Fluorenocarbazole tetradentate platinum(II) complex, organic light-emitting diode material, device, and apparatus

Abstract

The present invention relates to the field of organic electroluminescent material preparation technology, and particularly, to a fluorenocarbazole tetradentate platinum(II) complex, an organic light-emitting diode material, a device, and an apparatus. By means of introducing a fluorene ring system at the 3,4-position of carbazole and introducing a substituent at the ortho-position of the benzene ring at the upper left, a novel tetradentate platinum(II) complex-based blue phosphorescent material is obtained. The proportion of components of the localized state (3LE) is increased in the excited triplet state of the cyclic tetradentate platinum(II) complex, thereby achieving a low shoulder peak, improved emission color purity of material molecules, and enhanced stability of materials. The provided materials all have good chemical stability and thermal stability, thereby facilitating the preparation of evaporation-type OLED devices. The organic electroluminescent device manufactured using the above-described compound as the light-emitting layer has a significant improvement in both the blue light index (BI) and service life, and can also reduce the turn-on voltage.

Description

A fluorenecyclocarbazole tetradentate platinum(II) complex and an organic light-emitting diode material, device, apparatus Technical Field

[0001] This invention belongs to the field of organic electroluminescent material preparation technology, specifically relating to a fluorenecyclocarbazole tetradentate platinum(II) complex and organic light-emitting diode materials, devices, and apparatus. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technology. Compared to liquid crystal displays (LCDs), which suffer from slow response times, narrow viewing angles, the need for backlighting, and high energy consumption, OLEDs, as self-emissive devices, do not require backlighting, making them energy-efficient. They also feature low driving voltage, fast response times, high resolution and contrast, wide viewing angles, and excellent low-temperature performance. OLED devices can be made thinner and can be fabricated into flexible structures. Furthermore, they offer advantages such as low production costs, simple manufacturing processes, and the ability to be mass-produced. Therefore, OLEDs have broad and enormous application prospects in high-end electronics and aerospace. With increasing investment, further research and development, and upgrades to production equipment, OLEDs have a very wide range of application scenarios and development prospects in the future.

[0003] The core of OLED development lies in the design and development of luminescent materials. Currently, almost all OLED devices utilize a host-guest luminescence mechanism in their luminescent layers. This involves doping the host material with a guest luminescent material, where the host material generally has a higher energy level than the guest material. Energy is transferred from the host material to the guest material, exciting it and causing it to emit light. Commonly used organic phosphorescent guest materials are typically heavy metal atoms such as iridium(III), platinum(II), and palladium(II). Commonly used organic phosphorescent materials, mCBP and 2,6-mCPy, possess high efficiency and high triplet energy levels. When used as organic materials, triplet energy can be effectively transferred from the luminescent organic material to the guest phosphorescent material. However, due to the easy transport of holes and the difficult flow of electrons in mCBP, and the poor hole transport in 2,6-mCPy, the charge imbalance in the luminescent layer results in reduced device current efficiency. Furthermore, the currently used heavy metal phosphorescent organic complex molecules, specifically iridium(III) cyclic metal complexes, are limited in number. The abundance of platinum in the Earth's crust and its annual global production are approximately ten times that of iridium. The price of IrCl3·H2O, used to prepare iridium(III) complex phosphorescent materials, is also significantly higher than that of PtCl2 used to prepare platinum(II) complex phosphorescent materials. Furthermore, the preparation of iridium(III) complex phosphorescent materials involves four steps: iridium(III) dimer formation, iridium(III) intermediate ligand exchange, mer-iridium(III) complex synthesis, and mer-to-fac-iridium(III) complex isomer conversion. This significantly reduces the overall yield and the utilization rate of the raw material IrCl3·H2O, thus increasing the preparation cost of iridium(III) complex phosphorescent materials. In contrast, the preparation of platinum(II) complex phosphorescent materials only involves the final step of ligand metallization design of platinum salts, resulting in high platinum utilization and further reducing the preparation cost. Therefore, the preparation cost of platinum(II) complex phosphorescent materials is far lower than that of iridium(III) complex phosphorescent materials. However, the development of platinum complex materials and devices still faces some technical challenges. One key challenge is how to reduce the height of the shoulder peak in the emission spectrum to improve the color purity of the material's molecular luminescence. This problem is particularly important for blue and deep blue luminescent materials, as it significantly impacts the efficiency and energy utilization of top-emitting devices for commercial applications. Therefore, there is an urgent need to develop novel phosphorescent platinum(II) complexes. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a fluorene-based tetradentate platinum(II) complex of carbazole and organic light-emitting diode (OLED) materials, devices, and apparatuses. This invention introduces a fluorene ring system at the 3,4-position of carbazole, which increases the proportion of localized states (LE) in the excited triplet state of the tetradentate platinum(II) complex, resulting in a lower shoulder peak and improved purity of the emitted color. The complex provided by this invention, when used as a light-emitting layer material to prepare organic electroluminescent devices, enables the devices to exhibit excellent performance. It can improve the current efficiency of organic electroluminescent devices, enhance device lifetime, and reduce the operating voltage of the components.

