A fluorine-containing tetradentate platinum (II) complex, electronic device, apparatus and application thereof

Abstract

The present invention belongs to the field of organic electroluminescence, and specifically relates to a fluorine-containing tetradentate platinum (II) complex, an electronic device, an apparatus, and applications thereof. The present invention provides a fluorine-containing tetradentate platinum (II) complex having a structure as shown in formula (I) or formula (II): #imgabs0# In formula (I) or formula (II), F n The compound provided by the present invention has excellent chemical stability and can improve and balance the transport of holes and electrons, making the energy transfer between the host and the guest more efficient. This is specifically manifested in the improvement of the current efficiency and lifespan of the compound or composition of the present invention when used as an organic electroluminescent device, and has great application prospects in the field of OLED displays and lighting.

Description

Technical Field

[0001] The present invention belongs to the field of organic electroluminescence, and in particular relates to a fluorine-containing tetradentate platinum (II) complex, an electronic device, an apparatus and applications thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technology. Compared to liquid crystal displays, which have shortcomings such as slow response speed, small viewing angle, need for backlight, and high energy consumption, OLED, as an autonomous light-emitting device, does not require a backlight and is energy-efficient. It also has low driving voltage, fast response speed, high resolution and contrast, wide viewing angle, and outstanding low-temperature performance. OLED devices can be made thinner and can be made into flexible structures. In addition, it has the advantages of low production cost, simple production process, and large-scale production. Therefore, OLED has broad and huge application prospects in high-end electronic products and aerospace. With the gradual increase in investment, further in-depth research and development, and the upgrading and transformation of production equipment, OLEDs will have very broad application scenarios and development prospects in the future.

[0003] The core of OLED development lies in the design and development of luminescent materials. The luminescent layers of currently used OLED devices almost all utilize a host-guest luminescence mechanism. This involves doping a guest luminescent material into a host material. The host material generally has a higher energy system than the guest luminescent material, and energy is transferred from the host material to the guest material, exciting the guest material to emit light. Commonly used organic phosphorescent guest materials are 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 efficiently transferred from the luminescent organic material to the guest phosphorescent material. However, due to the easy hole transport properties of mCBP and the poor hole transport properties of 2,6-mCPy, the charge imbalance in the luminescent layer reduces the current efficiency of the device. Furthermore, currently used heavy metal phosphorescent organic complexes are cyclometallated iridium(III) complexes, and their availability is limited. The concentration of platinum in the Earth's crust and the annual global production are both approximately ten times that of iridium. The price of IrCl₃.H₂O, used to prepare iridium(III) complex phosphorescent materials, is 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: an iridium(III) dimer, ligand exchange with an iridium(III) intermediate, synthesis of a mer-iridium(III) complex, and conversion of the mer- to fac-iridium(III) complex isomers. This significantly reduces the overall yield, significantly lowers the utilization of the raw material IrCl₃.H₂O, and increases the preparation cost of iridium(III) complex phosphorescent materials. In contrast, the preparation of platinum(II) complex phosphorescent materials involves only the final step of ligand metallization, the design of a platinum salt. This allows for high platinum utilization, further reducing the preparation cost of platinum(II) complex phosphorescent materials. In summary, the preparation cost of platinum(II) complex phosphorescent materials is much lower than that of iridium(III) complex phosphorescent materials. However, the development of platinum complex materials and devices still faces some technical difficulties. Improving device efficiency and lifespan is a key research issue. Therefore, the development of new phosphorescent metal platinum(II) complexes is urgently needed. Summary of the Invention

[0004] The present invention provides a fluorinated tetradentate platinum (II) complex, an electronic device, an apparatus, and their applications. The fluorinated tetradentate platinum (II) complex of the present invention can be used as a guest phosphorescent material in a light-emitting layer to impart excellent device performance. Furthermore, combining it with specific host materials can improve the current efficiency of electronic devices, particularly organic electroluminescent devices, improve device lifespan, and reduce the operating voltage of the device.

[0005] The present invention provides a fluorine-containing tetradentate platinum (II) complex having a structure as shown in formula (I) or formula (II):

[0006]

[0007] In formula (I) or formula (II), F n Indicates that the benzene ring is substituted with one or more F, where n is a positive integer from 1 to 5;

[0008] R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, N, a C1-C30 alkyl group, a C1-C30 cycloalkyl group, and a C6-C60 aryl group.

[0009] Preferably, at least one hydrogen in R1, R2, R3, and R4 may be replaced by deuterium.

[0010] Furthermore, R1-R4 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C1-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C18 arylamine, substituted or unsubstituted C6-C18 heterocycloamine.

