CN114591372B

CN114591372B - Metal complex and application thereof

Info

Publication number: CN114591372B
Application number: CN202210186319.2A
Authority: CN
Inventors: 曹建华; 冯静; 郭文龙; 边坤; 唐怡杰; 邸庆童; 刘赛赛
Original assignee: Shanghai 800 Million Spacetime Advanced Material Co ltd
Current assignee: Shanghai 800 Million Spacetime Advanced Material Co ltd
Priority date: 2022-02-28
Filing date: 2022-02-28
Publication date: 2024-01-12
Anticipated expiration: 2042-02-28
Also published as: CN114591372A

Abstract

The invention relates to the technical field of organic electroluminescent display, in particular to a metal complex and application thereof. The metal complex is a novel carbazole, carboline or azacarbazole ligand, can be used as an electrophosphorescent luminescent material, is red in electroluminescence, high in luminous efficiency, good in thermal stability, easy to prepare and sublimate and purify, and has a very wide market prospect.

Description

Metal complex and application thereof

Technical Field

The invention relates to the technical field of organic electroluminescent display, in particular to a metal complex and application thereof.

Background

Organic Light Emitting Diodes (OLED) utilize organic thin films that emit light when a voltage is applied across the positive and negative electrodes of the device. OLEDs are becoming a technology in flat panel displays, lighting and backlight applications, which are becoming more and more attractive.

One application of phosphorescent emissive molecules is in full color displays, where industry standards for such displays require pixels adapted to emit specific colors. In particular, these standards require saturated red, green, and blue pixels, and the CIE coordinates, which are well known in the art, can be used to measure color.

An example of a red emitting molecule is di (1-phenylisoquinoline) iridium acetylacetonate, denoted Ir (piq) ₂ (acac) having the structure:

in this and the following formulae, the dative bond of metallic iridium to nitrogen is depicted as a straight line.

At present, the red phosphorescent material still has the problems of low luminous quantum efficiency and poor color purity. The main reason for this situation is that red light comes from the transition between energy levels with narrower energy gaps, while heavy metal complexes with narrow energy gaps have certain difficulty in ligand design, and secondly, the red light material system has stronger pi-pi bond interaction, and the ligands have strong charge transfer characteristics, so that more non-radiative relaxation channels exist in the narrow energy gaps, quenching of phosphors is enhanced, and quantum yield of the red light system is reduced. Therefore, the design and synthesis of metal complexes with excellent comprehensive performance will become an important subject for the research of organic electroluminescent materials.

The present invention has been made in view of the above-mentioned circumstances.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a metal complex and application thereof, and a luminescent material prepared by using the metal complex has good stability, and the metal complex is a red light phosphorescent material with excellent luminescent performance.

The first object of the present invention is to provide a metal complex, wherein the molecular formula of the metal complex is as follows: m (L) _A ) _x (L _C ) _y The method comprises the steps of carrying out a first treatment on the surface of the Wherein,

m is a metal atom having an atomic weight greater than 40;

x represents an integer 1, 2 or 3; y represents an integer 0 or 1; and x+y is equal to the oxidation valence state of the metal M;

L _A the method comprises the following steps:

wherein,

X ¹ 、X ² 、X ³ 、X ⁴ 、X ⁵ 、X ⁶ 、X ⁷ each independently represents CR ⁰ Or N;

y is selected from N, B, siR ¹ P or p=o;

at W ¹ 、W ² 、W ³ 、W ⁴ Any adjacent two groups of the formula (1) or (2) below,

g is selected from O, S, CR ² R ³ 、NR ⁴ 、SiR ² R ³ Or GeR ² R ³ The method comprises the steps of carrying out a first treatment on the surface of the Z are each identical or different and represent CR ⁵ Or N, and "≡" indicates L _A Corresponding adjacent groups W in (a) ¹ And W is ² 、W ² And W is ³ Or W ³ And W is ⁴ ；

R ⁰ 、R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ Each independently selected from one or more of a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, a cycloalkyl group, a heteroalkyl group, a heterocycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, an alkenyl group, a cycloalkenyl group, an isoalkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thio group, a sulfonyl group, a sulfinyl group, a phosphino group; any adjacent substituents are optionally joined or fused to form a multi-membered ring, preferably a five-membered ring or a six-membered ring;