[0005] To achieve the above-mentioned technical objectives, the technical solution of the present invention is as follows:

[0006] This invention provides a fluorenylcarbazole tetradentate platinum(II) complex having the general structure shown in formula (I):

[0007] In equation (I), R 1 –R 6 Each can be used independently to represent monosubstituted to the maximum amount of substitution, or no substitution; R 1 –R 6 Each of the following is independently selected from: hydrogen, deuterium, halogen, CN, C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, substituted or unsubstituted C3–C30 heterocycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 alkylsilyl, substituted or unsubstituted C6–C60 arylsilyl; and two adjacent substituents may be linked to form a ring;

[0008] R a and R b Each is independently selected from hydrogen, deuterium, C1–C30 alkyl, substituted or unsubstituted C1–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, and R a and R b They can be connected to form a ring;

[0009] R x Selected from C1–C30 alkyl, substituted or unsubstituted C1–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 diarylamino; R x It can be linked with adjacent substituents to form a ring;

[0010] In formula (I), when each substituent contains a substitution, the substitution is selected from one or more of hydrogen, deuterium, halogen, CN, C1–C14 alkyl, C3–C14 cycloalkyl, C6–C18 aryl, and C6–C18 heteroaryl.

[0011] Furthermore, the R 1 –R 6 R x , or R a and R b When cyclization occurs, the ring is a substituted or unsubstituted C3-C20 aliphatic ring, a substituted or unsubstituted C6-C20 aromatic ring, a substituted or unsubstituted C3-C20 aromatic heterocyclic ring, or a substituted or unsubstituted C10-C20 fused ring.

[0012] Furthermore, R 1 Independently selected from one or more of hydrogen, deuterium, phenyl, and tert-butyl-substituted phenyl groups; R 2 The substituent is independently selected from one or more of hydrogen, deuterium, substituted or unsubstituted C6–C30 aryl, substituted or unsubstituted C6–C30 hetero-N aryl, and trimethylsilyl, wherein the substituent is selected from deuterium, F, methyl, ethyl, propyl, isopropyl, and tert-butyl.

[0013] Furthermore, R 3 R 4 Each of the following is independently selected from one or more of hydrogen, deuterium, CN, methyl, ethyl, propyl, tert-butyl, CF3, methyl-substituted or unsubstituted cyclohexyl, carbazolyl-substituted or unsubstituted phenyl, carbazolyl, N-phenylcarbazolyl, substituted or unsubstituted indole, oxaindole, thioindole, substituted or unsubstituted N-oxaindole, and diphenylamino, wherein the substituent is selected from deuterium, F, methyl, ethyl, propyl, tert-butyl, fluorenyl, and carbazolyl.

[0014] Furthermore, the R 3 R 4 It can form a benzene ring, substituted or unsubstituted cyclohexane, indene, N-hedinyl, S-hedinyl, O-hedinyl when it contains a substituted substance, the substituted substance is selected from deuterium, F, methyl, ethyl, propyl, isopropyl, tert-butyl.

[0015] Furthermore, the R 5 The substituent is independently selected from deuterium, methyl, ethyl, propyl, tert-butyl, deuterated tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, dibenzofuranyl, dibenzothiopheneyl, trimethylsilyl, triarylsilyl, tetraarylsilyl, substituted or unsubstituted carbazole, methyl-substituted tetrahydronaphthyl, diisopropylamino, and cyclopentane, wherein the substituent is selected from one or more of deuterium, methyl, ethyl, propyl, tert-butyl, deuterated tert-butyl, and adamantyl.

[0016] Furthermore, R 6 The substituent is independently selected from one or more of hydrogen, deuterium, substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, substituted or unsubstituted C3–C30 heterocycloalkyl, substituted or unsubstituted C6–C30 aryl, substituted or unsubstituted C6–C30 heteroaryl, substituted or unsubstituted C6–C30 arylamino, C1–C30 alkylsilyl, and C6–C30 arylsilyl, wherein the substituent is selected from deuterium, methyl, ethyl, propyl, tert-butyl, and adamantyl.

[0017] Furthermore, the R 6 It is independently selected from one or more of hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, pentyl, hexyl, heptyl, cyclopentane, methylcyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, methylphenyl, tert-butylphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, methylcarbazolyl, azircyclopentyl, azircyclohexyl, diisopropylamino, trimethylsilyl, triarylsilyl, N-phenylcarbazolyl, and methylanthrayl.

[0018] Furthermore, R a and R b Each is independently selected from one or more of hydrogen, deuterium, CD3, F, CF3, CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, phenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, and di-tert-butylphenyl; R a and R b It can be selectively linked into cyclopentane, cyclohexane, adamantyl, fluorenyl, and tert-butylfluorenyl.

[0019] Furthermore, R x The substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C1–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 arylamino; when substituted, the substituted ...

[0020] Furthermore, the R xSelected from one or more of hydrogen, deuterium, CD3, F, CF3, CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, cyclopentane, cyclohexane, adamantyl, phenyl, biphenyl, terphenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, naphthyl, methyl-substituted tetrahydronaphthyl, indene, methyl-substituted indene, oxainyl, thiainyl, dibenzofuranyl, dibenzothiophenyl, carbazole, N-phenylcarbazoleyl, and diarylamino; R x It can fuse with adjacent substitution sites to synthesize tert-butyl-substituted or unsubstituted benzofuranyl, benzothiophenyl, and benzopyrroleyl.

[0021] Furthermore, hydrogen in all substituents in formula (I) can be replaced by deuterium.

[0022] Preferably, the fluorenylcarbazole tetradentate platinum(II) complex is selected from any one of the following chemical structures: where "D" represents deuterium:

[0023] Furthermore, the present invention also provides the application of the cyclocarbazole tetradentate platinum (II) complex having the structure shown in formula (I) above in the preparation of electronic devices.