[0011] Preferably, the fluorine-containing tetradentate platinum (II) complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035] Furthermore, the present invention also provides the use of the fluorine-containing tetradentate platinum (II) complex having a structure represented by formula (I) or formula (II) in electronic devices.

[0036] Furthermore, the electronic devices include organic electroluminescent devices (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 photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs) and organic laser diodes (O-lasers).

[0037] In another aspect, the present invention further provides an organic electroluminescent device comprising a cathode, an anode, and an organic functional layer disposed therebetween; the organic functional layer comprising the fluorinated tetradentate platinum (II) complex having a structure represented by formula (I) or formula (II) as described above.

[0038] Furthermore, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the fluorine-containing tetradentate platinum (II) complex having a structure represented by formula (I) or formula (II) as described above.

[0039] Furthermore, the light-emitting layer further comprises a fluorescent doping material; the fluorescent doping material is selected from compounds represented by formula (BN1) or formula (BN2):

[0040]

[0041] Wherein, X is O, S, Se or NR 300 , X1 is Se or N;

[0042] R a -R d Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R a -R d Each is independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl;

[0043] R5 and R6 are each independently selected from a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted carbazolyl group; when containing a substituent, the substituent is selected from deuterium, a C1-C30 alkyl group, and a C6-C30 aryl group.

[0044] Furthermore, the fluorescent doping material is selected from any one of the chemical structures shown below, wherein Ph represents a phenyl group:

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051] In another aspect, the present invention further 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. The organic light-emitting functional layer comprises a fluorinated tetradentate platinum (II) complex having a structure represented by formula (I) or formula (II). For example, the platinum (II) complex can be included in the organic light-emitting functional layer as a luminescent material.

[0052] Furthermore, the organic light-emitting functional layer further comprises a fluorescent doping material represented by formula (BN1) or formula (BN2) as above.

[0053] The present invention also provides a composition comprising a fluorine-containing tetradentate platinum (II) complex having a structure represented by formula (I) or formula (II). Preferably, the composition further comprises a fluorescent dopant material represented by formula (BN1) or formula (BN2).

[0054] The present invention also provides a preparation comprising a fluorinated tetradentate platinum (II) complex having a structure shown in formula (I) or formula (II) as above or a composition as described above and at least one solvent. The solvent is not particularly limited and may be an unsaturated hydrocarbon solvent such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran, tetrahydropyran, and ester solvents such as alkyl benzoate.

[0055] Preferably, the composition further comprises a fluorescent doping material represented by formula (BN1) or formula (BN2) as above.

[0056] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0057] Compared with the prior art, the present invention has the following beneficial effects:

[0058] The present invention provides a phosphorescent material of a fluorine-containing tetradentate platinum (II) complex. By introducing fluorine atoms at appropriate positions of its ligands, the charge distribution of its excited state is improved, so that the excited state of the material has more metal to pyridocarbene charge transfer states ( 3 MLCT) helps increase its radiation rate, thereby extending device life. The materials involved in this invention all have excellent chemical and thermal stability, making them easy to prepare vapor-deposited OLED devices. When combined with fluorescent doping materials, they can balance the transmission of holes and electrons, making the energy transfer between host and guest more efficient. Organic electroluminescent devices fabricated using the compounds of this invention as the light-emitting layer have significantly improved current efficiency and lifespan, and significantly reduced the turn-on voltage. In particular, their combined use with phosphorescent boron-containing compounds can improve the device's light color purity. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 This is the room temperature emission spectrum of platinum complexes Pt-169, Pt-170 and Pt-172 in dichloromethane solution. DETAILED DESCRIPTION

[0060] The following describes the present invention in detail. The description of the components described below may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0061] The term "substituted" as used herein is intended to include all permissible substituents of organic compounds. In a broad sense, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For suitable organic compounds, permissible substituents may be one or more, identical or different. For the purposes of the present invention, heteroatoms (e.g., nitrogen) can have hydrogen substituents and / or any permissible substituents of the organic compounds described herein that satisfy the valence of the heteroatoms. The present invention is not intended to impose any restrictions in any way on the permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" include the implicit condition that such substitution conforms to the permissible 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 transformation (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in certain aspects, unless explicitly stated to the contrary, individual substituents can be further optionally substituted (ie, further substituted or unsubstituted).

[0062] In defining various terms, "R1" to "R6" are used as general symbols in the present invention to represent various specific substituents. These symbols can be any substituents, not limited to those disclosed in the present invention, and when they are limited to certain substituents in one case, they may be limited to some other substituents in other cases.

