Narrowband tetradentate platinum (II) complex guest phosphorescent material with terphenyl structure, electronic device, device and application thereof

Abstract

The invention belongs to the technical field of preparation of organic electroluminescent materials, and particularly relates to a narrow-band tetradentate platinum (II) complex guest phosphorescent material with a terphenyl structure, an electronic device, a device and application thereof. According to the invention, substituted aryl is introduced to the ortho-position of N-heterocyclic carbene substituted phenyl to increase steric hindrance, so that red shift or luminescence quenching caused by molecular aggregation can be avoided; the photophysical properties of the material can be regulated and controlled by regulating the peripheral substituted functional groups of the ligands, so that fine regulation and control of light-emitting colors are realized; the chemical stability and the thermal stability can be improved by deuteration on the periphery of the ring metal ligand, and an evaporation type OLED device is easy to prepare. The current efficiency and the service life of an organic light-emitting device manufactured by taking the complex as a light-emitting layer material are obviously improved, and the organic light-emitting device has a great application prospect in the fields of OLED display and illumination.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of organic electroluminescent materials, and particularly relates to a narrow-band tetradentate platinum(II) complex guest phosphorescent material with a terphenyl structure, an electronic device, a device and their applications. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technologies. Compared with the disadvantages of liquid crystal displays such as slow response speed, small viewing angle, requiring a backlight, high energy consumption, etc., OLEDs, as a self-luminous device, do not require a backlight and are energy-saving; and they have a low driving voltage, fast response speed, high resolution and contrast, wide viewing angle, and excellent low-temperature performance; OLED devices can be made thinner and can be made into a flexible structure. In addition, they also have the advantages of low production cost, simple production process, and can be produced on a large scale. Therefore, OLEDs have broad and huge application prospects in high-end electronic products and aerospace; with the gradual increase of investment, further in-depth research and development, and the upgrading and transformation of production equipment, OLEDs will have a very wide range of application scenarios and development prospects in the future.

[0003] The core of the development of OLEDs is the design and development of luminescent materials. In early OLED devices, the luminescent materials were mainly organic small molecule fluorescent materials. However, spin statistical quantum mechanics shows that in the case of electroluminescence, the generated singlet excitons and triplet excitons are 25% and 75% respectively. Since traditional fluorescent materials can only utilize the singlet excitons, their maximum theoretical internal quantum efficiency is only 25%, and the remaining 75% of the triplet excitons are lost through non-radiative transitions. Due to the strong spin-orbit coupling effect of heavy metal atoms, excitons can more easily undergo intersystem crossing (ISC) from the singlet state to the triplet state, so that OLED devices can make full use of all singlet and triplet excitons generated by electrical excitation, and the theoretical internal quantum efficiency of the luminescent materials can reach 100%.

[0004] In currently applied OLED devices, almost all the light-emitting layers use the host-guest light-emitting system mechanism, that is, a guest light-emitting material is doped in the host material. The energy level of the host material is generally greater than that of the guest light-emitting material, and the energy is transferred from the host material to the guest material to excite the guest material to emit light. Commonly used organic phosphorescent guest materials are generally heavy metal atoms such as iridium(III), platinum(II), Pd(II), etc. Currently, the applied heavy metal phosphorescent organic complex molecules are cyclometalated iridium(III) complex molecules, and the number is limited. Traditional Ir(III) complex phosphorescent materials based on bidentate and tridentate ligands have a relatively large metal-to-ligand charge transfer state ( 3 MLCT) component because the electrons and holes in their excited states are on different ligands, and it is difficult to achieve a local state ( 3The regulation of the composition of LE), whose emission spectrum is mostly a Gaussian broad peak, makes it difficult to achieve narrow-band luminescence, especially difficult to meet the requirements of solving OLEDs on the production line. In contrast, Pt(II)-based phosphorescent materials based on tetradentate ligands are easy to achieve 3 MLCT and 3 The regulation of the composition of the LE excited state enables the two to be well integrated to achieve efficient and narrow-band luminescence. Narrow-band luminescent material molecules have always been urgently needed materials for industrial applications in this field. In particular, the design and development of green phosphorescent material molecules with stability, high efficiency and narrow-band high color purity are recognized as extremely challenging problems in this field, and at the same time, they are also bottleneck problems restricting the development of the OLED field. However, there are still some technical difficulties in the development of platinum complex materials and devices at present. How to improve the chemical stability and thermal stability of the materials, avoid the red shift or luminescence quenching caused by molecular aggregation, and then improve the device operation life, etc. This problem is particularly important for narrow-band luminescent materials, which has a great impact on the efficiency and energy utilization rate of top-emitting devices for commercial applications. Therefore, it is urgent to develop new phosphorescent platinum(II) complexes. Summary of the Invention

[0005] The purpose of the present invention is to provide a narrow-band tetradentate platinum(II) complex guest phosphorescent material, electronic device, device and its application with a terphenyl structure. The present invention increases the steric hindrance by introducing a substituted aryl group at the ortho position of the N-heterocyclic carbene-substituted phenyl group, which can avoid the red shift or luminescence quenching caused by molecular aggregation; by adjusting the substituents on the periphery of the ligand, the photophysical properties of the material can be regulated to achieve fine regulation of the emission color; deuteration on the periphery of the cyclometalated ligand can improve the chemical stability and thermal stability, and is easy to prepare vapor-deposited OLED devices. The organic electroluminescent device fabricated with the complex of the present invention as the luminescent layer material has obvious improvements in current efficiency and life, and has great application prospects in the fields of OLED display and lighting.

[0006] The purpose of the present invention is achieved through the following technical solutions;

[0007] In a specific embodiment, the present invention provides a platinum(II) complex guest phosphorescent material having the structure shown in formula (I):

[0008]

[0009] In formula (I), R a , R b , R c , R d , R e , R f , R g , R h , R i each independently represents mono-substituted or multi-substituted; Ra -R i Each independently represents one or more of hydrogen, deuterium, -CN, C1-C30 alkyl, C1-C30 deuterated alkyl, C1-C30 haloalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, C1-C30 alkoxy, C1-C30 alkylsilyl, C6-C30 arylsilyl, and adjacent substituents can optionally be connected to form a ring.

[0010] Preferably, R a -R e Each independently is selected from one or more of hydrogen, deuterium, -CN, C1-C12 alkyl, C1-C12 deuterated alkyl, C1-C12 fluoroalkyl, C3-C12 cycloalkyl, C3-C6 azacycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C3-C30 heteroaryl, C1-C12 alkoxy, C1-C12 alkylsilyl, C6-C18 arylsilyl, and two or more adjacent substituents independently can form a saturated or unsaturated C3-C18-membered aromatic ring or C3-C18-membered heteroaromatic ring with the carbon atom to which they are commonly attached, and the aromatic ring or heteroaromatic ring can be substituted or unsubstituted.

[0011] More preferably, R a is selected from one or more of hydrogen, deuterium, F, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, CD3, CF3, adamantyl, methoxy, aryl, methyl-substituted aryl, isopropyl-substituted aryl, tert-butyl-substituted aryl, carbazolyl, N-heterocyclopentyl.

[0012] More preferably, R b -R e Each independently is selected from one or more of hydrogen, deuterium, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, CD3, CF3, N-heterocyclopentyl, adamantyl, trimethylsilyl, triarylsilyl, carbazolyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, spirofluorene, methoxy, substituted or unsubstituted aryl; when containing a substitution, the substitution is selected from one or more of deuterium, F, -CN, C1-C10 alkyl.