[0024] Furthermore, the electronic devices include organic light-emitting diodes (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photosensors, organic optoelectronic devices, organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), and organic laser diodes (O-lasers).

[0025] In another aspect, the present invention also provides an organic electroluminescent device comprising a cathode, an anode, and an organic functional layer therebetween, the organic functional layer comprising a cyclocarbazole tetradentate platinum (II) complex having the structure shown in formula (I) as described above.

[0026] Preferably, the organic functional layer comprises a light-emitting layer containing a cyclocarbazole tetradentate platinum (II) complex having the structure shown in formula (I) as described above.

[0027] Furthermore, the light-emitting layer also contains a fluorescent dopant material; the fluorescent dopant material is preferably a boron-containing organic luminescent material.

[0028] In another aspect, the present invention also provides an organic optoelectronic device comprising: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; and a second electrode on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises a cyclocarbazole tetradentate platinum(II) complex having the structure shown in formula (I) above. For example, the platinum(II) complex can be included as a light-emitting material in the organic light-emitting functional layer.

[0029] Furthermore, the organic light-emitting functional layer also contains any one or more fluorescent doping materials, wherein the fluorescent doping material is preferably a boron-containing organic luminescent material, and more preferably a phosphorus-sensitive boron-containing compound.

[0030] In this invention, organic optoelectronic devices can be fabricated by depositing metals or conductive oxides and their alloys onto a substrate using methods such as sputtering, electron beam evaporation, and vacuum deposition to form the anode. A hole injection layer, hole transport layer, light-emitting layer, air-blocking layer, and electron transport layer are then sequentially deposited onto the surface of the anode, followed by the deposition of the cathode. Alternatively, organic electroluminescent devices can be fabricated by depositing the cathode, organic layer, and anode onto a substrate in that order. The organic layer can also include a multilayer structure comprising a hole injection layer, a hole transport layer, a light-emitting layer, a hole-blocking layer, and an electron transport layer. In this invention, the organic layer is prepared using polymer materials via solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing, or thermal imaging, etc.) instead of evaporation methods, which can reduce the number of device layers.

[0031] The present invention also provides a composition comprising a cyclocarbazole tetradentate platinum(II) complex having the structure shown in formula (I) above. Preferably, the composition further comprises a fluorescent dopant material, wherein the fluorescent dopant material is preferably a boron-containing organic luminescent material, and more preferably a phosphorescently sensitizable boron-containing compound.

[0032] The present invention also provides a formulation comprising a cyclocarbazole tetradentate platinum (II) complex having the structure shown in formula (I) as described above, or a composition as described above, and at least one solvent.

[0033] The solvent is not particularly limited and can be any solvent well known to those skilled in the art, such as unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents, halogenated unsaturated hydrocarbon solvents, ether solvents, or ester solvents; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetrahydronaphthalene, n-butylbenzene, sec-butylbenzene, or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene, or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; and the ester solvent is an alkyl benzoate ester.

[0034] The present invention also provides a display or lighting device comprising one or more of the organic optoelectronic devices described above.

[0035] Compared with the prior art, the beneficial effects of the present invention are:

[0036] This invention introduces a fluorene ring system at the 3,4-position of carbazole and a substituent at the ortho position of the benzene ring in the upper left corner, thereby designing and controlling the production of novel tetradentate platinum(II) complex blue phosphorescent materials, which also improves the device stability of the materials. Firstly, introducing a fluorene ring system at the 3,4-position of carbazole can appropriately enhance the localization of the excited triplet state in the tetradentate platinum(II) complex. 3 The composition ratio of LE (carbazole) results in a low shoulder peak, improving the purity of the material's luminescent color. Secondly, the large volume of the 3,4-fluorene ring system of carbazole suppresses intermolecular interactions, preventing a significant redshift in the emission spectrum. Thirdly, the introduction of substituents at the ortho position of the benzene ring in the upper left corner effectively reduces its conjugation with the carbene ring system, preventing a significant redshift in the emission spectrum. The materials in this invention generally possess excellent chemical and thermal stability, making them easy to fabricate vapor-deposited OLED devices. Organic electroluminescent devices prepared using the platinum(II) complex of this invention as the luminescent layer show significant improvements in blue light index (BI) and lifetime, while also reducing the turn-on voltage. Attached Figure Description

[0037] Figure 1 shows the room-temperature emission spectrum of Pt11 in toluene solution;

[0038] Figure 2 shows the room temperature emission spectrum of Pt12 in toluene solution;

[0039] Figure 3 shows the room temperature emission spectrum of Pt104 in toluene solution;

[0040] Figure 4 shows the room temperature emission spectrum of Pt219 in toluene solution;

[0041] Figure 5 shows the room temperature emission spectrum of Pt220 in toluene solution. Detailed Implementation

[0042] The present invention will now be described in detail. The descriptions of the constituent elements described below are sometimes based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0043] The term "substituted..." as used in this invention refers to substituted silyl, substituted alkyl, substituted cycloalkyl, substituted aryl, substituted heteroaryl, substituted heteroaryl, etc., meaning a group that is independently selected from, but not limited to, deuteryl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amino, etc., and preferably selected from deuteryl, methyl, ethyl, isopropyl, tert-butyl, etc. The following groups are monosubstituted or polysubstituted: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, benzo[a]phenanthrene, perylene, pyrene, benzyl, tolyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, diphenylamino, dimethylamino, carbazole, 9-phenylcarbazole, acridine, furanyl, thiophene, benzofuranyl, benzothiophene, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothiophene, phenothiazinyl, phenothiazinyl, and indole. Furthermore, the above substituents may also be substituted by one or more of the substituents described above, such as deuterium, halogen, cyano, alkyl, cycloalkyl, silyl, or aryl.