[0063] "R1", "R2", "R3" ... "R n "" (wherein n is an integer) may independently have one or more of the groups listed above. For example, if R 1 If the alkyl group is a straight chain alkyl group, then one of the hydrogen atoms of the alkyl group may be optionally substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halogen group, or the like. Depending on the group selected, the first group may be incorporated into the second group, or alternatively, the first group may be suspended, i.e., attached to the second group. For example, for the phrase "an alkyl group comprising an amino group," the amino group may be incorporated into the main chain of the alkyl group. Alternatively, the amino group may be attached to the main chain of the alkyl group. The nature of the selected group will determine whether the first group is embedded in or attached to the second group.

[0064] The term "alkyl" as used herein refers to a saturated hydrocarbon group of 1 to 60 carbon atoms, which is branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl 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, sulfo-oxo or sulfhydryl groups of the present invention.

[0065] The term "aryl" used in the present invention is a group containing any carbon-based aromatic group of 5 to 60 carbon atoms, and the carbon-based aromatic group includes but is not limited to phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group, and the aromatic group has at least one heteroatom introduced into the ring of the aromatic group. Examples of heteroatoms include but are not limited to nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group containing an aromatic group, and the aromatic group does not contain heteroatoms. Aryl can be substituted or unsubstituted. The aryl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, sulfo-oxo, or mercapto groups as described herein.

[0066] The compounds of the present invention may contain "optionally substituted" parts. Typically, the term "substituted" (whether or not the term "optionally" is present in the preceding) means that one or more hydrogens of the part indicated are replaced by a suitable substituent. Unless otherwise stated, "optionally substituted" groups may have a suitable substituent at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituent at each position may be the same or different. The substituent combinations envisioned by the present invention are preferably those that form stable or chemically feasible compounds. In some aspects, unless clearly indicated otherwise, it is also contemplated that each substituent may further be optionally substituted (that is, further substituted or unsubstituted).

[0067] The structure of the compound can be represented by the following formula:

[0068]

[0069] It is understood to be equivalent to the following formula:

[0070]

[0071] Where n is usually an integer. That is, R n is understood to mean five individual substituents R a(1) 、R a(2) 、R a(3) 、R a(4) 、R a (5) "Individual substituent" means that each R substituent can be defined independently. For example, if in one case R a(m) is a halogen, then in this case R a(n) Not necessarily halogen.

[0072] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be tuned by selecting appropriate ligands. In another aspect, the invention can exclude any one or more compounds, structures, or portions thereof specifically recited herein.

[0073] 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.

[0074] It should be noted that the above general description and the following detailed description are merely exemplary and explanatory and are not restrictive.

[0075] The present application may be understood more readily by reference to the following detailed description and the Examples included therein.

[0076] 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 otherwise indicated), or specific reagents (otherwise otherwise indicated), as these can of course vary. It should also be understood that the terms used in the present invention are only for the purpose of describing specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, exemplary methods and materials are described below. All raw materials and solvents in the synthetic examples were purchased commercially unless otherwise specified, and the solvents were used directly without further processing.

[0077] The substrate described in the present invention can be any substrate typically used in organic optoelectronic devices. It can be glass or transparent plastic, or an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have varying mechanical strength, thermal stability, transparency, surface smoothness, and water resistance, and their applications vary depending on the properties of the substrate. The materials used in the hole injection layer, hole transport layer, and electron injection layer can be any material from among those known to be used in OLED devices, and the present invention does not impose any specific limitations thereon.

[0078] Synthesis Example

[0079] The following examples of compound syntheses, compositions, devices, or methods are intended only to provide a general approach to the industry and are not intended to limit the scope of protection of this patent. While the data (quantities, temperatures, etc.) mentioned in the patent are as accurate as possible, some errors may exist. Unless otherwise noted, all weighings are separate, temperatures are in °C or at room temperature, and pressures are near atmospheric pressure.

[0080] The following examples provide methods for preparing novel compounds, but the preparation of such compounds is not limited to these methods. In this area of expertise, since the compounds protected herein are easily modified and prepared, they can be prepared using the methods listed below or other methods. The following examples are provided as examples only and are not intended to limit the scope of protection of this patent. Temperature, catalyst, concentration, reactants, and reaction process can all be varied to select different conditions for preparing the compounds for different reactants.