[0013] Preferably, R fSelected from hydrogen, deuterium, C1–C12 alkyl; R g 、R h 、R i are each independently selected from hydrogen, deuterium, F, -CN, C1–C12 alkyl, C1–C12 deuterated alkyl, C1–C12 fluoroalkyl, substituted or unsubstituted C3–C12 cycloalkyl, substituted or unsubstituted phenyl; when containing substitution, the substitution is selected from one or more of deuterium, F, -CN, C1-C10 alkyl.

[0014] More preferably, R f is selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; R g 、R h 、R i are each independently selected from hydrogen, deuterium, F, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, CD3, CF3, methyl-substituted or unsubstituted cyclopentyl, methyl-substituted or unsubstituted cyclohexyl, substituted or unsubstituted aryl; when containing substitution, the substitution is selected from one or more of deuterium, F, -CN, methyl, ethyl, isopropyl, tert-butyl.

[0015] Preferably, the hydrogen atoms in the platinum(II) complex of the structure shown in formula (I) can be partially or fully deuterated.

[0016] In many embodiments, the platinum(II) complex host phosphorescent material is selected from any one of the following chemical structures: where "D" represents deuterium and "OMe" represents methoxy:

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023] In many embodiments, the present invention also provides the use of the platinum(II) complex host phosphorescent material having the structure shown in formula (I) above in the preparation of electronic devices.

[0024] Further, the electronic device includes one or more of an organic electroluminescent device, an organic optoelectronic device, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light-emitting electrochemical cell, or an organic laser diode.

[0025] In many embodiments, the present invention provides an organic electroluminescent device, which includes: a cathode, an anode, and an organic functional layer therebetween, and the organic functional layer contains a platinum(II) complex guest phosphorescent material having the structure shown in formula (I) above.

[0026] Preferably, the organic functional layer contains a light-emitting layer, and the light-emitting layer contains a platinum(II) complex guest phosphorescent material having the structure shown in formula (I) above.

[0027] More preferably, the light-emitting layer further contains a fluorescent doping material; the fluorescent doping material is preferably a boron-containing organic molecular luminescent material, and more preferably a boron-containing compound.

[0028] In many embodiments, the present invention further provides an organic optoelectronic device, which includes: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; a second electrode on the organic light-emitting functional layer; wherein, the organic light-emitting functional layer contains a platinum(II) complex guest phosphorescent material having the structure shown in formula (I) above. For example, the platinum(II) complex can be included as a luminescent material in the organic light-emitting functional layer.

[0029] Further, the organic light-emitting functional layer further contains any one or more fluorescent doping materials, and the fluorescent doping material is preferably a boron-containing organic molecular luminescent material, and more preferably a boron-containing compound that can be phosphorescently sensitized.

[0030] In the present invention, for the organic optoelectronic device, an anode can be formed by sputtering coating, electron beam evaporation, vacuum evaporation or other methods to deposit a metal, a conductive oxide or their alloy on a substrate; a hole injection layer, a hole transport layer, a light-emitting layer, an air barrier layer and an electron transport layer are sequentially deposited on the surface of the prepared anode, and then a cathode is deposited. In addition to the above methods, an organic electroluminescent device can also be fabricated by depositing a cathode, an organic functional layer and an anode on a substrate in this order. The organic functional layer includes a light-emitting layer, and may also include a multi-layer structure such as a hole injection layer, a hole transport layer, a hole blocking layer and an electron transport layer. In the present invention, if the organic functional layer is prepared by using a polymer material according to solvent engineering (such as spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing or thermal-imaging, etc.) instead of the evaporation method, the number of device layers can be reduced.

[0031] The present invention also provides a composition, which contains a platinum(II) complex guest phosphorescent material having the structure shown in formula (I) above. Preferably, the composition further contains a fluorescent doping material, and the fluorescent doping material is preferably a boron-containing organic molecular luminescent material, and more preferably a boron-containing compound that can be phosphorescently sensitized.

[0032] The present invention also provides a preparation, which contains a platinum(II) complex guest phosphorescent material having the structure shown in formula (I) above and at least one solvent. The solvent is not particularly limited and can be those well-known to those skilled in the art.

[0033] The present invention also provides a display or lighting device, which contains one or more of the above-mentioned organic electroluminescent devices or organic optoelectronic devices.

[0034] The materials used in the organic electroluminescent device according to the present invention can be divided into top emission, bottom emission or double-sided emission.

[0035] The compounds of the organic electroluminescent device according to the embodiments of the present invention can be applied to electro-optic devices such as organic solar cells, lighting OLEDs, flexible OLEDs, organic photoreceptors, and organic thin-film transistors based on the principle similar to that of organic light-emitting devices.

[0036] Compared with the prior art, the beneficial effects of the present invention are:

[0037] (1) By introducing a substituted aryl group at the ortho position of the nitrogen heterocarbene-substituted phenyl to increase the steric hindrance, the red shift or luminescence quenching caused by molecular aggregation can be avoided;

[0038] (2) The optoelectronic properties of the material can be regulated by adjusting the substituents on the periphery of the ligand, enabling fine tuning of the emission color.

[0039] (3) Deuteration on the periphery of the cyclometalated ligand can improve the stability of C-H bonds, and thus endow the platinum(II) complex guest phosphorescent material shown in formula (I) with good chemical and thermal stability, making it easy to fabricate vapor-deposited OLED devices.

[0040] (4) When the phosphorescent material provided by the present invention is used as the emitting layer material to fabricate an organic electroluminescent device, more excellent performance improvement can be achieved; the energy transfer between the host and the guest becomes more efficient, resulting in significant improvements in both current efficiency and lifetime. At an initial brightness of 1000 cd / m 2 The estimated LT90 lifetime of the device based on the platinum(II) complex Pt3 emitter reaches 64,000 hours (n = 1.7), which is leading in the industry among green tetradentate platinum complexes, providing a better phosphorescent material solution for the commercial application of green-emitting guest materials in OLED full-color displays. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is the room-temperature emission spectrum of the platinum(II) complex Pt3 in dichloromethane and toluene solutions;

[0042] Figure 2 is the room-temperature emission spectrum of the platinum(II) complex Pt3 in solutions with different polarities;

[0043] Figure 3 is the CIE chromaticity coordinates of Device Example 1;

[0044] Figure 4 is the density functional theory calculation and natural orbital analysis diagrams of the frontier orbitals of the platinum(II) complex Pt3;

[0045] Figure 5 is the electroluminescence spectrum of Device Example 1;

[0046] Figure 6 is the operating lifetime diagram of Device Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0047] As used herein, the term "optional" or "optionally" means that the subsequent described event or circumstance may or may not occur, and the description includes both the case where the event or circumstance occurs and the case where it does not occur.

[0048] The term "substituted" as used in this invention is intended to include all permissible substituents of organic compounds. In broad aspects, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For suitable organic compounds, the permissible substituents can be one or more and can be the same or different. For the purposes of this invention, heteroatoms (such as nitrogen) can have hydrogen substituents and / or any permissible substituents of the organic compounds described herein, provided that the valency of the heteroatom is satisfied. This disclosure is not intended to be limiting in any way with respect to the permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" include the implicit proviso that such substitution is in accordance with the permissible valencies of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (such as by rearrangement, cyclization, elimination, etc.)). It is also contemplated that in certain aspects, unless explicitly stated to the contrary, individual substituents can further optionally be substituted (i.e., further substituted or unsubstituted).

[0049] In defining the various terms, R a -R i is used as a general symbol in this invention to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed in this invention, and when they are defined as certain substituents in one instance, they can be defined as some other substituents in other instances; R a -R i independently represents mono-substituted or multi-substituted, and the multi-substitution can be di-substituted, tri-substituted, tetra-substituted or up to the maximum number of substitutions.