[0044] For the purposes of this invention, it is not intended to limit the use of any substituents permitted in organic compounds. Similarly, the terms "substituted" or "substituted with" implicitly include the condition that such substitution conforms to the permitted valence 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 transformations (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in some respects, unless explicitly stated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0045] When defining various terms, "R" 1 "-"R 7 "In this invention, the general symbols are used to denote various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and while they may be defined as certain substituents in one case, they may be defined as other substituents in other cases. The 'R' used in this invention..." 1 “R” 2 "...R" n (where n is an integer) can independently have one or more of the groups listed above. For example, if R 1If it is a straight-chain alkyl group, then one hydrogen atom of the alkyl group can be optionally substituted with hydroxyl, alkyl, halogen, etc. Depending on the chosen group, the first group can be incorporated into the second group, or alternatively, the first group can be dangling, i.e., attached to the second group.

[0046] As used in this invention, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group with 1 to 60 carbon atoms, preferably 1 to 24 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, semi-alkyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, silyl, sulfoxo, or mercapto groups described in this invention.

[0047] The term "aryl" as used in this invention refers to the collective term for a monovalent group remaining after removing a hydrogen atom from the aromatic carbon atom of an aromatic compound molecule. It can be a monocyclic aryl, polycyclic aryl, or fused-ring aryl, preferably having 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl refers to an aryl molecule containing only one aromatic ring, such as phenyl, but not limited to this. The polycyclic aryl refers to an aryl molecule containing two or more independent aromatic rings, such as biphenyl, terphenyl, etc., but not limited to this. The fused-ring aryl refers to an aryl molecule containing two or more aromatic rings fused together by sharing two adjacent carbon atoms, such as naphthyl, anthracene, phenanthryl, pyrene, perylene, fluorene, benzo[a]fluorene, triphenylene, fluoranyl, spirodifluorene, etc., but not limited to this. The aryl group is preferably phenyl, biphenyl, terphenyl, naphthyl (preferably 2-naphthyl), fluorenyl, benzo[a]fluorenyl, triphenylene, spirodifluorenyl, etc.

[0048] The term "heteroaryl" as used in this invention refers to the general term for groups obtained by replacing one or more aromatic carbon atoms in an aryl group with heteroatoms. The heteroatoms include, but are not limited to, oxygen, sulfur, nitrogen, or phosphorus atoms, preferably having 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. The linking site of the heteroaryl group can be located on a cyclic carbon atom or on a cyclic nitrogen atom. The heteroaryl group can be a monocyclic heteroaryl, a polycyclic heteroaryl, or a fused-ring heteroaryl. The monocyclic heteroaryl groups include, but are not limited to, pyridinyl, pyrimidinyl, triazinyl, furanyl, thiopheneyl, pyrroleyl, imidazolyl, etc.; the polycyclic heteroaryl groups include, but are not limited to, bipyridinyl, bipyrimidinyl, phenylpyridinyl, etc.; the fused-ring heteroaryl groups include, but are not limited to, quinolinyl, isoquinolinyl, indolyl, benzothiopheneyl, benzofuranyl, benzoxazolyl, benzoimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiopheneyl, benzodibenzothiapheneyl, carbazolyl, benzocarbazolyl, acridinel, 9,10-dihydroacridinyl, phenoxazinyl, phenthiazinyl, phenoxthiazyl, etc., but are not limited to. The aforementioned heteroaryl groups are preferably pyridyl, pyrimidinyl, thiophene, furanyl, benzothiophene, benzofuranyl, benzooxazolyl, benzoimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothiophene, benzodibenzothiophene, benzodibenzofuranyl, carbazolyl, acridinel, phenoxazinyl, phenthiazinyl, and phenoxthialyl.

[0049] The cyclic structure described in this invention refers to two groups linked together by chemical bonds and optionally aromatized. Examples are shown below:

[0050] In this invention, the ring formed by the connection can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, an eight-membered ring, or a fused ring, such as benzene, naphthalene, fluorene, cyclopropane, cyclobutane, cyclopentene, cyclopentane, cyclohexene, cyclohexane, cyclopentanophenene, cyclohexanophenene, quinoline, isoquinoline, dibenzofuran, dibenzothiophene, phenanthrene, or pyrene, but is not limited thereto.

[0051] The compounds disclosed herein can exhibit desired properties and have emission and / or absorption spectra that can be tuned by selecting suitable ligands. On the other hand, the invention excludes any one or more compounds, structures, or portions thereof specifically described herein.

[0052] 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.

[0053] It should be noted that the general description above and the detailed description below are merely illustrative and explanatory, and not limiting. This application can be more easily understood by referring to the following specific embodiments and examples contained therein.

[0054] 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 synthetic methods (otherwise indicated) or specific reagents (otherwise indicated), as these are, of course, subject to variation. It should also be understood that the terminology used in this invention is for descriptive purposes only and is not intended to be limiting. While any methods and materials similar to or equivalent to those described in this invention may be used in this practice or experiment, exemplary methods and materials are described below. All raw materials and solvents used in the synthetic examples are commercially available unless otherwise specified, and the solvents were used directly without further processing.