[0081] 1 H NMR (500 MHz), 1 H NMR (400 MHz), 13 C NMR (126 MHz) spectra were measured on an ANANCE III (500M) nuclear magnetic resonance spectrometer. Unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR. 1 When CDCl3 was used as the solvent, TMS (δ = 0.00 ppm) was used as the internal standard for H NMR spectra. When DMSO-d6 was used as the solvent, TMS (δ = 0.00 ppm), the residual DMSO peak (δ = 2.50 ppm), or the residual water peak (δ = 3.33 ppm) was used as the internal standard. 13In the C NMR spectra, CDCl3 (δ = 77.00 ppm) or DMSO-d6 (δ = 39.52 ppm) was used as the internal standard. HPLC-MS was measured on an Agilent 6210TOF LC / MS mass spectrometer; HRMS spectra were measured on an Agilent 6210TOF LC / MS liquid chromatography-time of flight mass spectrometer. 1 In H NMR spectrum data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0082] Example 1: Synthesis of intermediate dF-NH2

[0083] The synthetic route of the intermediate dF-NH2 is as follows:

[0084]

[0085] Synthesis of intermediate (dBr-NH2): To a single-necked flask with a magnetic stirrer, add A (15.0 g, 100 mmol, 1.0 equivalent) and dissolve in dichloromethane (200 mL). N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equivalent) was slowly added at low temperature, and the mixture was allowed to react at room temperature for 48 hours. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using an 80:1 ratio of petroleum ether to ethyl acetate to afford 28.69 g of a red liquid in an 87% yield. The product was used directly in the next step without structural characterization.

[0086] Synthesis of the intermediate (dBr-NO2): To a three-necked flask with a magnetic stirrer, dBr-NH2 (13.3 g, 43.3 mmol, 1.0 equivalent) was added and dissolved in N-methylpyrrolidone (100 mL). Sodium hydride (5.20 g, 130 mmol, 3.0 equivalent) was slowly added at low temperature. Finally, o-fluoronitrobenzene (7.95 g, 56.3 mmol, 1.3 equivalent) was slowly added and the mixture was allowed to react at room temperature for 48 hours. After removing the solvent by distillation under reduced pressure, the crude product was separated by silica gel chromatography using a 50:1 ratio of petroleum ether to ethyl acetate to afford 13.61 g of a yellow solid in a 75% yield. The product was not structurally characterized and was used directly in the next step.

[0087] Synthesis of the intermediate (dBr-2NH2): To a three-necked flask equipped with a magnetic stirrer, add dBr-NO2 (29.6 g, 69.2 mmol / L, 1.0 equiv) and stannous chloride (29.6 g, 277 mmol / L, 4.0 equiv). The nitrogen atmosphere was then purged three times. Ethyl acetate (250 mL) and ethanol (250 mL) were added under nitrogen. The mixture was reacted in an oil bath at 78°C for 24 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using a 30:1-20:1 ratio of petroleum ether to ethyl acetate to afford 22.4 g of a white solid in an 81% yield. The product was used directly in the next step without structural characterization.

[0088] Synthesis of the intermediate (dF-NH2): To a three-necked flask equipped with a magnetic stirrer, dBr-2NH2 (15.0 g, 37.7 mmol, 1.0 equiv) was added, followed by p-fluorophenylboric acid (15.8 g, 113 mmol, 3.0 equiv), tetrakistriphenylphosphine palladium (871 mg, 0.75 mmol, 0.02 equiv), and sodium carbonate (12 g, 113 mmol, 3.0 equiv). The nitrogen atmosphere was then purged three times. Toluene (150 mL), ethanol (60 mL), and water (15 mL) were added under nitrogen. The mixture was reacted in a 90°C oil bath for 24 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using a 30:1-20:1 ratio of petroleum ether to ethyl acetate to afford 13.41 g of a white solid in an 83% yield. 1H NMR (400MHz, DMSO) δ7.43 (dd, J=8.4, 5.6Hz, 4H), 7.28 (s, 2H), 7.07 (t, J=8.8Hz, 4H), 6.35–6.2 7(m,2H),6.14(t,J=7.6Hz,1H),6.02(d,J=7.6Hz,1H),5.65(s,1H),4.48(s,2H),1.34(s,9H).

[0089] It should be noted that the above is only a feasible preparation scheme for one intermediate of the present invention. The intermediates required for each example can be prepared by referring to the synthesis process of the intermediate dF-NH2. The preparation of such intermediate compounds is not limited to this method. They can be prepared using the methods listed above or other methods known in the art. This is not intended to limit the scope of protection of the present invention.

[0090] Example 2: Synthesis of Pt-169

[0091] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-169 is as follows:

[0092]

[0093] Synthesis of Intermediate (M1): To a reaction flask, 2-methoxycarbazole (20 g, 101 mmol, 1.0 equiv), 4-(tert-butyl)-2-chloropyridine (20.6 g, 121.2 mmol, 1.2 equiv), trisdibenzylideneacetone dipalladium (925 mg, 1.01 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (904 mg, 3.03 mmol, 6 mol%), and sodium tert-butoxide (19.41 g, 202 mmol, 2.0 equiv) were added. Toluene (200 mL) was then added. The reaction was allowed to proceed at 110°C for 48 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 32.7 g of a white solid in 98% yield. The product was used directly in the next step without structural characterization.

