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

Abstract

The present invention relates to the technical field of preparation of organic electroluminescent materials, and particularly, to a fluorenocarbazole tetradentate platinum(II) complex-based organic light-emitting diode material, device, and apparatus. In the present invention, a tetradentate platinum(II) complex-based phosphorescent material is obtained by introducing a fluorene ring system at the 5,6-position of carbazole, so as to increase the proportion of components of the localized state (3LE) 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 materials provided by the present invention all have good chemical stability and thermal stability, thereby facilitating the preparation of evaporation-type OLED devices. The organic electroluminescent device manufactured by using the complex of the present invention as a light-emitting layer has a significant improvement in both the current efficiency and service life, and can also reduce the turn-on voltage.

Description

Fluorenylcarbazole tetradentate platinum(II) complex organic light-emitting diode materials, devices and apparatus Technical Field

[0001] This invention belongs to the field of organic electroluminescent material preparation technology, specifically relating to an organic light-emitting diode material, device, and apparatus of a fluorenecarbazole tetradentate platinum(II) complex. 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. Furthermore, they offer 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. In addition, they have 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 electronic products 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. The host material generally has a higher energy level than the guest material, transferring energy from the host to the guest material, thus exciting the guest material 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 phosphorescent organic materials, mCBP (3,3′-bis(9-carbazolyl)-biphenyl) and 2,6-mCPy (2,6-bis(9-carbazolyl)-pyridine), 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 are iridium(III) complex molecules, and their quantities are limited. 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. In addition, 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, greatly decreasing the utilization rate of the raw material IrCl3·H2O and 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 of platinum(II) complex phosphorescent materials. In summary, the preparation cost of platinum(II) complex phosphorescent materials is significantly 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 reducing the height of the shoulder peak in the emission spectrum to improve the color purity of the material's molecular luminescence. This issue is particularly important for blue and deep blue luminescent materials, as it greatly impacts the efficiency and energy utilization of top-emitting devices for commercial applications. Therefore, the development of novel phosphorescent platinum(II) complexes is urgently needed. Summary of the Invention

[0004] In view of this, the present invention provides an organic light-emitting diode material, device, and apparatus of a fluorene-carbazole tetradentate platinum(II) complex. The present invention obtains a tetradentate platinum(II) complex phosphorescent material by introducing a fluorene ring system at the 5,6-position of carbazole. This improves the localization of the excited triplet state in the tetradentate platinum(II) complex. 3 The proportion of LE components results in a low shoulder peak, improving the purity of the material's luminescent color and enhancing its stability. The complexes provided in this invention exhibit excellent chemical and thermal stability, facilitating the fabrication of vapor-deposited OLED devices. Using the complexes of this invention as the luminescent layer in organic electroluminescent devices significantly improves current efficiency and lifetime, while also reducing the turn-on voltage.

[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 7 Each can be used independently to represent monosubstituted to the maximum amount of substitution, or no substitution; R 1 –R 7 Each is independently selected from one or more of the following: hydrogen, deuterium, halogen, CN, substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 arylamino, C6–C60 arylsilyl, and C6–C60 alkylsilyl;

[0008] R a and R b Each 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 C6–C60 aryl, and substituted or unsubstituted C6–C60 heteroaryl.

[0009] R xThe substituents are selected from one or more of the following: substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 diarylamino, and C6–C60 arylsilyl; two or more substituents in formula (I) may be linked together to form a cyclic structure; when each substituent in formula (I) contains a substituted substance, the substituted substance is selected from one or more of the following: hydrogen, deuterium, halogen, CN, C1–C14 alkyl, C3–C14 cycloalkyl, C6–C18 aryl, and C6–C18 heteroaryl.

[0010] Furthermore, R 1 -R 7 Each is independently selected from one or more of the following: 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, 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, cyclopentane, cyclohexane, adamantyl, phenyl, biphenyl, tert-phenyl, naphthyl, methyl-substituted tetrahydronaphthyl, indyl, methyl-substituted indyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, diarylamino, and triphenylsilane.

[0011] Furthermore, R x 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, 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, cyclopentane, cyclohexane, adamantyl, phenyl, biphenyl, tert-phenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, naphthyl, methyl-substituted tetrahydronaphthyl, indene, methyl-substituted indene, oxainyl, thiainyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, diarylamino, triphenylsilane; R x It can fuse with adjacent substitution sites to form substituted or unsubstituted benzofuranyl, benzothiophenyl, and benzopyrroleyl groups.

[0012] R a and R bEach 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.

[0013] In formula (I), all hydrogen atoms in the substituents can be replaced by deuterium.

[0014] Preferably, the present invention provides a fluorenylcarbazole tetradentate platinum(II) complex selected from any one of the following chemical structures: where "D" represents deuterium:

[0015] Furthermore, the present invention also provides the application of the fluorenylcarbazole tetradentate platinum (II) complex having the structure shown in formula (I) in electronic devices.

[0016] 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).

[0017] 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 fluorenylcarbazole tetradentate platinum (II) complex having the structure shown in formula (I) as described above.

[0018] Preferably, the organic functional layer comprises a light-emitting layer containing a fluorenylcarbazole tetradentate platinum(II) complex having the structure shown in formula (I) as described above.

[0019] Furthermore, the light-emitting layer also contains a fluorescent dopant material; the fluorescent dopant material is preferably a boron-containing organic luminescent material.

[0020] 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 fluorene-carbazole 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.

[0021] 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.

[0022] 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.