[0050] The term "alkyl" as used in this invention is a saturated hydrocarbon group having 1 to 30 carbon atoms, which can be branched or unbranched. Preferred alkyl groups are those having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl can be cyclic or acyclic. The alkyl can be branched or unbranched. The alkyl can also be substituted or unsubstituted. For example, the alkyl can be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxy, nitro, silyl, sulfo-oxo or mercapto groups as described herein.

[0051] Throughout the specification, the term "alkyl" is generally used to refer to both unsubstituted alkyl and substituted alkyl; however, substituted alkyl is also specifically referred to in the present invention by identifying the specific substituents on the alkyl. For example, the term "haloalkyl" specifically refers to an alkyl substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "deuterated alkyl" specifically refers to an alkyl substituted with one or more deuterium atoms. The alkyl term "alkoxyalkyl" specifically refers to an alkyl substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl substituted with one or more amino groups, as described below, etc.

[0052] This practice is also used for other groups described in the present invention. That is, when terms such as "cycloalkyl" refer to both unsubstituted and substituted cycloalkyl moieties, the substituted moiety can be specifically identified in the present invention; for example, a specifically substituted cycloalkyl can be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy can be specifically referred to as, for example, "halogenated alkoxy", and a specific substituted alkenyl can be, for example, "enol", etc. Likewise, the practice of using a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" is not intended to imply that the general term does not simultaneously include the specific term.

[0053] The term "cycloalkyl" used in the present invention is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, adamantyl, etc. The term "heterocycloalkyl" is a class of cycloalkyl as defined above and is included in the meaning of the term "cycloalkyl", wherein at least one ring carbon atom is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocycloalkyl can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl can be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxy, nitro, silyl, sulfo-oxo, or mercapto as described in the present invention.

[0054] The term "aryl" as used in the present invention refers to any carbon-based aromatic group containing 6 to 60 carbon atoms. Preferred aryl groups are aromatic groups containing 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. The carbon-based aromatic groups include, but are not limited to, phenyl, naphthyl, phenylene, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group having at least one heteroatom within the ring introducing the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, silicon, and phosphorus. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azide, nitro, silyl, sulfo-oxo, or mercapto groups described in the present invention. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together by a fused ring structure, as in naphthalene, or two aryl groups joined by one or more carbon-carbon bonds, as in biphenyl.

[0055] In the compounds mentioned in the present invention, unless explicitly defined, for example, adjacent substituents can optionally be joined to form a ring, adjacent substituents in the compounds cannot be joined to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can optionally be joined to form a ring, which includes both the case where adjacent substituents can be joined to form a ring and the case where adjacent substituents are not joined to form a ring. When adjacent substituents can optionally be joined to form a ring, the formed ring can be a monocyclic or polycyclic ring (including spiro rings, bridged rings, fused rings, etc.), and an alicyclic, heteroalicyclic, aromatic, or heteroaromatic ring. The carbon atoms are preferably C3 - C30, more preferably C3 - C18. Even more preferably C3 - C6 in such a description. Adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further apart. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0056] The statement that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring. The statement 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. The statement 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 further removed from each other are linked to each other by a chemical bond to form a ring. In addition, the statement 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 two adjacent substituents represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring.

[0057] Compounds or complex complexes containing platinum are disclosed herein. The terms compound or complex are used interchangeably in the present invention. Additionally, the compounds disclosed herein have a neutral charge.

[0058] The compounds disclosed herein are suitable for a variety of optical and electro-optical devices, including but not limited to light absorption devices such as solar and photosensitive devices, organic light emitting diodes, light emitting devices or devices capable of compatible light absorption and emission, and as markers for biological applications.

[0059] As described above, the disclosed compounds are platinum complexes. Meanwhile, the compounds disclosed herein can be used as host materials for OLED applications, such as full-color displays.

[0060] The compounds disclosed herein can be used for various applications. As a luminescent material, the compound can be used in organic light emitting diodes (OLEDs), light emitting devices and displays, and other light emitting devices.

[0061] In addition, compared with traditional materials, the compounds in the present invention used in light emitting devices (such as OLEDs) can improve the luminescence efficiency and the operation time of the devices.

[0062] The compounds of the present invention can be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0063] The compounds disclosed in the embodiments of the present invention are suitable for a variety of optical and electro-optical devices, including but not limited to light absorption devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices or devices having both light absorption and light emission capabilities, and as markers for biological applications.

[0064] The compounds provided by the embodiments of the present invention can be used in a light-emitting device such as an OLED. The device includes at least one cathode, at least one anode, and at least one light-emitting layer, and at least one of the light-emitting layers includes a platinum(II) complex guest phosphorescent material having the structure shown in formula (I). Specifically, the light-emitting device may include an anode, a hole-transporting layer, a light-emitting layer, an electron-transporting layer, and a cathode sequentially deposited. Among them, the hole-transporting layer, the light-emitting layer, and the electron-transporting layer are all organic layers, and the anode and the cathode are electrically connected.

[0065] It should be noted that the above general description and the following detailed description are only exemplary and explanatory, and are not restrictive.

[0066] The present disclosure can be more easily understood by referring to the following specific embodiments and the examples included therein.

[0067] Before disclosing and describing the compounds, devices, and / or methods of the present invention, it should be understood that they are not limited to specific synthesis methods (otherwise specified), or specific reagents (otherwise specified), because this can of course vary. It should also be understood that the terms used in the present invention are only for the purpose of describing specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used in the practice or testing, exemplary methods and materials are described below.

[0068] Synthesis Examples

[0069] The following examples of compound synthesis, composition, device, or method are only to provide a general method to the industry field and are not used to limit the protection scope of the patent. For the data (quantity, temperature, etc.) mentioned in the patent, as much accuracy as possible is ensured, but there may still be some errors. Unless otherwise specified, weighing is done separately, the temperature is 25 °C, or room temperature, and the pressure is close to atmospheric pressure.

[0070] The following examples provide methods for preparing new compounds, but the preparation of such compounds is not limited to these methods. In this technical field, since the compounds protected in this patent are easy to modify and prepare, their preparation can adopt the methods listed below or other methods. The following examples are only for illustration and are not used to limit the protection scope of the patent. The temperature, catalyst, concentration, reactants, and reaction process can all be changed to select different conditions for preparing the compounds for different reactants.

[0071] Determined on an Agilent 6210TOF LC / MS type mass spectrometer; the HRMS spectrum was determined on an Agilent 6210TOF LC / MS type liquid chromatography-time-of-flight mass spectrometer; 11H NMR spectra were measured on a BRUKER-500 or BRUKER-400 nuclear magnetic resonance spectrometer.