[0094] Synthesis of Intermediate (M2): To a reaction flask, add M1 (32.7 g, 2.5 mmol, 1.0 equiv) and hydrogen bromide (80.1 g, 990 mmol, 10.0 equiv). Incubate at 120°C for 24 hours, cool to room temperature, separate the organic phase, concentrate, and chromatograph on a silica gel column to afford 862 g of a white solid in 97% yield. The product was used directly in the next step without structural characterization.

[0095] Synthesis of Intermediate (1b): To a reaction flask were added M2 (8.0 g, 25.3 mmol, 1.0 equiv), m-chlorobromobenzene (5.34 g, 27.8 mmol, 1.1 equiv), 2-pyridinecarboxylic acid (623 mg, 5.06 mmol, 20 mmol%), cuprous iodide (481 mg, 2.53 mmol, 10 mmol%), potassium phosphate (10.74 g, 50.6 mmol, 2.0 equiv), and dimethyl sulfoxide (80 mL). The reaction was continued at 100°C for 48 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 10.0 g of a white solid in a 93% yield. The product was used directly in the next step without structural characterization.

[0096] Synthesis of intermediate (La-169): To a Schlenk tube equipped with a magnetic stirrer, dF-NH2 (1.96 mg, 4.60 mmol, 1.0 equiv) was added, followed by 1b (2.32 mg, 5.52 mmol, 1.2 equiv), trisdibenzylideneacetone dipalladium (126 mg, 0.14 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (82 mg, 0.28 mmol, 6 mol%), and sodium tert-butoxide (884 mg, 9.20 mmol, 2.0 equiv). The nitrogen atmosphere was then purged three times, and toluene (5 mL) was added under nitrogen. The mixture was reacted in an oil bath at 110°C for 12 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using petroleum ether / ethyl acetate (60:1-20:1) as the eluent to obtain 2.60 g of a white solid in a 69% yield.

[0097] Ligand (L b -169) was synthesized by adding L into a Schlenk tube with a magnetic stirrer. a -169 (1.10 g, 1.30 mmol, 1.0 equiv) was added to ammonium hexafluorophosphate (423 mg, 2.6 mmol, 2.0 equiv). The nitrogen atmosphere was then evacuated three times, and triethyl orthoformate (5 mL) was added under nitrogen protection. The reaction was allowed to react in an 80°C oil bath for 8 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using a 1:1 ratio of petroleum ether to dichloromethane as the eluent to afford 806 g of a white solid in a 63% yield. 1 H NMR(500MHz, DMSO-d6)δ1.28(s,9H)1.44(s,9H),7.02(t,J=8.5Hz,4H),7.18(td,J=7.5,8.0,5.5Hz,2H),7.23–7.25(m,5H),7.34–7.39(m,2H) ,7.45–7.50(m,4H),7.53–7.59(m,2H),7.67–7.78(m,6H),8.26(d,J=7 .5Hz,1H),8.34(d,J=8.5Hz,1H),8.58(d,J=5.0Hz,1H),10.31(s,1H),.

[0098] Synthesis of Pt-169: Add L a -169 (700 g, 0.74 mmol, 1.0 equiv) was added to (1,5-cyclooctadiene)platinum(II) dichloride (271 mg, 0.78 mmol, 1.05 equiv) and sodium acetate (182 mg, 2.22 mmol, 3.0 equiv). The nitrogen atmosphere was then evacuated three times, and diethylene glycol dimethyl ether (10 mL) was added under nitrogen protection. Nitrogen was then bubbled through the mixture for 30 min to deoxygenate. The reaction was allowed to proceed in an oil bath at 120°C for 72 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using a 4:1 ratio of petroleum ether to dichloromethane to afford 250 mg of a bluish-yellow solid in a 33% yield. 1H NMR (500MHz, CDCl3) δ1.21 (s, 9H), 1.41 (s, 9H), 6.28 (dd, J = 6.0, 4.0Hz, 1H), 6 .86(d,J=8.0Hz,1H),7.06–7.09(m,5H),7.25–7.29(m,5H),7.34(d,J=8.0Hz, 1H),7.41–7.50(m,7H),7.81(d,J=8.0Hz,1H),7.85(d,J=7.5Hz,1H),7.92(d, J=2.0Hz,1H),8.02(d,J=8.0Hz,1H),8.11–8.13(m,1H),9.00(d,J=6.0Hz,1H).