[0023] The present invention also provides a composition comprising a fluorenylcarbazole 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.

[0024] The present invention also provides a formulation comprising a fluorenylcarbazole 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.

[0025] 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.

[0026] The present invention also provides a display or lighting device comprising one or more of the organic optoelectronic devices described above.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] This invention introduces a fluorene ring system at the 5,6-position of carbazole and a substituent at the ortho position of the benzene ring in the upper left corner, thereby obtaining a novel tetradentate platinum(II) complex blue phosphorescent material, which also improves the device stability of the material. Firstly, the introduction of a fluorene ring system at the 5,6-position of carbazole can appropriately improve 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 5,6-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 fabricated using the platinum(II) complex of this invention as the luminescent layer show significant improvements in current efficiency and lifetime, while also reducing the turn-on voltage. Attached Figure Description

[0029] Figure 1 shows the room temperature emission spectra of some compounds of the present invention and comparative compound R1 in toluene solution. Detailed Implementation

[0030] 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.

[0031] 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.

[0032] 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).

[0033] 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 1 If 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] The cyclic structure described in this invention refers to two groups linked together by chemical bonds and optionally aromatized. Examples are shown below:

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] Synthesis Examples

[0045] 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.

[0046] 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.

[0047] 1 H NMR (500MHz), 1 H NMR (400MHz), 13C10 NMR (126 MHz) spectra were measured on an ANANCE III (500 M) nuclear magnetic resonance spectrometer; unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for all 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) were used as internal standards. 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.

[0048] Synthetic route

[0049] Example 1: Tetradentate Platinum(II) Complex Phosphorescent Material Pt11

[0050] The synthesis route is as follows:

[0051] Synthesis of the intermediate (SBF-Bpin): 1-Bromo-9,9-spirodifluorene (5.0 g, 12.6 mmol, 1.0 equivalent) was dissolved in tetrahydrofuran (100 mL) in a reaction flask. After three N2 purgings, the mixture was cooled to -78 °C. Then, n-butyllithium (6 mL, 15.1 mmol, 2.5 M) was slowly added, and the mixture was stirred for 1 h. Finally, isopropanol pinacol borate (3.52 g, 18.90 mmol, 1.5 equivalent) was added. The reaction was then allowed to proceed at room temperature for 12 h, and the reaction was stopped. After cooling to room temperature, the organic phase was separated, concentrated, and purified by silica gel column chromatography to give 3.0 g of a white solid (54% yield). This solid was used directly in subsequent reactions. Molecular weight [M+H] + :316.1.

[0052] Synthesis of intermediate (SBF-NO2): SBF-Bpin (3.0 g, 9.51 mmol, 1.2 equivalences), 4-bromo-3-nitrobenzene ether (1.84 g, 7.92 mmol, 1.0 equivalences), tetrakis(triphenylphosphine)palladium (138 mg, 0.16 mmol, 2 mol%), potassium carbonate (2.19 g, 15.84 mmol, 2.0 equivalences), dioxane (40 mL), and water (10 mL) were added to a reaction flask. The reaction was stopped at 90 °C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 3.3 g of a yellow solid, yield 89%. 1 H NMR (500MHz, CDCl3): δ (ppm) 3.76 (s, 3H), 6.03 (d, J = 8.5Hz, 1H), 6.38 (dd, J = 8.5, 3.0Hz, 1H), 6.55 (d, J = 7.5Hz ,1H),6.67(d,J=7.5Hz,1H),6.75(d,J=7.5Hz,1H),6.94(dd,J=7.5,1.0Hz,1H),7.00(td,J=7.5,1.0Hz,1H),7. 03–7.09(m,2H),7.14(d,J=2.5Hz,1H),7.19(td,J=7.5,1.0Hz,1H),7.23(td,J=7.5,1.0Hz,1H),7.33–7.37(m, 2H), 7.40 (d, J=7.5Hz, 1H), 7.47 (t, J=7.5Hz, 1H), 7.87 (d, J=7.5Hz, 1H), 7.91 (dd, J=7.5, 1.0Hz, 1H). Molecular weight [M+H] + :468.5.

[0053] Synthesis of intermediate (SBF-Cz): (SBF-NO2) (3.3 g, 7.06 mmol, 1.0 equivalent) and triphenylphosphine (5.56 g, 21.18 mmol, 3.0 equivalent) were added to a reaction flask, along with 50 mL of o-dichlorobenzene. The reaction was carried out at 180 °C for 24 hours, then stopped. After cooling to room temperature, the organic phase was separated, concentrated, and purified by silica gel column chromatography to give 2.7 g of a brown solid, yield 88%. 1H NMR (400MHz, CDCl3): δ (ppm) 3.71 (s, 3H), 6.28 (dd, J=8.8, 2.4Hz, 1H), 6.43 (d, J= 8.8Hz,1H),6.59(d,J=7.6Hz,1H),6.68(d,J=2.4Hz,1H),6.76(d,J=7.6Hz,2H),6 .94–7.05(m,3H),7.29(t,J=7.2Hz,1H),7.37(t,J=7.6Hz,2H),7.47(d,J=8.0Hz, 1H), 7.80 (d, J=7.6Hz, 1H), 7.89 (d, J=8.0Hz, 1H), 7.99 (d, J=7.2Hz, 3H). Molecular weight [M+H] + :436.2.