[0072] Synthetic route

[0073] Example 1: Tetradentate cyclometalated platinum(II) complex Pt3

[0074] The synthetic route is as follows:

[0075]

[0076] Synthesis of intermediate 1-Br: To the reaction flask were successively added Cz-Br (1.2 equivalents), N-Br (1.0 equivalent), copper(I) iodide (0.1 equivalent), N-methylimidazole (0.2 equivalent) and lithium tert-butoxide (2.0 equivalents). Nitrogen was evacuated and replaced three times, and then toluene (250 mL) was added. The mixture was stirred at 130 °C for 35 h, filtered, and the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography with a eluent of petroleum ether:ethyl acetate = 30:1 to give 21 g of white solid 1-Br with a yield of 90%, MS: m / z 387.07 (M+H). + 。

[0077] Synthesis of intermediate DCz-Cl: To the reaction flask were successively added 1-Br (1.1 equivalents), Cz-Cl (1.0 equivalent), copper(I) iodide (0.2 equivalent), trans-cyclohexanediamine (0.4 equivalent) and potassium phosphate (2.0 equivalents). Nitrogen was evacuated and replaced three times, and then xylene (130 mL) was added. The mixture was stirred at 100 °C for 35 h, extracted three times with water / ethyl acetate, and the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography with a eluent of petroleum ether:ethyl acetate = 20:1 to give 17.40 g of white solid with a yield of 86%. 1H NMR (400 MHz, CDCl3) δ 1.40 (s, 9H), 7.26 (dd, J = 8.4, 2.0 Hz, 1H), 7.28–7.34 (m, 2H), 7.37–7.45 (m, 2H), 7.48 (m, 3H), 7.51–7.59 (td, J = 7.2, 1.2 Hz, 1H), 7.69 (d, J = 1.6 Hz, 1H), 7.84 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 2.0 Hz, 1H), 8.06 (d, J = 8.4 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.23 (d, J = 7.6 Hz, 1H), 8.34 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 5.6 Hz, 1H).

[0078]

[0079] Synthesis of Intermediate (2-1): Add DBr (50.00 g, 163.00 mmol, 1.0 equiv) and N,N-dimethylformamide (300 mL) into a three-necked flask equipped with a magnetic stir bar. After cooling to 0 °C in an ethanol bath, add sodium hydride (60%) (19.56 g, 489 mmol, 3.0 equiv). After stirring for 30 minutes, slowly add F-NO2 (29.91 g, 212.00 mmol, 1.0 equiv), and resume stirring at room temperature for 36 hours. Quench the reaction mixture with water, extract with ethyl acetate, and remove the solvent under reduced pressure. The crude product is separated and filtered through a silica gel chromatography column. The eluent is petroleum ether:ethyl acetate = 40:1, obtaining 34.40 g of a yellow solid with a yield of 49%. MS: m / z 425.96 (M+H) + .

[0080] Synthesis of Intermediate (2-2): Add 2-1 (34.40 g, 80.35 mmol, 1.0 equiv) and stannous chloride (60.90 g, 321.40 mmol, 4.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and replace with nitrogen three times. Under nitrogen protection, add ethanol (150 mL) and ethyl acetate (150 mL). After reacting in an 80 °C oil bath for 48 hours and cooling to room temperature, remove the solvent under reduced pressure, obtaining 31.23 g of a white solid with a yield of 99%. MS: m / z 395.98 (M+H) + .

[0081] Synthesis of Intermediate (2-3): Add 2-2 (10.00 g, 25.12 mmol, 1.0 equiv), DtBu-Bpin (14.70 g, 62.79 mmol, 2.5 equiv), tetrakis(triphenylphosphine)palladium (580.00 mg, 0.50 mmol, 2 mol%), and potassium carbonate (6.94 g, 50.24 mmol, 2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and replace with nitrogen three times. Under nitrogen protection, add toluene (40 mL), ethanol (20 mL), and water (10 mL). After reacting in a 100 °C oil bath for 18 hours and cooling to room temperature, extract with ethyl acetate, wash with water, dry over sodium sulfate, and remove the solvent under reduced pressure. The crude product is separated and filtered through a silica gel chromatography column. The eluent: petroleum ether, obtaining 13.00 g of a blue-gray solid with a yield of 85%. MS: m / z 616.48 (M+H) + , MS: m / z 616.48 (M+H) + .

[0082] Synthesis of Intermediate (2-4): Add 2-3 (11.00 g, 17.83 mmol, 1.0 equiv), DCz-Cl (9.36 g, 18.72 mmol, 1.05 equiv), tris(dibenzylideneacetone)dipalladium(0) (490 mg, 0.53 mmol, 3 mol%), 2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (XPhos) (510 mg, 1.07 mmol, 6 mol%) and sodium tert-butoxide (3.43 g, 35.66 mmol, 2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Flush with nitrogen three times, and then add toluene (140 mL) under nitrogen protection. After reacting in an oil bath at 110 °C for 28 h, cool to room temperature, filter, remove the solvent by rotary evaporation under reduced pressure, and separate the crude product by silica gel column chromatography. The eluent is petroleum ether:ethyl acetate = 30:1 - 20:1, to obtain 16.00 g of green solid with a yield of 84%, MS: m / z 1079.28 (M+H) + 。

[0083] Synthesis of Ligand L3: Add 2-4 (16.00 g, 14.81 mmol, 1.0 equiv), ammonium hexafluorophosphate (4.8 g, 29.61 mmol, 2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Flush with nitrogen three times, and then add triethyl orthoformate (70 mL) under nitrogen protection. After reacting in an oil bath at 75 °C for 1 h, cool to room temperature, remove the solvent by rotary evaporation under reduced pressure, and separate by silica gel column chromatography. The eluent is dichloromethane / methanol = 100:1, to obtain 14.50 g of brown solid with a yield of 80%, 11H NMR (500 MHz, CDCl3) δ 0.86 (s, 18H), 1.17 (s, 18H), 1.25 (s, 9H), 1.44 (s, 10H), 6.78 (t, J = 2 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H), 6.88 (td, J = 8.5, 1.0 Hz, 1H), 7.04 (td, J = 7.5, 1.0 Hz, 2H), 7.18–7.25 (m, 5H), 7.27 (d, J = 2.0 Hz, 2H), 7.30 (dd, J = 7.0, 1.0 Hz, 1H), 7.32 (d, J = 2.5 Hz, 1H), 7.40 (d, J = 2.0 Hz, 1H), 7.43 (td, J = 7.0, 1.0 Hz, 1H), 7.57 (d, J = 8.0 Hz, 1H), 7.59–7.65 (m, 2H), 7.70 (dd, J = 8.0, 2.0 Hz, 1H), 8.05 (dd, J = 8.0, 2.0 Hz, 2H), 8.10 (d, J = 7.5 Hz, 1H), 8.25 (d, J = 1.5 Hz, 1H), 8.30 (d, J = 8.0 Hz, 1H), 8.96 (d, J = 2.0 Hz, 1H), 8.99 (d, J = 6.0 Hz, 1H).

[0084] Synthesis of Pt3: Add L3 (6.00 g, 4.86 mmol, 1.0 equiv) and platinum(II) chloride (645.00 mg, 2.43 mmol, 1.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Evacuate and backfill with nitrogen three times. Under nitrogen protection, add o-dichlorobenzene (240 mL), and deoxygenate by nitrogen bubbling for 30 min. React in an oil bath at 125 °C for 72 h. After the reaction is cooled to room temperature, remove the solvent by rotary evaporation under reduced pressure. The crude product is separated by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 2:1, to obtain 4.20 g of a yellow solid with a yield of 36%. 11H NMR (500 MHz, CDCl3) δ 0.86 (s, 18H), 1.17 (s, 18H), 1.25 (s, 9H), 1.44 (s, 9H), 6.78 (t, J = 2.0 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H), 6.88 (td, J = 7.5, 1.0 Hz, 1H), 7.04 (ddd, J = 8.0, 3.5, 1.5 Hz, 2H), 7.21 (dd, J = 6.5, 2.0 Hz, 1H), 7.24 (dd, J = 6.0, 2.0 Hz, 3H), 7.27 (t, J = 2.0 Hz, 2H), 7.29–7.31 (m, 1H), 7.32 (d, J = 2.5 Hz, 1H), 7.40 (d, J = 2.0 Hz, 1H), 7.43 (ddd, J = 8.5, 7.0, 1.0 Hz, 1H), 7.57 (d, J = 7.5 Hz, 1H), 7.59–7.65 (m, 2H), 7.70 (dd, J = 8.0, 2.0 Hz, 1H), 8.05 (dd, J = 7.5, 2.0 Hz, 1H), 8.10 (d, J = 7.5 Hz, 1H), 8.25 (d, J = 1.5 Hz, 1H), 8.30 (d, J = 8.0 Hz, 1H), 8.96 (d, J = 2.0 Hz, 1H), 8.99 (d, J = 6.0 Hz, 1H).