[0099] Example 3: Synthesis of Pt-170

[0100] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-170 is as follows:

[0101]

[0102] Intermediate (L a Synthesis of 2-170: To a Schlenk tube equipped with a magnetic stirrer, 2a (dF-NH2, 850 mg, 1.98 mmol, 1.0 equiv) was added, followed by 2b (1.15 mg, 2.38 mmol, 1.2 equiv), trisdibenzylideneacetone dipalladium (55 mg, 0.06 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (36 mg, 0.12 mmol, 6 mol%), and sodium tert-butoxide (380 mg, 3.96 mmol, 2.0 equiv). The nitrogen atmosphere was then purged three times, and toluene (5 mL) was added under nitrogen. The mixture was reacted in an oil bath at 110°C for 12 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using petroleum ether / ethyl acetate (60:1-20:1) as the eluent to obtain 1.40 g of a white solid in an 81% yield.

[0103] Ligand (L b -170) was synthesized by adding L into a Schlenk tube with a magnetic stirrer. a-170 (1.40 g, 1.80 mmol, 1.0 equivalent) was added to ammonium hexafluorophosphate (586 mg, 3.6 mmol, 2.0 equivalent). The nitrogen atmosphere was then evacuated three times, and triethyl orthoformate (5 mL) was added under nitrogen protection. The reaction was allowed to react in an 80°C oil bath for 8 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using petroleum ether / dichloromethane (1:1) as the eluent to obtain 1.04 g of a white solid with a yield of 56%. 1H NMR(500MHz,DMSO-d6)δ1.27(s,9H)1.28(s,9H),1.44(s,9H),6.88(t,J=3.5Hz,1H) ,7.01(t,J=9.0Hz,4H),7.11(t,J=2.0Hz,1H),7.16–7.18(m,1H),7.21–7.24(m,4H), 7.33–7.36(m,1H),7.45–7.58(m,7H),7.66(d,J=1.5Hz,1H),7.72–7.76(m,4H),1H) ,8.25(d,J=8.0Hz,1H),8.33(d,J=8.5Hz,1H),8.57(d,J=5.5Hz,1H),10.27(s,1H),.

[0104] Synthesis of Pt-170: Add L to a sealed tube with a magnetic stirrer. a -170 (400 g, 0.39 mmol, 1.0 equiv) was added to (1,5-cyclooctadiene)platinum(II) dichloride (142 mg, 0.41 mmol, 1.05 equiv) and sodium acetate (96 mg, 1.17 mmol, 3.0 equiv). The nitrogen atmosphere was then evacuated three times, and diethylene glycol dimethyl ether (10 mL) was added under nitrogen protection. Nitrogen was then bubbled through the reaction mixture for 30 min. The mixture was reacted in an oil bath at 120°C for 72 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using a 4:1 ratio of petroleum ether to dichloromethane to afford 372 mg of a bluish-yellow solid in an 86% yield. 1 H NMR (500MHz, DMSO-d6) δ1.21(s,9H),1.39(s,9H),1.42(s,9H),5.97–6.24(m,2H),6.58(dd,J=6.5,4.5Hz,1H),),6.90–7.19(m,8H),7.35–7.62( m,8H),7.84(d,J=8.5Hz,1H),7.90(d,J=1.5Hz,1H),8.04(d,J=8.5Hz,1H),8.16(d,J=8.5Hz,1H),8.21(d,J=8.0Hz,1H),8.86(d,J=6.0Hz,1H),.

[0105] Example 4: Synthesis of Pt-172

[0106] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-172 is as follows:

[0107]

[0108] Intermediate (L a Synthesis of (-172): To a Schlenk tube equipped with a magnetic stirrer, 3a (dF-NH2, 500 mg, 1.17 mmol, 1.0 equiv) was added, followed by 3b (687 mg, 1.17 mmol, 1.2 equiv), trisdibenzylideneacetone dipalladium (32 mg, 0.04 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (20 mg, 0.07 mmol, 6 mol%), and sodium tert-butoxide (224 mg, 2.34 mmol, 2.0 equiv). The nitrogen atmosphere was then purged three times, and toluene (5 mL) was added under nitrogen. The reaction was allowed to react in an oil bath at 110°C for 12 hours, followed by cooling to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using petroleum ether / ethyl acetate (60:1-20:1) as the eluent to obtain 358 g of a white solid in a 40% yield.

[0109] Ligand (L b -172) was synthesized by adding L into a Schlenk tube with a magnetic stirrer. a -172 (250 mg, 0.26 mmol, 1.0 equiv) was added to ammonium hexafluorophosphate (83 mg, 0.52 mmol, 2.0 equiv). The nitrogen atmosphere was then evacuated three times, and triethyl orthoformate (5 mL) was added under nitrogen protection. The reaction was allowed to proceed in an 80°C oil bath for 8 hours, followed by cooling to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using petroleum ether / dichloromethane (1:1) as the eluent to obtain 110 mg of a white solid in a 37% yield. 1H NMR(500MHz,DMSO-d6)δ1.04-1.12(m,12H).1.28(s,9H),1.45(s,9H),6.86(s,1H),7.00(t ,J=8.5Hz,5H),7.19–7.23(m,3H),7.24–7.27(m,4H),7.32–7.35(m,2H),7.44–7.49(m,3H) ,7.53–7.59(m,2H),7.62–7.66(m,2H),7.69–7.70(m,1H),7.73–7.76(m,3H),7.81(d,J=8. 5Hz,1H),8.24(d,J=7.5Hz,1H),8.33(d,J=8.5Hz,1H),8.55(d,J=5.0Hz,1H),10.34(s,1H).