[0054] Synthesis of intermediate (SBF-OMe): (SBF-Cz) (2.7 g, 6.2 mmol, 1.0 equivalent), 4-(tert-butyl)-2-chloropyridine (1.26 g, 7.44 mmol, 1.2 equivalent), tris(dibenzylacetone)palladium (174 mg, 0.19 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (156 mg, 0.38 mmol, 6 mol%), and sodium tert-butoxide (1.19 g, 12.4 mmol, 2.0 equivalent) were added to a reaction flask, followed by toluene (50 mL). The reaction was carried out at 110 °C for 48 hours, then stopped. After cooling to room temperature, the organic phase was separated, concentrated, and purified by silica gel column chromatography to give 3.0 g of a brown solid (85% yield). This solid was used directly in subsequent reactions. Molecular weight [M+H] + 569.3.

[0055] Synthesis of intermediate (SBF-OH): 3.0 g (SBF-OMe, 5.28 mmol, 1.0 equivalent), pyridine hydrochloride (6.10 g, 52.8 mmol, 10.0 equivalent), and 5 mL of 1,3-dimethyl-2-imidazolinone were added to a reaction flask. The reaction was carried out at 180 °C for 48 hours, then stopped. After cooling to room temperature, the organic phase was separated, concentrated, and purified by silica gel column chromatography to give 2.6 g of a brown solid, yield 89%. 1H NMR (400MHz, DMSO): δ (ppm) 1.37 (s, 9H), 6.07 (dd, J = 8.4, 2.0Hz, 1H), 6.26 (d, J = 8.8Hz, 1H), 6.44 (d, J = 7.6Hz, 1H ),6.65(d,J=7.2Hz,2H),6.81(d,J=2.4Hz,1H),7.00(dd,J=7.2,1.0Hz,1H),7.09(td,J=7.2,0.8Hz,2H),7.29–7. 35(m,1H),7.45(td,J=7.6,1.2Hz,2H),7.53(dd,J=5.2,1.6Hz,1H),7.65(d,J=1.6Hz,1H),7.73(d,J=8.4Hz,1H), 7.94(d,J=7.6Hz,1H),8.03(d,J=8.4Hz,1H),8.19(d,J=7.6Hz,2H),8.64(d,J=5.2Hz,1H),9.48(s,1H).Molecular weight [M+H] + :555.2.

[0056] Synthesis of intermediate (SBF-Cl): (SBF-OH) (2.6 g, 4.69 mmol, 1.0 equivalent), 3-chloro-5-bromo-tert-butylbenzene (1.35 g, 7.04 mmol, 1.5 equivalent), 2-pyridinecarboxylic acid (116 mg, 0.94 mmol, 20 mmol%), cuprous iodide (90 mg, 0.47 mmol, 10 mmol%), and potassium phosphate (1.99 g, 9.38 mmol, 2.0 equivalent) were added to a reaction flask, followed by dimethyl sulfoxide (30 mL). The reaction was carried out at 110 °C for 12 hours, then stopped. After cooling to room temperature, the organic phase was separated, concentrated, and purified by silica gel column chromatography to give 2.65 g of a white solid (85% yield). 1 H NMR (400MHz, CDCl3): δ (ppm) 1.34 (s, 9H), 6.40 (dd, J = 8.8, 2.4Hz, 1H), 6.56 (d, J = 8.4Hz, 1H), 6 .60(d,J=7.6Hz,1H),6.74–6.83(m,3H),6.88(s,1H),7.00(t,J=8.0Hz,2H),7.04–7.10(m,3H) 7.14 (t, J = 8.0 Hz, 1H), 7.28–7.33 (m, 2H), 7.40 (t, J = 7.6 Hz, 2H), 7.50 (s, 1H), 7.83 (t, J = 8.0 Hz, 2H), 7.96 (d, J = 8.4 Hz, 1H), 7.99 (d, J = 7.2 Hz, 2H), 8.59 (d, J = 5.2 Hz, 1H). Molecular weight [M+H]+: 665.2.

[0057] Synthesis of intermediate L11-NH: NH2-1 (500 mg, 1.17 mmol, 1.2 equivalences) was added to a reaction flask, followed by SBF-Cl (651 mg, 0.98 mmol, 1.0 equivalences), tris(dibenzylacetone)dipalladium (37 mg, 0.04 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (33 mg, 0.08 mmol, 6 mol%), and sodium tert-butoxide (225 mg, 2.34 mmol, 2.0 equivalences), and then toluene (5 mL). The reaction was carried out at 110 °C for 3 hours, then stopped. After cooling to room temperature, the mixture was concentrated and purified by silica gel column chromatography to give 900 mg of a white solid, in 87% yield. This solid was used directly in subsequent reactions.

[0058] Synthesis of ligand L-Pt11: L11-NH (900 mg, 0.85 mmol, 1.0 equivalent), ammonium hexafluorophosphate (185 mg, 1.70 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was stopped at 70 °C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 868 mg of a white solid, yield 84%. Molecular weight [M] + :1070.6.

[0059] Synthesis of Pt11: L-Pt11 (868 mg, 0.71 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum(II) chloride (281 mg, 0.75 mmol, 1.05 equivalent), and sodium acetate (175 mg, 2.13 mmol, 3.0 equivalent) were added to a reaction flask, followed by diethylene glycol dimethyl ether (10 mL). The mixture was bubbled with nitrogen to remove oxygen for 30 minutes. The reaction was stopped at 120 °C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 340 mg of a pale yellow solid, yield 38%. Molecular weight [M] + :1262.5.