[0085] Example 2: The synthetic route of the tetradentate cyclometalated platinum(II) complex Pt4 is as follows:

[0086]

[0087] Synthesis of intermediate (3-1): Add NBr (1.0 equiv.) and N,N-dimethylformamide (200 mL) to a three-necked flask equipped with a magnetic stir bar. After cooling to 0 °C in an ethanol bath, add sodium hydride (60%) (3.0 equiv.). After stirring for 30 minutes, slowly add F-NO2 (1.0 equiv.). Resume stirring at room temperature and react for 36 hours. Quench the reaction mixture with water, extract with ethyl acetate, and remove the solvent under reduced pressure. The crude product is separated and filtered through a silica gel chromatography column. The eluent is petroleum ether:ethyl acetate = 40:1 to obtain 28 g of a yellow solid with a yield of 60%, MS: m / z 369.90 (M+H) + .

[0088] Synthesis of Intermediate (3-2): Add 3-1 (1.0 equivalent) and stannous chloride (4.0 equivalents) to a three-necked flask equipped with a magnetic stir bar. Then, evacuate and refill with nitrogen three times. Under nitrogen protection, add ethanol (150 mL) and ethyl acetate (150 mL). After reacting in an 80 °C oil bath for 24 hours, cool to room temperature. After removing the solvent by vacuum distillation, 23 g of white solid is obtained with a yield of 87%. MS: m / z 339.92 (M+H) + .

[0089] Synthesis of Intermediate (3-3): Add 3-2 (1.0 equivalent), P-Bpin (2.5 equivalents), tetrakis(triphenylphosphine)palladium(0) (2 mol%), and potassium carbonate (2.0 equivalents) to a three-necked flask equipped with a magnetic stir bar. Then, evacuate and refill with nitrogen three times. Under nitrogen protection, add toluene (60 mL), ethanol (30 mL), and water (15 mL). After reacting in a 90 °C oil bath for 13 hours, cool to room temperature. Extract with ethyl acetate, wash with water, dry over sodium sulfate, and after removing the solvent by vacuum distillation, separate and filter the crude product through a silica gel chromatography column. Eluent: petroleum ether, to obtain 15 g of blue-gray solid with a yield of 82%. MS: m / z 336.12 (M+H) + .

[0090] Synthesis of Intermediate (3-4): Add 3-3 (1.0 equivalent), DCz-Cl (1.05 equivalents), bis(dibenzylideneacetone)palladium(0) (3 mol%), 2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (XPhos) (6 mol%), and sodium tert-butoxide (2.0 equivalents) to a three-necked flask equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times. Under nitrogen protection, add toluene (150 mL). After reacting in a 100 °C oil bath for 28 hours, cool to room temperature, filter, and after removing the solvent by vacuum distillation, separate the crude product through a silica gel chromatography column. Eluent: petroleum ether:ethyl acetate = 30:1 - 20:1, to obtain 25.00 g of green solid with a yield of 80%. MS: m / z 799.37 (M+H) + .

[0091] Synthesis of Ligand L4: Add 3-4 (1.0 equivalent) and ammonium hexafluorophosphate (2.0 equivalents) to a three-necked flask equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times. Under nitrogen protection, add triethyl orthoformate (70 mL). After reacting in a 75 °C oil bath for 1 hour, cool to room temperature. After removing the solvent by vacuum distillation, separate through a silica gel chromatography column. Eluent: dichloromethane / methanol = 100:1, to obtain 20 g of brown solid with a yield of 75%. MS: m / z 810.36 (M+H) + .

[0092] Synthesis of Pt4: Add L4 (1.0 equivalent) and platinum dichloride (1.0 equivalent) into a three-necked flask equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times. Under nitrogen protection, add o-dichlorobenzene (240 mL), and deoxygenate by nitrogen bubbling for 30 min. React in an oil bath at 120 °C for 72 h. After the reaction is cooled to room temperature, remove the solvent by rotary evaporation under reduced pressure. The obtained crude product is separated by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 2:1, to obtain 5.30 g of a yellow solid with a yield of 28%. MS: m / z 1003.31 (M+H) + 。

[0093] Example 3: Tetradentate cyclometalated platinum(II) complex Pt6

[0094] Prepare the synthetic complex Pt6 by referring to the synthetic method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 128 mg of a yellow solid is obtained with a yield of 27%. MS: m / z 1339.68 (M+H) + 。

[0095] Example 4: Tetradentate cyclometalated platinum(II) complex Pt10

[0096] Prepare the synthetic complex Pt10 by referring to the synthetic method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 150 mg of a yellow solid is obtained with a yield of 32%. MS: m / z 1297.64 (M+H) + 。

[0097] Example 5: Tetradentate cyclometalated platinum(II) complex Pt12

[0098] Prepare the synthetic complex Pt12 by referring to the synthetic method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 124 mg of a yellow solid is obtained with a yield of 32%. MS: m / z 1339.66 (M+H) + 。

[0099] Example 6: Tetradentate cyclometalated platinum(II) complex Pt14

[0100] Prepare the synthetic complex Pt14 by referring to the synthetic method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 198 mg of a yellow solid is obtained with a yield of 36%. MS: m / z 1373.63 (M+H) + 。

[0101] Example 7: Tetradentate cyclometalated platinum(II) complex Pt15

[0102] The complex Pt15 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 128 mg of yellow solid was obtained with a yield of 30%. MS: m / z 1373.62 (M+H) + 。

[0103] Example 8: Tetradentate cyclometalated platinum(II) complex Pt17

[0104] The complex Pt17 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 124 mg of yellow solid was obtained with a yield of 25%. MS: m / z 1373.64 (M+H) + 。

[0105] Example 9: Tetradentate cyclometalated platinum(II) complex Pt20

[0106] The complex Pt20 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 105 mg of yellow solid was obtained with a yield of 38%. MS: m / z 1521.70 (M+H) + 。

[0107] Example 10: Tetradentate cyclometalated platinum(II) complex Pt21

[0108] The complex Pt21 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 135 mg of yellow solid was obtained with a yield of 29%. MS: m / z 1389.61 (M+H) + 。

[0109] Example 11: Tetradentate cyclometalated platinum(II) complex Pt23

[0110] The complex Pt23 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 127 mg of yellow solid was obtained with a yield of 33%. MS: m / z 1521.72 (M+H) + 。

[0111] Example 12: Tetradentate cyclometalated platinum(II) complex Pt24

[0112] The complex Pt24 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 122 mg of yellow solid was obtained with a yield of 21%. MS: m / z 1537.68 (M+H) +。

[0113] Example 13: Tetradentate cyclometalated platinum(II) complex Pt27

[0114] The complex Pt27 was synthesized by referring to the synthesis method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 128 mg of yellow solid was obtained, with a yield of 40%. MS: m / z 1521.71 (M+H) + 。

[0115] Example 14: Tetradentate cyclometalated platinum(II) complex Pt32

[0116] The complex Pt32 was synthesized by referring to the synthesis method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 125 mg of yellow solid was obtained, with a yield of 36%. MS: m / z 1373.63 (M+H) + 。