[0110] Synthesis of Pt-172: Add L to a sealed tube with a magnetic stirrer. a -172 (60 g, 0.05 mmol, 1.0 equiv) was added to (1,5-cyclooctadiene)platinum(II) dichloride (19 mg, 0.06 mmol, 1.05 equiv) and sodium acetate (13 mg, 1.17 mmol, 3.0 equiv). The nitrogen atmosphere was then evacuated three times, and diethylene glycol dimethyl ether (10 mL) was added under nitrogen protection. Nitrogen was then bubbled through the reaction mixture for 30 min. The reaction was allowed to react in an oil bath at 120°C for 72 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using a 4:1 ratio of petroleum ether to dichloromethane to afford 29 mg of a bluish-yellow solid in a 47% yield. 1 H NMR(500MHz,Chloroform-d)δ1.15–1.17(m,12H)1.22(s,9H),1.42(s,9H),6.29(dd,J=6.5,4.5Hz,1H),6.86–6.90(m,2H),7.05(t,J=7.5Hz,1H) ,7.17–7.20(m,2H),7.24–7.26(m,9H),7.34–7.51(m,7H),7.81–7.88(m, 3H), 7.94 (d, J = 2.0Hz, 1H), 8.12 (d, J = 7.0Hz, 1H), 9.03 (d, J = 6.0Hz, 1H).

[0111] Figure 1 This is the room temperature emission spectrum of the prepared complexes Pt-169, Pt-170 and Pt-172 in dichloromethane solution.

[0112] Depend on Figure 1It can be seen that the complexes Pt-169, Pt-170 and Pt-172 all emit deep blue light with high color purity. The maximum emission peak of Pt-169 is 457.4 nm, and its half-peak width is 20 nm. The present invention improves the charge distribution of its excited state by introducing fluorine atoms at appropriate positions of its ligands, so that the excited state of the material has more metal to pyridocarbene charge transfer states ( 3 This study improves the radiation rate and thus the device lifespan, providing an effective approach for designing platinum (II) complexes for high-quality blue-light phosphorescent materials.

[0113] Example 5: Synthesis of Pt-4

[0114] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-4 is as follows:

[0115]

[0116] Pt-4 was synthesized using the same synthesis steps and reaction conditions as compound Pt-169. The target product La-4 was obtained as a light green foamy solid (1.09 g, 74% yield). The target product Lb-4 was obtained as a light green foamy solid (801 mg, 65% yield). Molecular weight [M]: 896.3. The target product Pt-16 was obtained as a yellow solid (325 mg, 33% yield). Molecular weight [M+H]: 1089.4.

[0117] Example 6: Synthesis of Pt-52

[0118] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-52 is as follows:

[0119]

[0120] Pt-52 was synthesized using the same synthesis steps and reaction conditions as compound Pt-169. The target product, La-52, was obtained as a light green foamy solid (1.19 g, 67% yield). The target product, Lb-52, was obtained as a light green foamy solid (721 mg, 63% yield). Molecular weight [M]: 972.4. The target product, Pt-52, was obtained as a yellow solid (335 mg, 36% yield). Molecular weight [M+H]: 1165.3.

[0121] Example 7: Synthesis of Pt-86

[0122] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-86 is as follows:

[0123]

[0124] Pt-86 was synthesized using the same synthesis steps and reaction conditions as Pt-169. The target product, La-86, was obtained as a light green foamy solid (1.15 g, 72% yield). The target product, Lb-86, was obtained as a light green foamy solid (835 mg, 63% yield). Molecular weight [M]: 952.4. The target product, Pt16, was obtained as a yellow solid (319 mg, 30% yield). Molecular weight [M+H]: 1144.3.

[0125] Example 8: Synthesis of Pt-144

[0126] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material 1Pt-144 is as follows:

[0127]

[0128] Pt-144 was synthesized using the same synthesis steps and reaction conditions as Pt-169. The target product, La-144, was obtained as a light green foamy solid (1.23 g, 76% yield). The target product, Lb-144, was obtained as a light green foamy solid (823 mg, 65% yield). Molecular weight [M]: 990.4. The target product, Pt16, was obtained as a yellow solid (349 mg, 37% yield). Molecular weight [M+H]: 1127.5.