L _C the method comprises the following steps:

wherein,

R ⁶ 、R ⁷ 、R ⁸ each independently selected from one or more of a hydrogen atom, a deuterium atom, a halogen atom, an alkanyl, a cycloalkyl, a heteroalkyl, an aralkyl, an alkoxy, an aryloxy, an amino, a silyl, an alkenyl, a cycloalkenyl, a heteroalkenyl, an alkynyl, an aryl, a heteroaryl; and R is ⁶ 、R ⁷ 、R ⁸ Optionally bonded or fused between adjacent groups of (a) to form a multi-membered ring, preferably a five-membered ring or a six-membered ring;

the dotted line indicates ligand L _A Or L _C Coordination or bonding to the metal M.

Preferably, the metal M is selected from Ir or Pt.

Preferably, the L _A One or more selected from the following structures:

wherein X is ¹ 、X ² 、X ³ 、X ⁴ 、X ⁵ 、X ⁶ 、X ⁷ Each independently represents CR ⁰ Or N;

y is selected from N, B, siR ¹ P or p=o; g is selected from O, S, CR ² R ³ 、NR ⁴ 、SiR ² R ³ Or GeR ² R ³ ；

R ⁰ 、R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ Each independently selected from one or more of a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, a cycloalkyl group, a heteroalkyl group, a heterocycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, an alkenyl group, a cycloalkenyl group, an isoalkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thio group, a sulfonyl group, a sulfinyl group, a phosphino group; any adjacent substituents are optionally joined or fused into a multi-membered ring, preferably a five-membered ring or a six-membered ring.

Preferably, the L _A Selected from the group consisting of the following structural formulas:

wherein T is ¹ Selected from single bonds, O, S, C (CH) ₃ ) ₂ 、NR ⁴ Or Si (CH) ₃ ) ₂ ；

G、R ⁰ 、R ⁴ 、R ⁵ The meaning of (c) is as defined above.

Preferably, X ¹ 、X ² 、X ³ 、X ⁴ 、X ⁵ 、X ⁶ 、X ⁷ Each independently represents CR ⁰ Or N; y is selected from N or B; g is selected from O, S, CR ² R ³ Or NR (NR) ⁴ ；

R ⁰ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, R ^A1 -R ^A55 、R ^B1 -R ^B45 、R ^C1 -R ^C295 A group of groups; wherein,

R ^A1 -R ^A55 the structural formula is as follows:

R ^B1 -R ^B45 the structural formula is as follows:

R ^C1 -R ^C295 the structural formula is as follows:

/>

preferably, the L _A One selected from the formula LA 1-formula LA225, the specific structure of formula LA 1-formula LA225 is shown below:

/>

preferably, lc is selected from one of the formulas Lc 1-Lc 40, and the specific structure of the formulas Lc 1-Lc 40 is as follows:

preferably, the metal complex has the formula Ir (LAi) ₃ 、Ir(LAi) ₂ (LCw) or Pt (LAi) (LCw); wherein i is an integer of 1 to 225, and w is an integer of 1 to 40;

preferably, the metal complex has the formula Ir (LAi) ₃ Or Ir (LAi) ₂ (LCw)。

"halo", "halogen atom" or "halide" in the sense of the present invention include fluorine, bromine and iodine.

Alkyl in the sense of the present invention embraces both straight-chain and branched alkyl groups, preferred alkyl groups being those containing from 1 to 40 carbon atoms and in which the hydrogen atom or-CH is alone ₂ -alkyl groups, the groups of which may also be substituted, mainly include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.

Alkoxy is preferably an alkoxy group having 1 to 40 carbon atoms, which is taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octoxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2, 2-trifluoroethoxy.

Heteroalkyl is preferably an alkyl radical having from 1 to 40 carbon atoms, meaning in which the hydrogen atom or-CH is alone ₂ Groups which may be substituted by oxygen, sulfur, halogen atoms are considered to mean alkoxy, alkylthio, fluoroalkoxy, fluoroalkylthio, in particular methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, trifluoromethylthio, trifluoromethoxy, pentafluoroethoxy, pentafluoroethylthio, 2-trifluoroethoxy, 2-trifluoroethylthio, ethyleneoxy, ethylenethio, propyleneoxy, propylenethio, butylenethio, butyleneoxy, pentenyloxy, pentenylthio, cyclopentenyloxy, cyclopentenylthio, hexenyloxy, hexenylthio, cyclohexene thio, acetylenyloxy, acetylenylthio, propynyloxy, butynylthio, pentynyloxy, pentynylthio, hexyloxy, hexylynylthio.