[0117] Example 15: Tetradentate cyclometalated platinum(II) complex Pt35

[0118] The complex Pt35 was synthesized by referring to the synthesis method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 136 mg of yellow solid was obtained, with a yield of 22%. MS: m / z 1373.63 (M+H) + 。

[0119] Example 16: Tetradentate cyclometalated platinum(II) complex Pt36

[0120] The complex Pt36 was synthesized by referring to the synthesis method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 132 mg of yellow solid was obtained, with a yield of 36%. MS: m / z 1365.75 (M+H) + 。

[0121] Example 17: Tetradentate cyclometalated platinum(II) complex Pt38

[0122] The complex Pt38 was synthesized by referring to the synthesis method of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 127 mg of yellow solid was obtained, with a yield of 28%. MS: m / z 1449.66 (M+H) + 。

[0123] Example 18: Tetradentate cyclometalated platinum(II) complex Pt40

[0124] Prepare the synthetic complex Pt40 according to the synthetic method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw material of the corresponding fragment in Example 1 is replaced. Finally, 145 mg of yellow solid is obtained with a yield of 32%. MS: m / z 1655.81 (M+H) + 。

[0125] Example 19: Tetradentate cyclometalated platinum(II) complex Pt41

[0126] Prepare the synthetic complex Pt41 according to the synthetic method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw material of the corresponding fragment in Example 1 is replaced. Finally, 163 mg of yellow solid is obtained with a yield of 27%. MS: m / z 1378.70 (M+H) + 。

[0127] Example 20: Tetradentate cyclometalated platinum(II) complex Pt44

[0128] Prepare the synthetic complex Pt44 according to the synthetic method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw material of the corresponding fragment in Example 1 is replaced. Finally, 134 mg of yellow solid is obtained with a yield of 30%. MS: m / z 1469.73 (M+H) + 。

[0129] Example 21: Tetradentate cyclometalated platinum(II) complex Pt46

[0130] Prepare the synthetic complex Pt46 according to the synthetic method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw material of the corresponding fragment in Example 1 is replaced. Finally, 140 mg of yellow solid is obtained with a yield of 29%. MS: m / z1353.70 (M+H) + 。

[0131] Example 22: Tetradentate cyclometalated platinum(II) complex Pt48

[0132] Prepare the synthetic complex Pt48 according to the synthetic method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw material of the corresponding fragment in Example 1 is replaced. Finally, 142 mg of yellow solid is obtained with a yield of 31%. MS: m / z 1029.69 (M+H) + 。

[0133] Example 23: Tetradentate cyclometalated platinum(II) complex Pt50

[0134] Prepare the synthetic complex Pt50 according to the synthetic method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw material of the corresponding fragment in Example 1 is replaced. Finally, 131 mg of yellow solid is obtained with a yield of 29%. MS: m / z 1547.72 (M+H)+ .

[0135] Example 24: Tetradentate cyclometalated platinum(II) complex Pt51

[0136] Prepared the synthetic complex Pt51 by referring to the synthetic method of the complex Pt3 in Reference Example 1, with the difference being only the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 153 mg of a yellow solid was obtained with a yield of 32%. MS: m / z 1436.72 (M+H) + .

[0137] Example 25: Tetradentate cyclometalated platinum(II) complex Pt54

[0138] Prepared the synthetic complex Pt54 by referring to the synthetic method of the complex Pt3 in Reference Example 1, with the difference being only the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 136 mg of a yellow solid was obtained with a yield of 36%. MS: m / z 1488.64 (M+H) + .

[0139] Example 26: Tetradentate cyclometalated platinum(II) complex Pt56

[0140] Prepared the synthetic complex Pt56 by referring to the synthetic method of the complex Pt3 in Reference Example 1, with the difference being only the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 136 mg of a yellow solid was obtained with a yield of 29%. MS: m / z 1308.62 (M+H) + .

[0141] Example 27: Tetradentate cyclometalated platinum(II) complex Pt60

[0142] Prepared the synthetic complex Pt60 by referring to the synthetic method of the complex Pt3 in Reference Example 1, with the difference being only the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 131 mg of a yellow solid was obtained with a yield of 29%. MS: m / z 1675.78 (M+H) + .

[0143] Example 28: Tetradentate cyclometalated platinum(II) complex Pt61

[0144] Prepared the synthetic complex Pt61 by referring to the synthetic method of the complex Pt3 in Reference Example 1, with the difference being only the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 125 mg of a yellow solid was obtained with a yield of 31%. MS: m / z 1441.69 (M+H) + .

[0145] Example 29: Tetradentate cyclometalated platinum(II) complex Pt63

[0146] Prepare the synthetic complex Pt63 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 158 mg of yellow solid was obtained with a yield of 30%. MS: m / z 1415.68 (M+H) + 。

[0147] Example 30: Tetradentate cyclometalated platinum(II) complex Pt65

[0148] Prepare the synthetic complex Pt65 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 131 mg of yellow solid was obtained with a yield of 29%. MS: m / z 1415.68 (M+H) + 。

[0149] Example 31: Tetradentate cyclometalated platinum(II) complex Pt66

[0150] Prepare the synthetic complex Pt66 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 162 mg of yellow solid was obtained with a yield of 29%. MS: m / z 1448.68 (M+H) + 。

[0151] Example 32: Tetradentate cyclometalated platinum(II) complex Pt70

[0152] Prepare the synthetic complex Pt70 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 138 mg of yellow solid was obtained with a yield of 27%. MS: m / z 1308.62 (M+H) + 。

[0153] Example 33: Tetradentate cyclometalated platinum(II) complex Pt72

[0154] Prepare the synthetic complex Pt72 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 177 mg of yellow solid was obtained with a yield of 31%. MS: m / z 1443.75 (M+H) + 。

[0155] Example 34: Tetradentate cyclometalated platinum(II) complex Pt75

[0156] Prepare the synthetic complex Pt75 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 145 mg of yellow solid was obtained with a yield of 33%. MS: m / z 1415.72 (M+H)+ .

[0157] Example 35: Tetradentate cyclometalated platinum(II) complex Pt79

[0158] The complex Pt79 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw materials of the corresponding fragments in Example 1 were replaced. Finally, 142 mg of yellow solid was obtained, with a yield of 27%. MS: m / z 1387.68 (M+H) + .

[0159] Example 36: Tetradentate cyclometalated platinum(II) complex Pt80

[0160] The complex Pt80 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw materials of the corresponding fragments in Example 1 were replaced. Finally, 133 mg of yellow solid was obtained, with a yield of 32%. MS: m / z 1448.68 (M+H) + .

[0161] Example 37: Tetradentate cyclometalated platinum(II) complex Pt81

[0162] The complex Pt81 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw materials of the corresponding fragments in Example 1 were replaced. Finally, 143 mg of yellow solid was obtained, with a yield of 25%. MS: m / z 1415.72 (M+H) + .

[0163] Example 38: Tetradentate cyclometalated platinum(II) complex Pt82

[0164] The complex Pt82 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw materials of the corresponding fragments in Example 1 were replaced. Finally, 129 mg of yellow solid was obtained, with a yield of 25%. MS: m / z 1505.73 (M+H) + .

[0165] Example 39: Tetradentate cyclometalated platinum(II) complex Pt85

[0166] The complex Pt85 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being that the ligand raw materials of the corresponding fragments in Example 1 were replaced. Finally, 140 mg of yellow solid was obtained, with a yield of 36%. MS: m / z 1427.64 (M+H) + .