[0060] Example 2: Tetradentate Platinum(II) Complex Phosphorescent Material Pt23

[0061] The synthesis route is as follows:

[0062] Synthesis of intermediate L23-NH: NH2-2 (383 mg, 0.9 mmol, 1.2 equivalences) was added to a reaction flask, followed by SBF-Cl (500 mg, 0.75 mmol, 1.0 equivalences), tris(dibenzylacetone)palladium (18 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxybiphenyl (16 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (144 mg, 1.5 mmol, 2.0 equivalences), and then toluene (5 mL). The reaction was carried out at 110 °C for 3 hours, then stopped. After cooling to room temperature, the mixture was concentrated and purified by silica gel column chromatography to give 704 mg of a white solid, in 89% yield. This solid was used directly in subsequent reactions.

[0063] Synthesis of ligand L-Pt23: L23-NH (704 mg, 0.67 mmol, 1.0 equivalent), ammonium hexafluorophosphate (218 mg, 1.34 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was stopped at 70 °C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 649 mg of a white solid, yield 80%. Molecular weight [M] + :1065.5.

[0064] Synthesis of Pt23: L-Pt23 (704 mg, 0.58 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum(II) chloride (228 mg, 0.61 mmol, 1.05 equivalent), and sodium acetate (143 mg, 1.74 mmol, 3.0 equivalent) were added to a reaction flask, followed by diethylene glycol dimethyl ether (10 mL). The mixture was bubbled with nitrogen to remove oxygen for 30 minutes. The reaction was stopped at 120 °C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 248 mg of a pale yellow solid, yield 34%. Molecular weight [M] + :1259.5.

[0065] Example 3: Tetradentate Platinum(II) Complex Phosphorescent Material Pt35

[0066] The synthesis route is as follows:

[0067] Synthesis of intermediate L35-NH: NH2-3 (462 mg, 0.9 mmol, 1.2 equivalences) was added to a reaction flask, followed by SBF-Cl (500 mg, 0.75 mmol, 1.0 equivalences), tris(dibenzylacetone)palladium (18 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (16 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (144 mg, 1.5 mmol, 2.0 equivalences), and then toluene (5 mL). The reaction was carried out at 110 °C for 3 hours, then stopped. After cooling to room temperature, the mixture was concentrated and purified by silica gel column chromatography to give 683 mg of a white solid, in 82% yield. This solid was used directly in subsequent reactions.

[0068] Synthesis of ligand L-Pt35: L35-NH (683 mg, 0.61 mmol, 1.0 equivalent), ammonium hexafluorophosphate (199 mg, 1.22 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was stopped at 70 °C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 673 mg of a white solid, yield 87%. Molecular weight [M] + :1121.6.

[0069] Synthesis of Pt35: L-Pt35 (673 mg, 0.53 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum(II) chloride (210 mg, 0.56 mmol, 1.05 equivalent), and sodium acetate (130 mg, 1.59 mmol, 3.0 equivalent) were added to a reaction flask, followed by diethylene glycol dimethyl ether (10 mL). The mixture was bubbled with nitrogen to remove oxygen for 30 minutes. The reaction was stopped at 120 °C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 216 mg of a pale yellow solid, yield 31%. Molecular weight [M] + :1314.6.

[0070] Example 4: Tetradentate Platinum(II) Complex Phosphorescent Material Pt107

[0071] The synthesis route is as follows:

[0072] Synthesis of intermediate L107-NH: NH2-4 (483 mg, 0.9 mmol, 1.2 equivalences) was added to a reaction flask, followed by SBF-Cl (500 mg, 0.75 mmol, 1.0 equivalences), tris(dibenzylacetone)dipalladium (18 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (16 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (144 mg, 1.5 mmol, 2.0 equivalences), and then toluene (5 mL). The reaction was carried out at 110 °C for 3 hours, then stopped. After cooling to room temperature, the mixture was concentrated and purified by silica gel column chromatography to give 751 mg of a white solid, in 86% yield. This solid was used directly in subsequent reactions.

[0073] Synthesis of ligand L-Pt107: L107-NH (751 mg, 0.64 mmol, 1.0 equivalent), ammonium hexafluorophosphate (209 mg, 1.28 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was stopped at 70 °C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 745 mg of a white solid, yield 88%. Molecular weight [M] + :1176.6.

[0074] Synthesis of Pt107: L-Pt107 (745 mg, 0.56 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum(II) chloride (221 mg, 0.59 mmol, 1.05 equivalent), and sodium acetate (139 mg, 1.68 mmol, 3.0 equivalent) were added to a reaction flask, followed by diethylene glycol dimethyl ether (10 mL). The mixture was bubbled with nitrogen to remove oxygen for 30 minutes. The reaction was stopped at 120 °C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 292 mg of a pale yellow solid, yield 38%. Molecular weight [M] + :1370.5.

[0075] Example 5: Tetradentate Platinum(II) Complex Phosphorescent Material Pt127

[0076] The synthesis route is as follows:

[0077] Synthesis of intermediate L127-NH: NH2-5 (302 mg, 0.9 mmol, 1.2 equivalences) was added to a reaction flask, followed by SBF-Cl (500 mg, 0.75 mmol, 1.0 equivalences), tris(dibenzylacetone)dipalladium (18 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (16 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (144 mg, 1.5 mmol, 2.0 equivalences), and then toluene (5 mL). The reaction was carried out at 110 °C for 3 hours, then stopped. After cooling to room temperature, the mixture was concentrated and purified by silica gel column chromatography to give 651 mg of a white solid (90% yield). This solid was used directly in subsequent reactions.