[0055] The substrate described in this invention can be any substrate typically used in organic optoelectronic devices. It can be a glass or transparent plastic substrate, an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance, and their applications vary depending on their properties. As materials for the hole injection layer, hole transport layer, and electron injection layer, any known materials used in OLED devices can be selected, and this invention does not impose specific limitations.

[0056] Synthesis Examples

[0057] The examples of compound synthesis, composition, devices, or methods below are intended to provide a general approach to the industry and are not intended to limit the scope of this patent. While we have striven to ensure the accuracy of data (quantities, temperatures, etc.) mentioned in the patent, some errors may still exist. Unless otherwise specified, weighings are performed separately, temperatures are in °C or room temperature, and pressures are close to atmospheric pressure.

[0058] The examples below provide methods for preparing novel compounds, but the preparation of such compounds is not limited to these methods. In this field of expertise, since the compounds protected in this invention are easily modified and prepared, their preparation can be carried out using the methods listed below or other methods. The examples below are merely illustrative and are not intended to limit the scope of this patent. Temperature, catalyst, concentration, reactants, and reaction process can all be varied to select different conditions for preparing the compounds with different reactants.

[0059] 1 H NMR (500MHz), 1 H NMR (400MHz), 13C10 NMR (126 MHz) spectra were measured on an ANANCE III (500 M) NMR spectrometer; unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR measurements. 1 When using CDCl3 as the solvent in ¹H NMR spectroscopy, TMS (δ = 0.00 ppm) is used as the internal standard; when using DMSO-d6 as the solvent, TMS (δ = 0.00 ppm), residual DMSO peak (δ = 2.50 ppm), or residual water peak (δ = 3.33 ppm) are used as the internal standard. 13 In the 10⁻⁶ C NMR spectra, CDCl₃ (δ = 77.00 ppm) or DMSO-d₆ (δ = 39.52 ppm) was used as an internal standard. HPLC-MS was performed on an Agilent 6210 TOF LC / MS mass spectrometer; HRMS spectra were performed on an Agilent 6210 TOF LC / MS liquid chromatography-time-of-flight mass spectrometer. 1 In the H NMR spectral data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0060] Synthetic route

[0061] Example 1: The synthetic route for the tetradentate cyclic platinum(II) complex Pt11 is as follows:

[0062] (1) Synthesis of intermediate C: B (15.40 g, 55.76 mmol, 1.0 equivalent), cuprous chloride (552 mg, 5.58 mmol, 0.1 equivalent), lithium tert-butoxide (8.92 g, 111.52 mmol, 2.0 equivalent) were added sequentially to a dry three-necked flask equipped with a magnetic rotor. Nitrogen gas was purged three times. Under nitrogen protection, A (13.13 g, 61.34 mmol, 1.1 equivalent), 1-methylimidazole (916 mg, 11.15 mmol, 0.2 equivalent), and toluene (300 mL) were added. The mixture was stirred in an oil bath at 130 °C for 2 hours. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The organic phases were combined and washed once with brine. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography with petroleum ether / ethyl acetate as eluent at a ratio of 40:1 to 20:1, yielding product C, 21 g of white solid, in 92% yield. MS: m / z 409.08 (M+H) + .

[0063] (2) Synthesis of intermediate D: C (21.0 g, 51.30 mmol, 1.0 equivalent) was added sequentially to a dry three-necked flask equipped with a magnetic rotor. Nitrogen gas was purged three times. Tetrahydrofuran (150 mL) was added under nitrogen protection. The mixture was placed in an ethanol bath at -78 °C and 2.5 M n-butyllithium (22.57 mL, 51.30 mmol, 1.1 equivalent) was slowly injected and maintained for 2 hours. Isopropanol pinacol borate (14.32 g, 76.95 mmol, 1.5 equivalent) was added. The mixture was slowly brought back to room temperature and stirred for 12 hours. The mixture was quenched with saturated ammonium chloride water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The organic phases were combined and washed once with brine. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography with petroleum ether / ethyl acetate as eluent at a ratio of 40:1 to 20:1, yielding product D, a yellow oily liquid, 17.5 g in yield (75%). MS: m / z 457.27 (M+H). + .

[0064] (3) Synthesis of intermediate 1-Br: D (17.5 g, 38.34 mmol, 1.0 equivalent), tetra(triphenylphosphine)palladium (1.33 g, 1.15 mmol, 0.03 equivalent) and potassium carbonate (10.6 g, 76.68 mmol, 2.0 equivalent) were added sequentially to a dry three-necked flask equipped with a magnetic rotor. Nitrogen gas was purged three times. Under nitrogen protection, o-bromoiodobenzene (13 g, 46 mmol, 1.2 equivalent) and 1,4-dioxane / water (400 / 100 mL) were added. The mixture was stirred in an oil bath at 95 °C for 1 day. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The organic phases were combined and washed once with brine. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography with petroleum ether / ethyl acetate at a ratio of 20:1 to 10:1, yielding product 1-Br, a white solid, 17.1 g, in 92% yield. MS: m / z 485.12 (M+H) + .