In general, cycloalkyl, cycloalkenyl groups according to the invention may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, wherein one or more-CH ₂ -the groups may be replaced by alkyl or alkoxy groups as described above; in addition, one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups.

Alkynyl groups in the sense of the present invention include straight-chain and branched alkynyl groups, preferably alkynyl groups are alkynyl groups containing 2 to 40 carbon atoms.

Alkenyl groups in the sense of the present invention include straight chain and branched alkenyl groups, preferably alkenyl groups are alkenyl groups containing 2 to 40 carbon atoms.

"aralkyl" or "arylalkyl" in the sense of the present invention is used interchangeably and includes alkyl groups having aromatic groups as substituents, in addition, aralkyl groups may be optionally substituted.

Aryl or aromatic groups in the sense of the present invention contain 5 to 60 carbon atoms, heteroaryl groups in the sense of the present invention contain 2 to 60 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5; the heteroatom is preferably selected from N, O or S. Aryl or heteroaryl groups herein encompass both monocyclic groups and polycyclic systems. The polycyclic ring may have two or more rings shared by two adjacent rings or referred to as "fused" wherein at least one of the rings is aromatic, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl.

Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclyl, aryl, and heteroaryl may be optionally substituted with one or more substituents selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof.

As described herein, "substituted" means that a substituent other than hydrogen is bonded to a relevant position, such as carbon. Thus, for example, at R ⁰ When monosubstituted, one R ⁰ Must not be hydrogen. Similarly, at R ⁰ When disubstituted, then two R ⁰ Must not be hydrogen. Similarly, at R ⁰ When not substituted, R ⁰ Hydrogen for all available sites.

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 as if it were a fragment, e.g., phenyl, phenylene, naphthyl, dibenzofuranyl, or as if it were an entire molecule. These different ways of naming substituents or linked fragments are considered equivalent.

The second object of the invention is to provide the application of the metal complex in preparing an organic electroluminescent element or the application in preparing an organic electroluminescent material.

A third object of the present invention is to provide an organic electroluminescent element comprising a substrate, an anode, a cathode, a capping layer, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex described above.

In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises at least one selected from the group consisting of the following chemical groups: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5, 9-dioxa-13 b-boronaphtho [3,2,1-de ]]Anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza- (5, 9-diaza-13 b-boronaphtho [3,2, 1-de)]Anthracene), wherein any substituent in the host group is a non-fused substituent independently selected from the group consisting of: c (C) _n H _2n+1 、OC _n H _2n+1 、OAr ¹ 、N(C _n H _2n+1 ) ₂ 、NAr ¹ Ar ² 、CH＝CH-C _n H _2n+1 、C≡CC _n H _2n+1 、Ar ¹ 、Ar ¹ -Ar ² 、C _n H _2n -Ar ¹ Or no substituent, wherein n is an integer from 1 to 10; and wherein Ar is ¹ With Ar ² Independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

The host material contained in the organic layer may be, for example, a host material selected from the group consisting of:

and combinations thereof.

In some embodiments, the organic layer may further comprise a host and a dopant, wherein the dopant comprises the metal complexes disclosed herein.

In some embodiments, the metal complex as described herein may be a sensitizer; wherein the device may further comprise a recipient; and wherein the receptor may be selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

In yet another aspect, the OLEDs disclosed herein can further comprise an emissive region comprising a compound as disclosed in the above compound section of the disclosure.

In general, an OLED includes at least one organic layer disposed between and electrically connected to an anode and a cathode. Fig. 1 shows a schematic diagram of an organic electroluminescent device 100. The illustrations are not necessarily drawn to scale. The organic electroluminescent device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 may be fabricated by sequentially depositing the layers described.