[0078] Synthesis of ligand L-Pt127: L127-NH (651 mg, 0.68 mmol, 1.0 equivalent), ammonium hexafluorophosphate (222 mg, 1.36 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was stopped at 70 °C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 679 mg of a white solid, yield 89%. Molecular weight [M] + :975.4.

[0079] Synthesis of Pt127: L-Pt127 (679 mg, 0.61 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum(II) chloride (239 mg, 0.64 mmol, 1.05 equivalent), and sodium acetate (150 mg, 1.83 mmol, 3.0 equivalent) were added to a reaction flask, followed by diethylene glycol dimethyl ether (10 mL). The mixture was bubbled with nitrogen to remove oxygen for 30 minutes. The reaction was stopped at 120 °C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 292 mg of a pale yellow solid, yield 41%. Molecular weight [M] + :1168.4.

[0080] Example 6: Tetradentate Platinum(II) Complex Phosphorescent Material Pt131

[0081] The synthesis route is as follows:

[0082] Synthesis of intermediate L131-NH: NH2-6 (352 mg, 0.9 mmol, 1.2 equivalences) was added to a reaction flask, followed by SBF-Cl (500 mg, 0.75 mmol, 1.0 equivalences), tris(dibenzylacetone)palladium (18 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (16 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (144 mg, 1.5 mmol, 2.0 equivalences), and then toluene (5 mL). The reaction was carried out at 110 °C for 3 hours, then stopped. After cooling to room temperature, the mixture was concentrated and purified by silica gel column chromatography to give 697 mg of a white solid, in 91% yield. This solid was used directly in subsequent reactions.

[0083] Synthesis of ligand L-Pt31: L131-NH (697 mg, 0.68 mmol, 1.0 equivalent), ammonium hexafluorophosphate (222 mg, 1.36 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was stopped at 70 °C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 737 mg of a white solid, yield 92%. Molecular weight [M] + :1031.5.

[0084] Synthesis of Pt131: L-Pt131 (737 mg, 0.63 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum(II) chloride (239 mg, 0.66 mmol, 1.05 equivalent), and sodium acetate (155 mg, 1.89 mmol, 3.0 equivalent) were added to a reaction flask, followed by diethylene glycol dimethyl ether (10 mL). The mixture was bubbled with nitrogen to remove oxygen for 30 minutes. The reaction was stopped at 120 °C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 332 mg of a pale yellow solid, yield 43%. Molecular weight [M] + :1225.4.

[0085] Example 7: Tetradentate Platinum(II) Complex Phosphorescent Material Pt199

[0086] The synthesis route is as follows:

[0087] Synthesis of intermediate L199-NH: NH₇₇ (554 mg, 0.9 mmol, 1.2 equivalences) was added to a reaction flask, followed by SBF-Cl (500 mg, 0.75 mmol, 1.0 equivalences), tris(dibenzylacetone)palladium (18 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (16 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (144 mg, 1.5 mmol, 2.0 equivalences), and then toluene (5 mL). The reaction was carried out at 110 °C for 3 hours, then stopped. After cooling to room temperature, the mixture was concentrated and purified by silica gel column chromatography to give 793 mg of a white solid, in 85% yield. This solid was used directly in subsequent reactions.

[0088] Synthesis of ligand L-Pt199: L199-NH (793 mg, 0.64 mmol, 1.0 equivalent), ammonium hexafluorophosphate (209 mg, 1.28 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was stopped at 70 °C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 825 mg of a white solid, yield 92%. 1 H NMR (400MHz, CDCl3): δ (ppm) 1.01 (s, 36H), 1.39 (s, 9H), 1.50 (s, 9H), 6.40–6.45 (m, 2H), 6.56 (d, J = 8 .0Hz,1H),6.62(dd,J=8.8,3.6Hz,2H),6.80(d,J=7.6Hz,2H),6.91–7.09(m,9H),7.18(s,2H),7.23(s ,1H),7.29–7.40(m,6H),7.42(d,J=7.6Hz,2H),7.57(d,J=1.6Hz,1H),7.67(s,2H),7.82(dd,J=11.6 ,7.6Hz,2H),7.98(d,J=8.4Hz,1H),8.02(d,J=7.6Hz,2H),8.59(d,J=5.2Hz,1H),9.08(s,1H).Molecular weight [M] + :1256.7.

[0089] Synthesis of Pt199: L-Pt199 (825 mg, 0.59 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum(II) chloride (239 mg, 0.66 mmol, 1.05 equivalent), and sodium acetate (155 mg, 1.89 mmol, 3.0 equivalent) were added to a reaction flask, followed by diethylene glycol dimethyl ether (10 mL). The mixture was bubbled with nitrogen to remove oxygen for 30 minutes. The reaction was stopped at 120 °C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 342 mg of a pale yellow solid, yield 40%. Molecular weight [M] + :1449.7.

[0090] Example 8: Tetradentate Platinum(II) Complex Phosphorescent Material Pt12

[0091] The synthesis route is as follows:

[0092] Pt12 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product L12-NH, a light green foamy solid, was obtained in 981 mg, with a yield of 86%. The target product L-Pt12, a light green foamy solid, was obtained in 841 mg, with a yield of 82%. Molecular weight [M] + 1179.7. Target product Pt12, yellow solid, 385 mg, yield 31%. Molecular weight [M+H] + :1373.6.