[0167] Example 40: Tetradentate cyclometalated platinum(II) complex Pt86

[0168] Prepare the synthetic complex Pt86 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 142 mg of a yellow solid was obtained with a yield of 34%. MS: m / z 1227.56 (M+H) + 。

[0169] Example 41: Tetradentate cyclometalated platinum(II) complex Pt89

[0170] Prepare the synthetic complex Pt89 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 167 mg of a yellow solid was obtained with a yield of 31%. MS: m / z 1279.59 (M+H) + 。

[0171] Example 42: Tetradentate cyclometalated platinum(II) complex Pt93

[0172] Prepare the synthetic complex Pt93 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 133 mg of a yellow solid was obtained with a yield of 37%. MS: m / z 1109.36 (M+H) + 。

[0173] Example 43: Tetradentate cyclometalated platinum(II) complex Pt94

[0174] Prepare the synthetic complex Pt94 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 132 mg of a yellow solid was obtained with a yield of 30%. MS: m / z 1808.96 (M+H) + 。

[0175] Example 44: Tetradentate cyclometalated platinum(II) complex Pt98

[0176] Prepare the synthetic complex Pt98 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 141 mg of a yellow solid was obtained with a yield of 34%. MS: m / z 1385.39 (M+H) + 。

[0177] Example 45: Tetradentate cyclometalated platinum(II) complex Pt99

[0178] Prepare the synthetic complex Pt99 in the same way as the synthesis of complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 134 mg of a yellow solid was obtained with a yield of 30%. MS: m / z 1283.62 (M+H)+ .

[0179] Example 46: Tetradentate cyclometalated platinum(II) complex Pt102

[0180] The complex Pt102 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 163 mg of yellow solid was obtained with a yield of 28%. MS: m / z 1303.59 (M+H) + .

[0181] Example 47: Tetradentate cyclometalated platinum(II) complex Pt103

[0182] The complex Pt103 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 115 mg of yellow solid was obtained with a yield of 22%. MS: m / z 1296.62 (M+H) + .

[0183] Example 48: Tetradentate cyclometalated platinum(II) complex Pt105

[0184] The complex Pt105 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 101 mg of yellow solid was obtained with a yield of 31%. MS: m / z 1241.57 (M+H) + .

[0185] Example 49: Tetradentate cyclometalated platinum(II) complex Pt108

[0186] The complex Pt108 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 122 mg of yellow solid was obtained with a yield of 29%. MS: m / z 1378.60 (M+H) + .

[0187] Example 50: Tetradentate cyclometalated platinum(II) complex Pt109

[0188] The complex Pt109 was synthesized by referring to the synthesis method of the complex Pt3 in Reference Example 1, with the only difference being the replacement of the ligand raw material in the corresponding fragment in Example 1. Finally, 131 mg of yellow solid was obtained with a yield of 31%. MS: m / z 1361.67 (M+H) + .

[0189] Example 51: Tetradentate cyclometalated platinum(II) complex Pt114

[0190] The complex Pt114 was synthesized by referring to the synthesis method of the complex Pt3 in Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 106 mg of yellow solid was obtained with a yield of 31%. MS: m / z 1297.64 (M+H) + 。

[0191] Example 52: Tetradentate cyclometalated platinum(II) complex Pt121

[0192] The complex Pt121 was synthesized by referring to the synthesis method of the complex Pt3 in Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 135 mg of yellow solid was obtained with a yield of 28%. MS: m / z 1069.43 (M+H) + 。

[0193] Example 53: Tetradentate cyclometalated platinum(II) complex Pt122

[0194] The complex Pt122 was synthesized by referring to the synthesis method of the complex Pt3 in Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 161 mg of yellow solid was obtained with a yield of 37%. MS: m / z 1292.68 (M+H) + 。

[0195] Example 54: Tetradentate cyclometalated platinum(II) complex Pt126

[0196] The complex Pt126 was synthesized by referring to the synthesis method of the complex Pt3 in Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 186 mg of yellow solid was obtained with a yield of 31%. MS: m / z 1090.57 (M+H) + 。

[0197] Example 55: Tetradentate cyclometalated platinum(II) complex Pt129

[0198] The complex Pt129 was synthesized by referring to the synthesis method of the complex Pt3 in Example 1, with the only difference being the replacement of the ligand raw materials for the corresponding fragments in Example 1. Finally, 111 mg of yellow solid was obtained with a yield of 33%. MS: m / z 1300.73 (M+H) + 。

[0199] Example 56: Tetradentate cyclometalated platinum(II) complex Pt133

[0200] The complex Pt133 was synthesized by referring to the synthesis method of the complex Pt3 in Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 131 mg of yellow solid was obtained with a yield of 25%. MS: m / z 1299.72 (M+H) + .

[0201] Example 57: Tetradentate cyclometalated platinum(II) complex Pt135

[0202] The complex Pt135 was synthesized by referring to the synthesis method of the complex Pt3 in Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 124 mg of yellow solid was obtained with a yield of 27%. MS: m / z 1288.65 (M+H) + .

[0203] Example 58: Tetradentate cyclometalated platinum(II) complex Pt136

[0204] The complex Pt136 was synthesized by referring to the synthesis method of the complex Pt3 in Example 1, with the only difference being the replacement of the ligand raw materials in the corresponding fragments in Example 1. Finally, 138 mg of yellow solid was obtained with a yield of 35%. MS: m / z 1297.71 (M+H) + .

[0205] Photophysical properties:

[0206] Figure 1 It is the room-temperature emission spectrum of the platinum(II) complex Pt3 in dichloromethane (DCM) and toluene solutions. Table 1 shows the photophysical property test results of some metal platinum(II) complexes of the present invention in dichloromethane and toluene solutions at room temperature.

[0207] Table 1. Photophysical property test results of some metal platinum(II) complexes of the present invention in toluene solution at room temperature

[0208]

[0209]

[0210] From Figure 1 and the data in Table 1, it can be seen that the emission wavelength of the platinum metal complex phosphorescent material is in the green light emission region around 530 nm; the full width at half maximum is small, all below 35 nm, having a high color purity. Its quantum efficiency in polymethyl methacrylate (PMMA) is high, and the quantum efficiency of Pt3 is 82%. Deuteration of the periphery of the ligand of the general formula structure of this application can ensure the improvement of material stability while hardly affecting the emission wavelength and full width at half maximum; in addition, by R a 、R b 、Rc , R d , R e , R f , R g , R h , R i By regulating the substituents, fine tuning of the emission wavelength can be achieved.

[0211] Fabrication of OLED devices:

[0212] On the surface or anode of ITO glass with a light-emitting area of 2.5 mm × 2.5 mm, a p-doped material is evaporated or the p-doped material is co-evaporated with a hole injection material at a concentration of 1% - 50% to form a hole injection layer (HIL) with a thickness of 5 - 100 nm and a hole transport layer (HTL) with a thickness of 5 - 200 nm. Subsequently, a light-emitting layer (EML) with a thickness of 10 - 100 nm (which may contain the compound of the present invention) is formed on the hole transport layer, and an electron transport layer (ETL) with a thickness of 20 - 200 nm and a cathode with a thickness of 50 - 200 nm are formed; if necessary, an electron blocking layer (EBL) is added between the HTL and EML layers, and an electron injection layer (EIL) is added between the ETL and the cathode to fabricate an OLED device. And the OLED is tested by standard methods. The device materials involved in the present invention can be obtained by known synthesis methods unless otherwise specified.

