(La)2(Lc) or Ir (La)(Lc)2).
According to one embodiment of the present invention, wherein La has a structure as shown in formula 3 and comprises at least one structural unit selected from the group consisting of a 6-membered and 6-membered aromatic ring, a 6-membered and 6-membered heteroaromatic ring, a 6-membered and 5-membered aromatic ring and a 6-membered and 5-membered heteroaromatic ring.
According to an embodiment of the present invention, in the organic electroluminescent device, La has a structure as shown in formula 3 and includes at least one structural unit selected from the group consisting of naphthalene, phenanthrene, quinoline, isoquinoline and azaphenanthrene.
According to one embodiment of the invention, in the organic electroluminescent device, the phosphorescent light emitting material is an Ir complex and comprises a ligand La, the La being, for each occurrence, identically or differently any one selected from the group consisting of the following structures:
According to one embodiment of the invention, wherein in the organic electroluminescent device the phosphorescent light emitting material is an Ir complex and comprises a ligand Lb, the Lb is, for each occurrence, identically or differently, selected from any one of the group consisting of the following structures:
According to an embodiment of the present invention, in the organic electroluminescent device, the phosphorescent light emitting material is selected from the group consisting of:
According to another embodiment of the present invention, there is also disclosed a compound composition comprising a compound having a structure represented by formula 1, the specific structure of the compound being as shown in any one of the preceding embodiments.
According to one embodiment of the invention, wherein the compound composition comprises a second compound as described in any of the previous embodiments.
According to another embodiment of the present invention, an electronic device is also disclosed, which includes an organic electroluminescent device, and the specific structure of the organic electroluminescent device is as shown in any one of the foregoing embodiments.
Combined with other materials
The materials described herein for specific layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application 2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
Materials described herein as useful for specific layers in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, the compounds disclosed herein may be used in combination with a variety of light-emitting dopants, hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. 2015/0349273A1, paragraphs 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
In the examples of material synthesis, all reactions were carried out under nitrogen protection, unless otherwise indicated. All reaction solvents were anhydrous and used as received from commercial sources. The synthetic products were subjected to structural confirmation and characterization testing using one or more equipment conventional in the art (including, but not limited to, bruker's nuclear magnetic resonance apparatus, shimadzu's liquid chromatograph, liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, shanghai's optical technique fluorescence spectrophotometer, wuhan Koste's electrochemical workstation, anhui Bei Yi g sublimator, etc.), in a manner well known to those skilled in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, the evaporator manufactured by Angstrom Engineering, the optical test system manufactured by Frieda, st. O. F. And the lifetime test system, ellipsometer manufactured by Beijing, etc.), in a manner well known to those skilled in the art. Since those skilled in the art are aware of the relevant contents of the device usage and the testing method, and can obtain the intrinsic data of the sample certainly and uninfluenced, the relevant contents are not further described in this patent.
Material synthesis examples:
The preparation method of the compound of the present invention is not limited, and is typically, but not limited to, exemplified by the following compounds, the synthetic routes and preparation methods thereof are as follows:
synthesis example 1: synthesis of Compound A-1
Step 1: synthesis of intermediate 1
2, 6-Dibromonaphthalene (10 g,35 mmol), dibenzofuran-1-boronic acid (7.5 g,35 mmol), tetrakis (triphenylphosphine) palladium (0.4 g,0.35 mmol), potassium carbonate (14.5 g,105 mmol), tetrahydrofuran (120 mL), and water (60 mL) were added to a three-necked flask under nitrogen atmosphere, and reacted at 70℃for 16h. After the reaction was completed, cooled to room temperature, extracted with dichloromethane, the organic phase was washed with water, concentrated to remove the solvent, and the crude product was purified by column chromatography (PE/dcm=9:1) to give intermediate 1 (6.2 g, yield: 48%) as a white solid.
Step 2: synthesis of intermediate 3
Intermediate 1 (6.2 g,16.7 mmol), intermediate 2 (6.4 g,25 mmol), pd (dppf) Cl2 (1.2 g,1.6 mmol), potassium acetate (4.9 g,50 mmol) and toluene (80 ml) were added to a three-necked flask under nitrogen and reacted at 100℃for 16h. After the reaction was completed, cooled to room temperature, filtered to obtain a liquid, extracted with dichloromethane, the organic phase was washed with water, and the solvent was concentrated to remove the solvent, and the crude product was purified by column chromatography using PE/dcm=2/1 to obtain intermediate 3 (6.5 g, yield: 92%) as a white solid.