[0093] Example 9: Tetradentate Platinum(II) Complex Phosphorescent Material Pt22

[0094] The synthesis route is as follows:

[0095] Pt22 was synthesized following the synthetic steps and reaction conditions of the complexes in Examples 1-15. The target product L22-NH was obtained as 883 mg of a light green, foamy solid, with a yield of 85%. The target product L-Pt12 was obtained as 893 mg of a light green, foamy solid, with a yield of 89%. Molecular weight [M] + 1036.4. Target product Pt22, yellow solid, 385 mg, yield 37%. Molecular weight [M+H] + :1229.5.

[0096] Example 10: Tetradentate Platinum(II) Complex Phosphorescent Material Pt37

[0097] The synthesis route is as follows:

[0098] Pt37 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product L37-NH was obtained as 893 mg of a light green, foamy solid, with a yield of 88%. The target product L-Pt37 was obtained as 872 mg of a light green, foamy solid, with a yield of 84%. Molecular weight [M] + 1037.6. Target product Pt37, yellow solid, 389 mg, yield 39%. Molecular weight [M+H] + :1231.6.

[0099] Example 11: Tetradentate Platinum(II) Complex Phosphorescent Material Pt88

[0100] The synthesis route is as follows:

[0101] Pt88 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product L88-NH was obtained as 853 mg of a light green, foamy solid, with a yield of 83%. The target product L-Pt88 was obtained as 872 mg of a light green, foamy solid, with a yield of 87%. Molecular weight [M] + 1243.8. Target product Pt88, yellow solid, 403 mg, yield 41%. Molecular weight [M+H] + :1467.8.

[0102] Example 12: Tetradentate Platinum(II) Complex Phosphorescent Material Pt114

[0103] The synthesis route is as follows:

[0104] Pt114 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product L114-NH, a light green foamy solid, was obtained in 841 mg yield (81%). The target product L-Pt114, a light green foamy solid, was obtained in 863 mg yield (82%). Molecular weight [M] + 1011.5. Target product Pt114, yellow solid, 335 mg, yield 33%. Molecular weight [M+H] + :1205.5.

[0105] Example 13: Tetradentate Platinum(II) Complex Phosphorescent Material Pt155

[0106] The synthesis route is as follows:

[0107] Pt155 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product L155-NH, a light green foamy solid, was obtained in 846 mg, with a yield of 85%. The target product L-Pt155, a light green foamy solid, was obtained in 867 mg, with a yield of 86%. Molecular weight [M] + 1199.7. Target product Pt155, yellow solid, 435 mg, yield 43%. Molecular weight [M+H] + :1393.6.

[0108] Example 14: Tetradentate Platinum(II) Complex Phosphorescent Material Pt177

[0109] The synthesis route is as follows:

[0110] Pt177 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product L155-NH was obtained as 876 mg of a light green, foamy solid, with a yield of 84%. The target product L-Pt177 was obtained as 869 mg of a light green, foamy solid, with a yield of 82%. Molecular weight [M] + 1033.6. Target product Pt177, yellow solid, 335 mg, yield 34%. Molecular weight [M+H] + :1227.5.

[0111] Example 15: Tetradentate Platinum(II) Complex Phosphorescent Material Pt299

[0112] The synthesis route is as follows:

[0113] Pt299 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product L299-NH, a light green foamy solid, was obtained in 878 mg, with a yield of 87%. The target product L-Pt299, a light green foamy solid, was obtained in 899 mg, with a yield of 85%. Molecular weight [M] + 1288.7. Target product Pt299, yellow solid, 355 mg, yield 37%. Molecular weight [M+H] + :1482.6.

[0114] Example 16: Synthesis of Pt4

[0115] Pt4 was synthesized following the synthesis steps and reaction conditions of the complexes in Examples 1-15. The target product was obtained as a yellow solid, 305 mg, with a yield of 32%. Molecular weight [M+H] + :1486.9.

[0116] Example 17: Synthesis of Pt67

[0117] Pt67 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 321 mg, with a yield of 38%. Molecular weight [M+H] + :1313.8.

[0118] Example 18: Synthesis of Pt69

[0119] Pt69 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 362 mg, with a yield of 37%. Molecular weight [M+H] + :1190.6.

[0120] Example 19: Synthesis of Pt92

[0121] Pt92 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 395 mg, with a yield of 43%. Molecular weight [M+H] + :1440.8.

[0122] Example 20: Synthesis of Pt97

[0123] Pt97 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 364 mg, in yield of 35%. Molecular weight [M+H] + :1231.6.

[0124] Example 21: Synthesis of Pt100

[0125] Pt100 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 371 mg, with a yield of 33%. Molecular weight [M+H] + :1273.9.

[0126] Example 22: Synthesis of Pt103

[0127] Pt103 was synthesized following the synthesis steps and reaction conditions of the complexes in Examples 1-15. The target product was obtained as a yellow solid, 405 mg, with a yield of 44%. Molecular weight [M+H] + :1350.5.

[0128] Example 23: Synthesis of Pt110

[0129] Pt110 was synthesized following the synthesis steps and reaction conditions of the complexes in Examples 1-15. The target product was obtained as a yellow solid, 343 mg, with a yield of 31%. Molecular weight [M+H]+ :1395.4.

[0130] Example 24: Synthesis of Pt116

[0131] Pt116 was synthesized following the synthetic steps and reaction conditions of the complexes in Examples 1-15. The target product was obtained as a yellow solid, 389 mg, with a yield of 37%. Molecular weight [M+H] + :1386.7.