Fig. 2 shows a schematic diagram of an inverted organic electroluminescent device 200. The organic electroluminescent device 200 includes a substrate 201, a cathode 202, a light emitting layer 203, a hole transporting layer 204, and an anode 205. The organic electroluminescent device 200 may be prepared by sequentially depositing the described layers. Because the most common OLED device has a cathode disposed on an anode, and the organic electroluminescent device 200 has a cathode 202 disposed under an anode 205, the organic electroluminescent device 200 may be referred to as an "inverted" organic light emitting device. In the corresponding layers of the organic electroluminescent device 200, materials similar to those described with respect to the organic electroluminescent device 100 may be used. Fig. 2 provides one example of how some layers may be omitted from the structure of the organic electroluminescent device 100.

The simple layered structure illustrated in fig. 1 and 2 is provided as a non-limiting example, and it should be understood that embodiments of the present invention may be used in conjunction with a wide variety of other structures. The particular materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be implemented by combining the various layers described in different ways based on design, performance, and cost factors, or several layers may be omitted entirely. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it will be understood that combinations of materials may be used, such as mixtures of host and dopant, or more generally, mixtures. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in the organic electroluminescent device 200, the hole transport layer 204 transports holes and injects holes into the light emitting layer 203, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an organic layer disposed between a cathode and an anode. This organic layer may comprise a single layer or may further comprise multiple layers of different organic materials as described in fig. 1 and 2.

Structures and materials not specifically described, such as PLEDs comprising polymeric materials, may also be used. As another example, an OLED with a single organic layer or multiple stacks may be used. The OLED structure may deviate from the simple layered structure illustrated in fig. 1 and 2. For example, the substrate may include an angled reflective surface to improve optical coupling.

Any of the layers of the various embodiments may be deposited by any suitable method unless otherwise specified. For organic layers, preferred methods include thermal evaporation, organic vapor deposition methods, or application of one or more layers by means of carrier gas sublimation, wherein at 10 ^-5 The material is applied at a pressure between mbar and 1 bar. A particular example of this method is the organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured. Other suitable deposition methodsIncluding for example, by spin coating, or by any desired printing method such as screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet printing, or nozzle printing. Soluble compounds the soluble compounds are obtained, for example, by suitable substitution of compounds of the general formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition.

Devices made in accordance with embodiments of the present invention may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damage due to exposure to harmful substances in the environment, including moisture, vapors and/or gases, etc. The barrier layer may be deposited on or under the substrate, electrode, or beside the substrate, electrode, or on any other portion of the device, including the edge. The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed by a variety of known chemical vapor deposition techniques and may comprise a composition having a single phase as well as a composition having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds or both. Preferably, the barrier layer comprises a mixture of polymeric and non-polymeric materials. To be considered as a mixture, the aforementioned polymeric and non-polymeric materials that make up the barrier layer should be deposited under the same conditions and/or at the same time. The weight ratio of polymeric material to non-polymeric material may be in the range of 95/5 to 5/95. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

In any of the above mentioned compounds used in each layer of the above mentioned OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any of the specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, and the like, can be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their non-deuterated, partially deuterated, and fully deuterated forms.

The materials and structures described herein may be applied in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. Further, such materials and structures may be used for organic devices such as organic transistors.

In some embodiments, the organic layer comprises an emissive layer, and the metal complex is an emissive material.

In some embodiments, the organic layer further comprises a host material.

In some embodiments, the organic layer further comprises at least two host materials.

Materials described herein as suitable for use in particular 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 emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one of ordinary skill in the art may readily review the literature to identify other materials that may be used in combination.

A fourth object of the present invention is to provide a consumer product comprising an OLED, wherein the OLED comprises an anode, a cathode and an organic layer disposed between the anode and the cathode, the organic layer comprising the metal complex described above.

In some embodiments, the consumer product may be one of the following products: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular telephones, tablet computers, tablet handsets, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays with a diagonal of less than 2 inches, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising a plurality of displays tiled together, theatre or gym screens, phototherapy devices, and billboards.

The preparation methods are generally known to those of ordinary skill in the art and they can be applied to the organic electroluminescent element comprising the metal complex according to the present invention without inventive effort.

According to one embodiment, novel ligands for metal complexes are disclosed. The inventors have found that the introduction of these ligands unexpectedly narrows the emission spectrum, lowers the sublimation temperature, and increases the luminous efficiency of the device.