Step 3: synthesis of Compound A-1
Intermediate 3 (3 g,7.1 mmol), intermediate 4 (2.8 g,7.1 mmol), tetrakis (triphenylphosphine) palladium (823mg, 0.7 mmol), potassium carbonate (2.9 g,21.0 mmol), toluene (120 mL), ethanol (30 mL), water (30 mL) were added to a three-necked flask under nitrogen atmosphere and reacted at 100℃for 16h. After the completion of the reaction, the reaction mixture was cooled to room temperature, a large amount of solid was precipitated, and the solid was obtained by filtration, and after washing with water and ethanol three times, the crude product was recrystallized from toluene to obtain a white solid compound A-1 (2.5 g, yield: 54%). The product was identified as the target product and had a molecular weight of 651.2.
Those skilled in the art will recognize that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other compound structures of the present invention.
Device embodiment
First, a glass substrate having a 120nm thick Indium Tin Oxide (ITO) anode was cleaned, and then treated with UV ozone and oxygen plasma. After the treatment, the substrate was baked in a glove box filled with nitrogen gas to remove moisture, and then mounted on a substrate holder and loaded into a vacuum chamber. The organic layer specified below was prepared under a vacuum of about 10-8 TorrIs evaporated on the ITO anode in sequence by thermal vacuum. Co-evaporation of Compound HT and Compound HI as Hole Injection Layer (HIL) with thicknessThe compound HT is used as a Hole Transport Layer (HTL) with a thicknessCompound EB is used as Electron Blocking Layer (EBL) with a thicknessThen co-evaporating the compound A-1 of the present invention as a first host and the compound H-137 as a second host and the compound RD as a dopant to be used as an emitting layer (EML) with a thicknessUsing Compound HB as a Hole Blocking Layer (HBL), thickness isOn the hole blocking layer, the compound ET and 8-hydroxyquinoline-lithium (Liq) are co-evaporated to form an Electron Transport Layer (ETL) with the thickness ofFinally, vapor depositionThickness of 8-hydroxyquinoline-lithium (Liq) as Electron Injection Layer (EIL), and evaporationIs used as a cathode. The device was then transferred back to the glove box and packaged with a glass lid to complete the device.
Device comparative example 1
The embodiment of device comparative example 1 is the same as device example 1 except that compound B is used as the first host in place of the inventive compound a-1 in the light emitting layer (EML).
Device comparative example 2
The embodiment of device comparative example 2 is the same as device example 1 except that compound C is used as the first host in place of the inventive compound a-1 in the light emitting layer (EML).
The detailed device layer structure and thickness are shown in the following table. Wherein more than one layer of the material used is doped with different compounds in the weight proportions described.
Table 1 partial device structures of device examples and comparative examples
The material structure used in the device is as follows:
The maximum emission wavelength (. Lamda.max), voltage (voltage), power Efficiency (PE) of the device examples and device comparative examples measured at a constant current of 15mA/cm2 are shown in Table 2.
Table 2 device data
| Device ID | λmax(nm) | Voltage[V] | PE(lm/W) |
| Example 1 | 619 | 3.85 | 21.4 |
| Comparative example 1 | 620 | 4.02 | 20.2 |
| Comparative example 2 | 618 | 3.89 | 20.4 |
Discussion:
As can be seen from the data in table 2, the maximum emission wavelengths of the examples and comparative examples are substantially identical. In terms of power efficiency, the power efficiency of comparative example 1 and comparative example 2 has reached very high levels of 20.2lm/W and 20.4lm/W, respectively, but it is difficult and expensive that the compound of the present invention further improves the power efficiency of example 1 by 5.9% and 4.9% respectively. In terms of operating voltage, the example 1 voltage was also reduced by 0.17V and 0.04V, respectively.
The above data indicate that the compounds of formula 1 according to the present invention, wherein the triazine group is linked to the (aza) naphthyl- (aza) dibenzofuran (dibenzothiophene, dibenzoselenophene) group and to the (aza) phenyl- (aza) naphthyl group at specific positions, respectively, exhibit more excellent properties. From the above results, it can be seen that the compound of the present invention can improve the efficiency of the device and reduce the voltage of the device, and proves the unique advantages of the compound of the present invention, thus having wide commercial development prospect and application value.
It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. Thus, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific and preferred embodiments described herein. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. It is to be understood that the various theories as to why the present invention works are not intended to be limiting.