[0132] Example 25: Synthesis of Pt117

[0133] Pt117 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 364 mg, with a yield of 34%. Molecular weight [M+H] + :1047.3.

[0134] Example 26: Synthesis of Pt140

[0135] Pt140 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 375 mg, in yield of 36%. Molecular weight [M+H] + :1393.6.

[0136] Example 27: Synthesis of Pt143

[0137] Pt143 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 396 mg, with a yield of 38%. Molecular weight [M+H] + :1355.6.

[0138] Example 28: Synthesis of Pt145

[0139] Pt145 was synthesized following the synthetic steps and reaction conditions of the complexes in Examples 1-15. The target product was obtained as a yellow solid, 372 mg, in yield of 36%. Molecular weight [M+H] + :1386.7.

[0140] Example 29: Synthesis of Pt161

[0141] Pt161 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 366 mg, with a yield of 37%. Molecular weight [M+H] + :1331.6.

[0142] Example 30: Synthesis of Pt214

[0143] Pt214 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 381 mg, with a yield of 38%. Molecular weight [M+H] + :1187.7.

[0144] Example 31: Synthesis of Pt220

[0145] Pt220 was synthesized following the synthesis steps and reaction conditions of the complexes in Examples 1-15. The target product was obtained as a yellow solid, 402 mg, with a yield of 39%. Molecular weight [M+H] + :1197.5.

[0146] Example 32: Synthesis of Pt223

[0147] Pt223 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 376 mg, with a yield of 36%. Molecular weight [M+H] + :1286.5.

[0148] Example 33: Synthesis of Pt256

[0149] Pt256 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 391 mg, in 40% yield. Molecular weight [M+H] + :1449.7.

[0150] Example 34: Synthesis of Pt287

[0151] Pt287 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 403 mg, with a yield of 42%. Molecular weight [M+H] + :1234.5.

[0152] Example 35: Synthesis of Pt351

[0153] Pt351 was synthesized following the synthetic steps and reaction conditions of the complexes in Examples 1-15. The target product was obtained as a yellow solid, 395 mg, with a yield of 37%. Molecular weight [M+H] + :1368.6.

[0154] Example 36: Synthesis of Pt369

[0155] Pt369 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 322 mg, with a yield of 32%. Molecular weight [M+H] + :1230.6.

[0156] Example 37: Synthesis of Pt371

[0157] Pt371 was synthesized following the synthetic steps and reaction conditions of the complexes in Examples 1-15. The target product was obtained as a yellow solid, 357 mg, with a yield of 38%. Molecular weight [M+H] + :1397.6.

[0158] Example 38: Synthesis of Pt373

[0159] Pt373 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 381 mg, with a yield of 37%. Molecular weight [M+H] + :1395.5.

[0160] Example 39: Synthesis of Pt380

[0161] Pt380 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 390 mg, with a yield of 39%. Molecular weight [M+H] + :1490.9.

[0162] Example 40: Synthesis of Pt382

[0163] Pt382 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 357 mg, with a yield of 33%. Molecular weight [M+H] + :1618.8.

[0164] Example 41: Synthesis of Pt383

[0165] Pt383 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 363 mg, with a yield of 33%. Molecular weight [M+H] + :1670.9.

[0166] Example 42: Synthesis of Pt384

[0167] Pt384 was synthesized following the synthetic steps and reaction conditions of Examples 1-15. The target product was obtained as a yellow solid, 342 mg, in 30% yield. Molecular weight [M+H] + :1645.7.

[0168] Theoretical calculations demonstrate that 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.

[0169] Table 1. Electrons and holes in the T1 excited state of some metal complexes of the present invention

[0170] As shown in Table 1, the tetradentate platinum(II) complex phosphorescent material provided by this invention introduces a fluorene ring system at the 5,6-position of carbazole, which enhances the localization of the excited triplet state in the tetradentate platinum(II) complex. 3 The proportion of LE (emissive light) components results in a low shoulder peak, which improves the purity of the material's luminescent color and enhances its stability. This leads to higher color purity, meeting the requirements for blue light materials.

[0171] Photophysical properties:

[0172] Table 2. Photophysical properties of some metal complexes in toluene solution

[0173] Figure 1 shows the room-temperature emission spectra of some compounds of this invention and the comparative complex R1 in toluene solution. Table 2 shows the photophysical properties of compound Pt199 and the comparative complex R1 in toluene solution. As shown in Figure 1 and Table 2, compared with complex R1, the maximum emission peak of complex Pt199 exhibits a 1 nm blue shift and a lower half-width of 14.4 nm. The tetradentate platinum(II) complex phosphorescent material provided by this invention introduces a fluorene ring system at the 5,6-position of carbazole, improving the localization of the excited triplet state in the tetradentate platinum(II) complex. 3 The proportion of LE components is adjusted to give it a low shoulder peak, which improves the purity of the material's molecular luminescence color; at the same time, the molecules are precisely controlled.

[0174] Manufacturing of OLED devices:

[0175] 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.

[0176] In a preferred embodiment, the structure of the device example 1 provided by the present invention is: ITO / P-4 (10nm) / NPD (60nm) / HTH-85 (5nm) / platinum (II) complex:HTH-85:ETH-45 (25nm) (Pt11:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-6 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0177] Device Examples 2-42 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 3. The luminescence properties of the comparative examples and each device example were tested using standard methods, and the data are shown in Table 3. The structural formulas of the devices involved are as follows: where P-4 is HATCN.