[0065] (4) i) Synthesis of intermediate 1-OMe: 1-Br (17.1 g, 35.22 mmol, 1.0 equivalent) was added sequentially to a dry three-necked flask equipped with a magnetic rotor. Nitrogen was purged three times. Under nitrogen protection, dry tetrahydrofuran (250 mL) was added and cooled to -78 °C. 2.5 M n-butyllithium (15.5 mL, 38.74 mmol, 1.1 equivalent) was slowly added and maintained for 1 hour. 1-O (6.98 g, 38.74 mmol, 1.1 equivalent) was dissolved in tetrahydrofuran solution and added dropwise. The mixture was slowly restored to room temperature and stirred for 12 hours. Methanol (20 mL) was added to quench the quenching and the mixture was concentrated under reduced pressure to obtain the crude product. ii) The crude product was dissolved in acetic acid (200 mL) and concentrated hydrochloric acid (20 mL) and refluxed for 12 hours. Then, it was cooled to room temperature and added to ice water (500 mL) at 0 °C. The organic phase was extracted with dichloromethane and washed with a saturated aqueous solution of sodium thiosulfate. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated. The residue was purified by silica gel chromatography. Product 1-OMe was recrystallized from dichloromethane / n-hexane to give 14 g of a white powder, with a two-step yield of 92%. MS: m / z 569.27 (M+H) + .

[0066] (5) Synthesis of intermediate 1-OH: 1-OMe (14.0 g, 24.61 mmol, 1.0 equivalent) and dichloromethane (200 mL) were added sequentially to a dry three-necked flask equipped with a magnetic rotor and cooled to 0 °C. Boron tribromide (12.33 g, 49.22 mmol, 2.0 equivalent) was added dropwise. After stirring at room temperature for 2 hours, the pH was adjusted to 7-8 with saturated sodium bicarbonate aqueous solution. The mixture was extracted three times with dichloromethane / water. The organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography with petroleum ether / ethyl acetate as eluent at a ratio of 3:1-2:1 to obtain product 1-OH, a white solid of 11.2 g, in 80% yield. MS: m / z 555.26 (M+H) + .

[0067] (6) Synthesis of intermediate 1-Cl: 1-OH (11.2 g, 20.19 mmol, 1.0 equivalent), cuprous iodide (384 mg, 2.02 mmol, 0.1 equivalent), 2-pyridinecarboxylic acid (497 mg, 4.04 mmol, 0.2 equivalent), and potassium phosphate (497 mg, 4.04 mmol, 2.0 equivalent) were added sequentially to a dry three-necked flask equipped with a magnetic rotor. Nitrogen gas was purged three times. Under nitrogen protection, m-chlorobromobenzene (5.8 g, 30.29 mmol, 1.5 equivalent) and dimethyl sulfoxide (150 mL) were injected. The mixture was stirred in an oil bath at 120 °C for 1 day. After cooling to room temperature, the mixture was washed with water and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate. The organic phases were combined and washed once with brine. The mixture was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography with petroleum ether / ethyl acetate at a ratio of 20:1 to 10:1, yielding product 1-Cl, a white solid, 11.4 g, in 85% yield. MS: m / z 665.25 (M+H) + .

[0068] (7) Synthesis of intermediate A11: 1-Cl (11.4 g, 17.16 mmol, 1.0 equivalent), 1-NH2 (8.09 g, 18.88 mmol, 1.1 equivalent), tris(dibenzylacetone)palladium (471 mg, 0.51 mmol, 0.03 equivalent), 2-(di-tert-butylphosphine)biphenyl (307 mg, 1.03 mmol, 0.06 equivalent), and sodium tert-butoxide (3.30 g, 34.32 mmol, 2.0 equivalent) were added sequentially to a dry three-necked flask equipped with a magnetic rotor. Nitrogen gas was purged three times, and toluene (150 mL) was injected under nitrogen protection. The mixture was placed in an oil bath at 90 °C and stirred for 12 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography with petroleum ether / ethyl acetate as eluent at a ratio of 20:1 to 10:1, yielding product A11, a white, foamy solid, 16.3 g in volume, with a yield of 90%. MS: m / z 1057.60 (M+H) + .

[0069] (8) Synthesis of ligand L11: A11 (16.3 g, 15.63 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (5.1 g, 31.26 mmol, 2.0 equivalent) were added sequentially to a dry sealed tube equipped with a magnetic rotor. Nitrogen was purged three times. Under nitrogen protection, triethyl orthoformate (30 mL) was added. The mixture was stirred in an oil bath at 80 °C for 5 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography with dichloromethane / ethyl acetate as eluent (100:1-4:1) to obtain product L11, a white foamy solid, 15.91 g, yield 85%. MS: m / z 1067.59 (M-PF6) + .

[0070] (9) Synthesis of Pt11: Al1 (15.91 g, 13.11 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum dichloride (5.15 g, 13.77 mmol, 1.05 equivalent), and sodium acetate (3.23 g, 39.33 mmol, 3.0 equivalent) were added sequentially to a dry sealed tube equipped with a magnetic rotor. Nitrogen gas was then purged three times. Diethylene glycol dimethyl ether (780 mL) was added under nitrogen protection, and the mixture was bubbled with nitrogen for 30 minutes. The mixture was then placed in an oil bath at 120 °C and stirred for 3 days. After cooling to room temperature, the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography with petroleum ether / dichloromethane as eluent at a ratio of 3:1 to 2:1 to obtain product Pt11, a pale yellow solid, 6.9 g, yield 42%. MS: m / z 1260.55 (M+H) + .