The method for producing the organic electroluminescent element of the present invention is not limited to the following, and may be variously modified by those skilled in the art based on the common general knowledge in the art. The preparation method comprises the following steps:

and (3) cleaning: cleaning the glass substrate with ITO by using cleaning agents, deionized water, organic solvents and the like;

a step of forming a hole injection layer: forming a hole injection layer containing the metal complex of the present invention on the substrate by vapor deposition of a hole injection layer forming material containing the metal complex of the present invention on the anode layer by vacuum vapor deposition;

a step of forming a hole transport layer: forming a hole transport layer on the hole injection layer by vacuum evaporation;

a step of forming an organic light-emitting layer: forming an organic light-emitting layer containing the metal complex of the present invention on the hole transport layer by vacuum vapor deposition of an organic light-emitting layer forming material containing the material of the present invention on the hole transport layer;

a step of forming an electron transport layer: forming an electron transport layer containing the metal complex of the present invention on the organic light-emitting layer by vacuum evaporation of an electron transport layer forming material containing the metal complex of the present invention on the organic light-emitting layer;

a step of forming a cathode layer: a cathode forming material is vapor deposited, sputtered, or spin coated on the electron transport layer to form a cathode layer.

Compared with the prior art, the invention has the beneficial effects that:

the metal complex is a novel carbazole, carboline or azacarbazole ligand, can be used as an electrophosphorescent luminescent material, is red in electroluminescence, high in luminous efficiency, good in thermal stability, easy to prepare and sublimate and purify, and has a very wide market prospect.

Drawings

Fig. 1 is a schematic view of an organic electroluminescent device 100 according to the present invention;

in fig. 1, 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light emitting layer, 107 is a hole blocking layer, 108 is an electron transport layer, 109 is an electron injection layer, 110 is a cathode layer, and 111 is a CPL layer.

FIG. 2 is a schematic diagram of an inverted organic electroluminescent device 200 according to the present invention;

in fig. 2, 201 is a substrate, 202 is a cathode, 203 is a light-emitting layer, 204 is a hole-transporting layer, and 205 is an anode.

FIG. 3 is a perspective view of the compound of example 3.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.

In the invention, the preparation methods are all conventional methods unless otherwise specified. All materials used, unless otherwise indicated, are commercially available from the disclosure and percentages such as percentages by mass unless otherwise indicated. The novel series of metal complexes provided by the present invention, all reactions being carried out under well known suitable conditions, involve some simple organic preparation, for example the preparation of phenylboronic acid derivatives can be synthesised by skilled operating skills and are not described in detail in the present invention.

Example 1

Ir compound (LA 1) ₂ Preparation of (LC 16):

ir metal complex (LA 1) ₂ The preparation method of (LC 16) comprises the following steps:

the first step: preparation of Compound LA1

20.0mmol of carbazole is dissolved in 100mL of dry THF, the temperature is reduced to 0 ℃ under the protection of nitrogen, 24.0mmol of 65% sodium hydride is added in portions, stirring reaction is carried out for 30 minutes, 20.0mmol of 1-chloroisoquinoline is added dropwise into the solution dissolved in THF, stirring reaction is carried out for 12 hours at room temperature, 50mL of saturated ammonium chloride aqueous solution is added, an organic phase is separated, the aqueous phase is extracted by ethyl acetate, the organic phase is collected and dried, the filtrate is concentrated to dryness under reduced pressure, and the compound LA1 is obtained by separating and purifying by a silica gel column, yellow solid is obtained, and the yield is: 87%, GC-MS:294.12[ M ]] ⁺ ， ¹ HNMR(δ、CDCl ₃ )：8.29～8.27(1H,d)；8.15～8.12(3H,m)；7.97～7.95(3H,m)；7.65～7.61(1H,m)；7.56～7.52(1H,t)；7.48～7.44(2H,m)；7.35～7.31(2H,m)；7.25～7.23(1H,m)。

And a second step of: preparation of Compound Int-1

10.0mmol of compound LA1 and 5.0mmol of IrCl ₃ ·3H ₂ O is dispersed in 30mL of ethylene glycol diethyl ether and 10mL of water, under the protection of nitrogen, the temperature is raised, the reflux reaction is carried out for 24 hours, the mixture is cooled to room temperature, the mixture is filtered, a filter cake is washed with water and dried in vacuum, and the compound Int-1, red solid and the yield are obtained: 72%.