[0178] Table 3. Device Light Emitting Characteristics Data Table

[0179] As shown in Table 3, compared with Comparative Example 1, Device Examples 1-42 prepared in this application exhibit excellent device performance in terms of driving voltage, current efficiency, 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 current efficiency, device lifetime, and color purity. This indicates that the compound provided by this invention has certain commercial application value. Furthermore, the devices prepared by this invention are all deep blue light devices.

[0180] In a preferred embodiment, the structure of device example 43 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-6 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0181] Device Examples 44 and 51 were fabricated using structures similar to those in Device Example 43, the only difference being that the platinum(II) complex and boron-containing compound in Device Example 43 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 3.

[0182] Table 4. Device Structure and Luminescent Properties Data

[0183] 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.

[0184] In a preferred embodiment, the present invention provides a top-emitting device D1, wherein the device D1 has the following structure: ITO / HT-1:P-5(97:3) / HT-1(126nm) / p-host(5nm) / p-host:ETH-45:Pt199(60:32:8,350nm) / mSiTRz(5nm) / ET-1:LiQ(50:50,30nm) / Yb(1nm) / Ag(14nm) / CPL(60nm). Device D-R1 is fabricated using a similar structure to D1, the only difference being that Pt199 in device D1 is replaced with PtON-TBBI. The luminescence data are shown in Table 5. The structural formulas of the involved device materials are as follows:

[0185] Table 5. Top-Emitting Device Characteristic Data Sheet

[0186] As shown in Table 5, using the compound Pt199 of this invention as a deep blue light-emitting material, together with R1, as a light-emitting material in devices, significantly improves the emission spectrum's full width at half maximum (FWHM), color purity, external quantum efficiency, blue light index, and lifetime; simultaneously, it achieves high brightness of 1000 cd / m². 2 The driving voltage was also significantly reduced. The above data indicates that the deep blue luminescent material of this invention has enormous application potential.

[0187] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the technical scope disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A fluorenazine-carbazole tetradentate platinum(II) complex, characterized in that, having the general structure of Formula (I): In formula (I), R 1 –R 7 each independently represents mono-substitution to the maximum amount of substitution, or no substitution; R 1 –R 7 each independently is selected from one or more of: hydrogen, deuterium, halogen, CN, substituted or unsubstituted C1–C30 alkyl, substituted or unsubstituted C3–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl, substituted or unsubstituted C6–C60 heteroaryl, substituted or unsubstituted C6–C60 arylamino, C6–C60 arylsilyl, C6–C60 alkylsilyl; R a and R b each independently is selected from one or more of hydrogen, deuterium, substituted or unsubstituted C1–C30alkyl, substituted or unsubstituted C3–C30cycloalkyl, substituted or unsubstituted C6–C60aryl, substituted or unsubstituted C6–C60heteroaryl; R x one or more selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 heteroaryl, substituted or unsubstituted C6-C60 diarylamine group, C6-C60 arylsilyl group; two or more substituents in formula (I) can be linked to each other to form a cyclic structure.

2. The fluorene-carbazole tetradentate Pt(II) complex according to claim 1, characterized in that, R 1 -R 7 Each is independently selected from one or more of the following: 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, 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, cyclopentane, cyclohexane, adamantyl, phenyl, biphenyl, tert-phenyl, naphthyl, methyl-substituted tetrahydronaphthyl, indyl, methyl-substituted indyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, diarylamino, and triphenylsilane.

3. The fluorene-carbazole tetradentate Pt(II) complex according to claim 1, characterized in that, R x It is 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, 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, cyclopentane, cyclohexane, adamantyl, phenyl, biphenyl, tert-phenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, naphthyl, methyl-substituted tetrahydronaphthyl, indene, methyl-substituted indene, oxainyl, thiainyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, diarylamino, and triphenylsilane.

4. The fluorene-carbazole tetradentate Pt(II) complex according to claim 1, characterized in that, R a and R b each independently is selected from one or more of hydrogen, deuterium, CD3, F, CF3, CN, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, hexyl, heptyl, phenyl, methylphenyl, i-propylphenyl, t-butylphenyl, di-t-butylphenyl.

5. The fluorene-carbazole tetradentate Pt(II) complex of claim 1, wherein, The complex is selected from any of the chemical structures shown below, where "D" represents deuterium and Ph represents phenyl:

6. The use of the fluorenylcarbazole tetradentate platinum(II) complex according to any one of claims 1-5 in the preparation of electronic devices.

7. Use according to claim 6, characterized in that, The electronic devices mentioned are organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic optoelectronic devices, organic solar cells, organic optical detectors, organic photosensors, organic field quenching devices, luminescent electrochemical cells, or organic laser diodes.

8. An organic electroluminescent device, characterized by 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 1-5.

9. The organic electroluminescent device according to claim 8, characterized in that The organic functional layer contains a fluorescent dopant material, which is a boron-containing compound.

10. 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 1-5.

11. The organic optoelectronic device according to claim 10, characterized in that The organic light-emitting functional layer also contains a fluorescent dopant material, which is a boron-containing compound.

12. A composition characterized in that, The composition comprises the fluorenylcarbazole tetradentate platinum(II) complex according to any one of claims 1-5.

13. A formulation characterized in that, The formulation comprises the fluorenylcarbazole tetradentate platinum(II) complex according to any one of claims 1-5 and at least one solvent.

14. A display or lighting device, characterized in that, The device comprises one or more of the organic electroluminescent device as described in any one of claims 8-9 or the organic optoelectronic device as described in any one of claims 10-11.

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