[0071] Following the synthesis method of complex Pt11 in Example 1, the following tetradentate cyclic platinum(II) complexes were prepared, as shown in Table 1:

[0072] Table 1. Examples of preparation of tetradentate ring platinum(II) complexes

[0073] Theoretical calculations: The geometry of the ground state (S0) molecule was optimized using density functional theory (DFT). DFT calculations were performed using the B3LYP functional, with the C, H, O, and N atoms using the 6-31G(d) basis set and the Pt atom using the LANL2DZ basis set.

[0074] Table 2. Electron and hole distribution and energy levels of some metal complexes of the present invention in the excited state (T1).

[0075] Figure 1 shows the room-temperature emission spectrum of Pt11 in toluene solution; Figure 2 shows the room-temperature emission spectrum of Pt12 in toluene solution; Figure 3 shows the room-temperature emission spectrum of Pt104 in toluene solution; Figure 4 shows the room-temperature emission spectrum of Pt219 in toluene solution; Figure 5 shows the room-temperature emission spectrum of Pt220 in toluene solution. In Figures 1-5, SM is the Yellow-Ries factor, defined as the ratio of the shoulder peak height to the main peak height. According to Figures 1-5 and the data in Table 2, it can be seen that the introduction of the fluorene ring system at the 3,4-position of carbazole expands the conjugated system and increases the distribution of local excited states, which can lower the emission shoulder peak and narrow the half-maximum width, resulting in higher color purity, which can meet the requirements of blue light materials.

[0076] Manufacturing of OLED devices:

[0077] As a reference fabrication method for a device embodiment, this invention involves depositing p-doped material onto the surface or anode of an ITO glass with a light-emitting area of ​​2 mm × 2 mm, or co-evaporating the p-doped material with a hole injection material at a concentration of 1% to 50% to form a 5-100 nm hole injection layer (HIL) and a 5-200 nm hole transport layer (HTL). Subsequently, a 10-100 nm light-emitting layer (EML) (which may contain the compound described in this invention) is formed on the hole transport layer, followed by a 20-200 nm electron transport layer (ETL) and a 50-200 nm cathode. 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, thereby fabricating an OLED device. The OLED is then tested using standard methods. Unless otherwise specified, the device materials involved in this invention can be obtained using known synthesis methods.

[0078] In a preferred embodiment, the structure of the top device example 1 provided by the present invention is as follows: ITO / HT-1:P-5(97:3) / HT-1(126nm) / p-host(5nm) / p-host:ETH-45:Pt11(60:32:8,350nm) / mSiTRz(5nm) / ET-1:Liq(50:50,30nm) / Yb(1nm) / Ag(14nm) / CPL(60nm); the comparison device D-R1 is that Pt11 in device D1 is replaced by R1; the data is shown in Table 3.

[0079] Device Examples 2-62 and Comparative Example 1 were prepared using structures similar to those in Device Example 1, the only difference being that Pt11 in Device Example 1 was replaced with compounds from Table 1. The luminescence properties of the comparative examples and each device example prepared above were tested using standard methods, and the data are shown in Table 3.

[0080] Table 3. Device Light Emitting Characteristics Data Table

[0081] As shown in Table 3, compared with Comparative Example 1, Device Examples 1-62 prepared in this application exhibit excellent device performance in terms of driving voltage, blue light index (BI), and device lifetime; in addition, the color purity of the devices is also greatly improved. The performance improvement of each device example is based on the fact that the specific compound material of this invention has a small emission shoulder and better electron transport capability. It can be seen that using it as a light-emitting layer material to prepare electronic devices can reduce the driving voltage while achieving higher device lifetime and color purity. This indicates that the compound provided by this invention has certain commercial application value. The devices prepared by this invention are all deep blue light devices.

[0082] In a preferred embodiment, the structure of device example 63 provided by the present invention is as follows: ITO / P-4 (10nm) / NPD (60nm) / HTH-85 (5nm) / platinum (II) complex: boron-containing compound: HTH-85:ETH-45 (25nm) (Pt11:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0083] Devices 64-70 were fabricated using structures similar to those in Device Example 63, the only difference being that the platinum(II) complex and boron-containing compound in Device Example 63 were replaced with compounds listed in Table 4. The structural formulas of the devices involved are as follows, and the device structure and luminescence characteristic data are shown in Table 4.

[0084] Table 4. Device Structure and Luminescent Properties Data

[0085] As shown in Table 4, when the compounds of this invention are used as sensitizing materials, together with boron-containing compounds as luminescent materials in devices, the performance of each device is significantly improved. This further demonstrates that the compounds provided by this invention have certain commercial application value. Adding boron-containing compounds to sensitize the device structure can further reduce the CIEy value, thereby improving the purity of the emitted color.

[0086] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A fluorenazine-carbazole tetradentate platinum(II) complex, characterized in that, It has a general formula structure as shown in equation (I): In equation (I), R 1 –R 6 Each can be used independently to represent monosubstituted to the maximum amount of substitution, or no substitution; R 1 –R 6 Each of the following is independently selected from: hydrogen, deuterium, halogen, CN, C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, substituted or unsubstituted C3–C30 heterocycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 alkylsilyl, substituted or unsubstituted C6–C60 arylsilyl; and two adjacent substituents may be linked to form a ring; R a and R b Each is independently selected from hydrogen, deuterium, C1–C30 alkyl, substituted or unsubstituted C1–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, and R a and R b They can be connected to form a ring; R x Selected from C1–C30 alkyl, substituted or unsubstituted C1–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 diarylamino; R x It can be linked with adjacent substituents to form a ring; In formula (I), when each substituent contains a substitution, the substitution is selected from one or more of hydrogen, deuterium, halogen, CN, C1–C14 alkyl, C3–C14 cycloalkyl, C6–C18 aryl, and C6–C18 heteroaryl.