And a third step of: ir compound (LA 1) ₂ (LC 16) preparation

5.0mmol of compound Int-1 and 15.0mmol of LC16 and 25.0mmol of anhydrous potassium carbonate are dispersed in 40mL of acetonitrile and 40mL of chloroform, the mixture is heated and refluxed for 24 hours under the protection of nitrogen, cooled to room temperature, the reaction solution is poured into water and extracted with dichloromethane, the organic phase is dried, filtered, the filtrate is concentrated under reduced pressure to dryness, and the residue is separated and purified by a silica gel column to obtain the compound Ir (LA 1) ₂ (LC 16), red solid, yield: 52%, HRMS:1018.3782[ M ]] ⁺ ， ¹ HNMR(δ、CDCl ₃ )：9.38～9.37(2H,d)；8.56～8.54(2H,m)；8.46～8.43(2H,m)；8.15～8.09(4H,m)；8.05～7.96(6H,m)；7.76～7.62(8H,m)；7.43～7.39(2H,m)；5.13(1H,s)；1.68～1.51(4H,m)；1.29～1.05(10H,m)；0.67(6H,s)；0.63(6H,s)。

Example 2

Ir compound (LA 26) ₂ Preparation of (LC 4):

ir metal complex (LA 26) ₂ The preparation method of (LC 4) comprises the following steps:

the first step: preparation of Compound Int-2

5.0mmol of compound LA26 and 2.5mmol of IrCl ₃ ·3H ₂ Dispersing O in 24mL of ethylene glycol diethyl ether and 8mL of water, heating and refluxing for reaction for 24 hours under the protection of nitrogen, cooling to room temperature, filtering, washing a filter cake with water, and drying in vacuum to obtain a compound Int-2, a red solid and the yield: 59%.

And a second step of: ir compound (LA 26) ₂ (LC 4) preparation

5.0mmol of compound Int-2 and 15.0mmol of LC4 and 25.0mmol of anhydrous sodium carbonate are dispersed in 40ml of acetonitrile and 40ml of chloroform, the mixture is heated and refluxed for 24 hours under the protection of nitrogen, cooled to room temperature, the reaction solution is poured into water and extracted with dichloromethane, the organic phase is dried, filtered, the filtrate is concentrated under reduced pressure to dryness, and the residue is separated and purified by a silica gel column to obtain the compound Ir (LA 26) ₂ (LC 4), red solid, yield: 55%, HRMS:1046.4095[ M ]] ⁺ ， ¹ HNMR(δ、CDCl ₃ )：8.87～8.85(2H,m)；8.72～8.70(2H,d)；8.51～8.49(2H,m)；8.24～8.20(2H,m)；7.99～7.78(10H,m)；7.38～7.36(2H,d)；7.09～7.07(2H,d)；5.21(1H,s)；2.68～2.61(1H,m)；2.54(6H,s)；2.43(6H,s)；1.73～1.63(3H,m)；1.49～1.38(2H,m)；1.29～1.09(4H,m)；0.79(6H,m)；0.74(6H,m)。

Example 3

Referring to the preparation methods of example 1 and example 2, the compounds were prepared: ir (LA 1) ₂ (LC 4) A three-dimensional structure of the compound is shown in FIG. 3.

Example 4

Referring to the preparation methods of example 1 and example 2, the compounds were prepared: ir (LAi) ₂ (LCw), i is an integer of 1 to 225, and w is an integer of 1 to 40.

Example 5

Ir compound (LA 1) ₃ Is prepared from the following steps:

5.0mmol Ir (LA 1) prepared in example 4 ₂ (LC 1) and 20.0mmol of LA1 are dispersed in 50mL of glycerin, and the mixture is heated to 180 ℃ under the protection of nitrogen, stirred and reacted for 10 hours, cooled to room temperature, dropwise added into 100mL of 1N diluted hydrochloric acid, filtered, and the filter cake is washed with water and ethanol, and separated and purified by a silica gel column to obtain a compound Ir (LA 1) ₃ Red brown solid, yield: 44%, HRMS:1072.2847[ M ]] ⁺ ， ¹ HNMR(δ、CDCl ₃ )：9.25～9.23(1H,d)；8.58～8.56(1H,m)；8.36～8.34(1H,m)；8.26～8.24(1H,m)；8.15～8.10(2H,m)；7.96～7.91(2H,m)；7.85～7.83(1H,d)；7.75～7.71(2H,m)；7.64～7.59(1H,m)；7.51～7.49(1H,m)。

Example 6

Referring to the preparation of example 5, the compound was prepared: ir (LAi) ₃ I is an integer from 1 to 225.