[0213] In a preferred specific embodiment, the structure of the top-emitting device Example 1 provided by the present invention is: ITO / Ag / ITO (12 nm / 100 nm / 10 nm) / BFSFA:FCN (97:3, 10 nm) / BFSFA (145 nm) / BFSFAtBu (50 nm) / premixed-host1:premixed-host2:Pt3 (45:45:10, 30 nm) / NAPPBI:Liq (50:50, 35 nm) / Yb (1 nm) / Ag:Mg (90:10, 14 nm) / BPNBNBA (70 nm).

[0214] Devices Example 2 - Devices Example 38 and Comparative Example 1 are respectively fabricated using a structure similar to that of Devices Example 1, with the only difference being that the Pt3 in Devices Example 1 is replaced by the platinum (II) complexes in Table 2. The luminescence characteristics of the above-prepared Devices Examples and Comparative Examples are tested by standard methods, and the data are shown in Table 2. The device structural formulas involved are as follows:

[0215]

[0216] Table 2. Luminescence characteristic data of some compounds after being fabricated into devices

[0217]

[0218]

[0219] As can be seen from Table 2, compared with Comparative Example 1, Device Examples 1-38 prepared in this application all exhibit good device performance in terms of driving voltage, current efficiency, and device lifetime; the performance improvement of each device example is based on the specific compound material of the present invention having high chemical stability and better electron transport ability.

[0220] Figure 3 are the CIE chromaticity coordinates of Device Example 1; from Figure 3 it can be seen that the CIE coordinates of the Pt3 emitter are (0.23, 0.75), which is close to the ideal green light CIE (0.17, 0.79) in the BT.2020 standard, indicating that the prepared devices are all green light devices, and the CIEy values are all around 0.75, which is suitable for high color saturation display technology. Figure 4 are the density functional theory calculation diagram and natural orbital analysis diagram of the frontier orbitals of the platinum(II) complex Pt3; from Figure 4 it can be seen that Pt3 presents a local excited state, which is consistent with its emission spectrum showing narrow-band emission.

[0221] Figure 5 is the electroluminescence spectrum diagram of Device Example 1; from Figure 5 it can be seen that the maximum emission wavelength of the platinum(II) complex Pt3 emitter is 532 nm, and the full width at half maximum (FWHM) is 14.8 nm.

[0222] Figure 6 is the operating lifetime diagram of Device Example 1. From Figure 6 it can be seen that when the initial brightness (L0) is 44634 candela per square meter (cd m -2 ), at a current density of 50 milliamperes per square centimeter, the time (LT 90 ) required for the brightness to decay from the initial value to 90% of it is 101 h. According to the power-law decay model estimation formula for OLED brightness lifetime:

[0223]

[0224] When n = 1.7, it is estimated that when the initial brightness (L0) is 1000 cd m -2 , its LT 90 is 64,000 h.

[0225] It can be seen that when it is used as a light-emitting layer material to prepare an electronic device, it has higher current efficiency, device lifetime, and color purity while reducing the driving voltage. It shows that the compound provided by the present invention has certain commercial application value.

[0226] As described above, it is only the preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes should be covered within the protection scope of the present invention.

Claims

1. A platinum(II) complex guest phosphorescent material, characterized in that, It has the structure shown in formula (I): In formula (I), R a , R b , R c , R d , R e , R f , R g , R h , R i each independently represents mono-substituted or multi-substituted; R a -R i each independently represents one or more of hydrogen, deuterium, -CN, C1-C30 alkyl, C1-C30 deuterated alkyl, C1-C30 haloalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, C1-C30 alkoxy, C1-C30 alkylsilyl, C6-C30 arylsilyl, and adjacent substituents can optionally be linked to form a ring.

2. The platinum (II) complex guest phosphorescent material according to claim 1, wherein R a -R e Each independently selected from hydrogen, deuterium, -CN, C1-C12 alkyl, C1-C12 deuterated alkyl, C1-C12 fluoroalkyl, C3-C12 cycloalkyl, C3-C6 azacycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C3-C30 heteroaryl, C1-C12 alkoxy, C1-C12 alkylsilyl, C6-C18 arylsilyl, and one or more of them, and two or more adjacent substituents independently may form a saturated or unsaturated C3-C18 aryl ring or C3-C18 heteroaryl ring with the carbon atom to which they are commonly attached, and the aryl ring or heteroaryl ring may be substituted or unsubstituted.

3. The platinum (II) complex guest phosphorescent material according to claim 1, wherein R a selected from one or more of hydrogen, deuterium, F, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, CD3, CF3, adamantyl, methoxy, aryl, methyl-substituted aryl, isopropyl-substituted aryl, tert-butyl-substituted aryl, carbazolyl, N-heterocyclopentyl.

4. The platinum (II) complex guest phosphorescent material according to claim 1, wherein R b -R e each independently selected from hydrogen, deuterium, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, tert-decyl, CD3, CF3, N-heteropentyl, adamantyl, trimethylsilyl, triarylsilyl, carbazolyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, spirofluorenyl, methoxy, one or more of substituted or unsubstituted aryl; when containing substitution, the substitution is selected from one or more of deuterium, F, -CN, C1-C10 alkyl.

5. The platinum(II) complex guest phosphorescent material according to claim 1, wherein R f selected from hydrogen, deuterium, C1–C12 alkyl; R g , R h , R i each independently selected from hydrogen, deuterium, F, -CN, C1–C12 alkyl, C1–C12 deuterated alkyl, C1–C12 fluoroalkyl, substituted or unsubstituted C3–C12 cycloalkyl, substituted or unsubstituted phenyl; when containing a substitution, the substitution is selected from one or more of deuterium, F, -CN, C1-C10 alkyl.

6. The platinum (II) complex guest phosphorescent material according to claim 1, characterized in that, R f selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; R g 、R h 、R i each independently selected from hydrogen, deuterium, F, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, CD3, CF3, methyl-substituted or unsubstituted cyclopentyl, methyl-substituted or unsubstituted cyclohexyl, substituted or unsubstituted aryl; when containing a substitution, the substitution is selected from one or more of deuterium, F, -CN, methyl, ethyl, isopropyl, tert-butyl.

7. The platinum(II) complex guest phosphorescent material according to claim 1, wherein In the platinum (II) complex with the structure shown in formula (I), the hydrogen atoms can be partially or fully deuterated.

8. The platinum (II) complex guest phosphorescent material according to claim 1, wherein The phosphorescent material is selected from any one of the chemical structures shown below, where "D" represents deuterium and "OMe" represents methoxy:

9. Use of the platinum (II) complex guest phosphorescent material according to any one of claims 1-8 in the preparation of electronic devices.

10. The application according to claim 9, characterized in that The electronic devices include one or more of organic light-emitting devices, organic optoelectronic devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light-emitting electrochemical cells or organic laser diodes.

11. An organic electroluminescent device, characterized in that, The organic light-emitting device includes a cathode, an anode and an organic functional layer therebetween; the organic functional layer includes a light-emitting layer, and the light-emitting layer includes the platinum (II) complex guest phosphorescent material according to any one of claims 1-8.

12. An organic optoelectronic device, characterized in that, The organic optoelectronic device includes: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; a second electrode on the organic light-emitting functional layer; wherein, the organic light-emitting functional layer includes the platinum (II) complex guest phosphorescent material according to any one of claims 1-8.

13. A composition, characterized in that, The composition includes the platinum (II) complex guest phosphorescent material according to any one of claims 1-8.

14. A preparation, characterized in that, The preparation includes the platinum (II) complex guest phosphorescent material according to any one of claims 1-8 and at least one solvent.

15. A display or lighting device, characterized in that, The device includes one or more of the organic light-emitting device according to claim 11 and / or the organic optoelectronic device according to claim 12.

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