2. The fluorenylcarbazole tetradentate platinum(II) complex according to claim 1, characterized in that, R 1 –R 6 R x , or R a and R b When cyclization occurs, the ring is a substituted or unsubstituted C3-C20 aliphatic ring, a substituted or unsubstituted C6-C20 aromatic ring, a substituted or unsubstituted C3-C20 aromatic heterocyclic ring, or a substituted or unsubstituted C10-C20 fused ring.

3. The fluorenylcarbazole tetradentate platinum(II) complex according to claim 1, characterized in that, R 1 Independently selected from one or more of hydrogen, deuterium, phenyl, and tert-butyl-substituted phenyl groups; R 2 The substituent is independently selected from one or more of hydrogen, deuterium, substituted or unsubstituted C6–C30 aryl, substituted or unsubstituted C6–C30 hetero-N aryl, and trimethylsilyl, wherein the substituent is selected from deuterium, F, methyl, ethyl, propyl, isopropyl, and tert-butyl.

4. The fluorenylcarbazole tetradentate platinum(II) complex according to claim 1, characterized in that, R 3 R 4 Each of the following is independently selected from one or more of hydrogen, deuterium, CN, methyl, ethyl, propyl, tert-butyl, CF3, methyl-substituted or unsubstituted cyclohexyl, carbazolyl-substituted or unsubstituted phenyl, carbazolyl, N-phenylcarbazolyl, substituted or unsubstituted indole, oxaindole, thioindole, substituted or unsubstituted N-oxaindole, and diphenylamino, wherein the substituent is selected from deuterium, F, methyl, ethyl, propyl, tert-butyl, fluorenyl, and carbazolyl.

5. The fluorenylcarbazole tetradentate platinum(II) complex according to claim 1, characterized in that, The R 5 The substituent is independently selected from deuterium, methyl, ethyl, propyl, tert-butyl, deuterated tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, dibenzofuranyl, dibenzothiopheneyl, trimethylsilyl, triarylsilyl, tetraarylsilyl, substituted or unsubstituted carbazole, methyl-substituted tetrahydronaphthyl, diisopropylamino, and cyclopentane, wherein the substituent is selected from one or more of deuterium, methyl, ethyl, propyl, tert-butyl, deuterated tert-butyl, and adamantyl.

6. The fluorenylcarbazole tetradentate platinum(II) complex according to claim 1, characterized in that, R 6 The substituent is independently selected from one or more of hydrogen, deuterium, substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, substituted or unsubstituted C3–C30 heterocycloalkyl, substituted or unsubstituted C6–C30 aryl, substituted or unsubstituted C6–C30 heteroaryl, substituted or unsubstituted C6–C30 arylamino, C1–C30 alkylsilyl, and C6–C30 arylsilyl, wherein the substituent is selected from deuterium, methyl, ethyl, propyl, tert-butyl, and adamantyl.

7. The fluorenylcarbazole tetradentate platinum(II) complex according to claim 1, characterized in that, R a and R b Each is independently selected from one or more of hydrogen, deuterium, CD3, F, CF3, CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, phenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, and di-tert-butylphenyl; R a and R b It can be selectively linked into cyclopentane, cyclohexane, adamantyl, fluorenyl, and tert-butylfluorenyl.

8. The fluorenylcarbazole tetradentate platinum(II) complex according to claim 1, characterized in that, R x The substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C1–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 arylamino; when substituted, the substituted ...

9. The fluorenylcarbazole tetradentate platinum(II) complex according to claim 1, characterized in that, The fluorenylcarbazole tetradentate platinum(II) complex is selected from any of the following chemical structures, where "D" represents deuterium and Ph represents phenyl:

10. The use of the fluorenylcarbazole tetradentate platinum(II) complex according to any one of claims 1-9 in the preparation of electronic devices.

11. An organic electroluminescent device, characterized in that, The organic electroluminescent device comprises a cathode, an anode, and an organic functional layer between them; the organic functional layer contains the fluorenylcarbazole tetradentate platinum(II) complex as described in any one of claims 1-9.

12. The organic electroluminescent device according to claim 11, characterized in that, The organic functional layer contains a fluorescent dopant material, which is a boron-containing compound.

13. An organic optoelectronic device, characterized in that, The organic optoelectronic device comprises: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; and a second electrode on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises the fluorene-carbazole tetradentate platinum(II) complex according to any one of claims 1-9.

14. The organic optoelectronic device according to claim 13, characterized in that, The organic light-emitting functional layer also contains a fluorescent dopant material, which is a boron-containing compound.

15. A composition, characterized in that, The composition comprises the fluorenylcarbazole tetradentate platinum(II) complex according to any one of claims 1-9.

16. A formulation, characterized in that, The formulation comprises the fluorenylcarbazole tetradentate platinum(II) complex according to any one of claims 1-9.

17. A display or lighting device, characterized in that, The device comprises one or more of the organic electroluminescent device of claim 11 or the organic optoelectronic device of claim 13.

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