Example 7

The embodiment provides an OLED device, as shown in fig. 1, where the preparation method of the OLED device includes the following steps:

(1) Ultrasonic treating the glass substrate coated with the ITO conductive layer in a cleaning agent for 30 minutes, flushing in deionized water, ultrasonic treating in an acetone/ethanol mixed solvent for 30 minutes, baking in a clean environment until the glass substrate is completely dried, irradiating for 10 minutes by an ultraviolet cleaning machine, and bombarding the surface by a low-energy cation beam;

(2) Placing the above ITO glass substrate in vacuum chamber, and vacuumizing to 1×10 ^-5 -9×10 ^-3 Pa, depositing metallic aluminum as an anode layer on the ITO film, the thickness of the deposited film beingContinuing to vapor deposit compound HI01 as hole injection layer, and vapor deposition film thickness is +.>Continuously evaporating HTM as hole transport layer on the hole injection layer film to obtain an evaporating film with a thickness of +.>

(3) Continuously evaporating a layer of compound RP as electron blocking layer on the hole transport layer to obtain an evaporating film with a thickness of

(4) The metal complex and TDC of the invention are continuously evaporated on the electron blocking layer to be used as the light-emitting layer of the device,wherein TDC is the main material and the metal complex of the invention is the doping material, the doping concentration of the metal complex of the invention is 3%, and the thickness of the evaporated film is

(5) And continuing to vapor-deposit a layer of LiQ and ET material on the light-emitting layer to serve as an electron transport layer of the device, wherein the mass ratio of LiQ to ET is 3:2, and the vapor-deposited film thickness isFinally, sequentially evaporating a magnesium/silver alloy layer on the electron transport layer to serve as a cathode layer of the device, wherein the mass ratio of the magnesium/silver alloy layer to the electron transport layer is 3:7, and the evaporated film thickness is +.>

Comparative example 1

A comparative device EL-1 was prepared in the same manner as in example 7, except that the metal complex doping material of the present invention was replaced with RD-A.

Comparative example 2

A comparative device EL-2 was prepared in the same manner as in example 7, except that the metal complex doping material of the present invention was replaced with RD-B.

The specific structures of the materials used in example 7 and comparative examples 1 and 2 are as follows:

test examples

Devices EL-3 through EL-20 were fabricated using the different metal complexes prepared according to the present invention as doping materials according to the method of example 7, the data were normalized with respect to EL-1,

the roll-off ratio is calculated according to the following equation:

roll-off ratio= [1- (at current density of 50 mA/cm) ² Efficiency/maximum luminous efficiency at the lower part]X 100%, knotThe results are shown in Table 1.

TABLE 1

The metal complex of the invention is used as the doping material of the luminous layer, the driving voltage of the devices EL-3 to EL-20 is low, the luminous efficiency is improved compared with the devices EL-1 and EL-2, and the initial current density is 50mA/cm ² Under the condition, the LT95% life attenuation of the device is obviously improved, and a more gentle attenuation curve is shown from the data of the roll-off ratio.

The present invention also carried out the above tests on the metal complexes prepared in the other examples, the results were substantially identical and, due to the limited space, they are not listed.

While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims

1. A metal complex, characterized in that the metal complex has the formula: ir (L) _A ) ₃ Or Ir (L) _A ) ₂ (L _C ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein,

L _A one selected from the formula LA 1-formula LA225, the specific structure of formula LA 1-formula LA225 is shown below:

lc is selected from one of the following specific structures:

2. an organic electroluminescent element comprising a substrate, an anode, a cathode, a capping layer, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex of claim 1.

3. A consumer product comprising an OLED, wherein the OLED comprises an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising the metal complex of claim 1.