[0129] Example 9: Synthesis of Pt-171

[0130] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-171 is as follows:

[0131]

[0132] Pt-171 was synthesized using the same synthesis steps and reaction conditions as Pt-169. The target product, La-171, was obtained as a light green foamy solid (1.49 g, 79% yield). The target product, Lb-171, was obtained as a light green foamy solid (793 mg, 63% yield). Molecular weight [M]: 906.3. The target product, Pt-171, was obtained as a yellow solid (325 mg, 33% yield). Molecular weight [M+H]: 1099.3.

[0133] Example 10: Synthesis of Pt-312

[0134] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-312 is as follows:

[0135]

[0136] Pt-312 was synthesized using the same synthesis steps and reaction conditions as compound Pt-169. The target product, La-312, was obtained as a light green foamy solid (1.22 g, 77% yield). The target product, Lb-312, was obtained as a light green foamy solid (811 mg, 66% yield). Molecular weight [M]: 1046.5. The target product, Pt312, was obtained as a yellow solid (315 mg, 32% yield). Molecular weight [M+H]: 1267.6.

[0137] Example 11: Synthesis of Pt-338

[0138] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-338 is as follows:

[0139]

[0140] Pt-338 was synthesized using the same synthesis steps and reaction conditions as compound Pt-169. The target product, La-338, was obtained as a light green foamy solid (1.19 g, 72% yield). The target product, Lb-338, was obtained as a light green foamy solid (813 mg, 64% yield). Molecular weight [M]: 998.2. The target product, Pt-338, was obtained as a yellow solid (319 mg, 30% yield). Molecular weight [M+H]: 1191.5.

[0141] Example 13: Synthesis of Pt-394

[0142] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-394 is as follows:

[0143]

[0144] Pt-394 was synthesized using the same synthesis steps and reaction conditions as those for compound Pt-169. The target product, La-394, was obtained as a light green foamy solid (1.24 g, 77% yield). The target product, Lb-394, was obtained as a light green foamy solid (811 mg, 65% yield). Molecular weight [M]: 922.3. The target product, Pt-394, was obtained as a yellow solid (309 mg, 30% yield). Molecular weight [M+H]: 1115.3.

[0145] Example 14: Synthesis of Pt-422

[0146] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-422 is as follows:

[0147]

[0148] Pt-422 was synthesized using the same synthesis steps and reaction conditions as Pt-169. The target product La-422 was obtained as a light green foamy solid (1.16 g) in a 77% yield. The target product Lb-422 was obtained as a light green foamy solid (803 mg) in a 63% yield. Molecular weight [M] + :960.3. The target product Pt-422 was obtained as a yellow solid 315 mg, with a yield of 30%. Molecular weight [M+H] + :1181.4.

[0149] Example 15: Synthesis of Pt-478

[0150] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-478 is as follows:

[0151]

[0152] Pt-478 was synthesized using the same synthesis steps and reaction conditions as Pt-169. The target product La-478 was obtained as a light green foamy solid (1.17 g) in a 77% yield. The target product Lb-478 was obtained as a light green foamy solid (814 mg) in a 66% yield. Molecular weight [M] + :958.2. The target product Pt-478 was obtained as a yellow solid 326 mg, with a yield of 34%. Molecular weight [M+H] + :1151.3.

[0153] Example 16: Synthesis of Pt-646

[0154] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-646 is as follows:

[0155]

[0156] Pt-646 was synthesized using the same synthesis steps and reaction conditions as Pt-169. The target product La-646 was obtained as a light green foamy solid (1.19 g) with a yield of 77%. The target product Lb-646 was obtained as a light green foamy solid (823 mg) with a yield of 66%. Molecular weight [M] + :1030.2. The target product Pt-646 was synthesized as a yellow solid 314 mg with a yield of 30%. Molecular weight [M+H] + :1246.6.

[0157] Theoretical calculation instructions

[0158] Density functional theory (DFT) was used to optimize the ground state (S0) molecular geometry. DFT calculations were performed using the B3LYP functional with the 6-31G(d) basis set for C, H, O, and N atoms and the LANL2DZ basis set for Pt atoms.

[0159] Table 1. Frontier orbital energy levels of some metal complexes of the present invention

[0160]

[0161]

[0162]

[0163]

[0164]

[0165] From the above calculation data, it can be seen that the compound materials provided by the present invention have a large energy gap (>2.86eV), which can meet the needs of blue light materials. In addition, it can be seen that the frontier orbital energy levels (HOMO and LUMO) of the platinum (II) complex can be adjusted by regulating the ligand structure. The LUMO of the pyridocarbene platinum (II) complex is mostly located in the pyridocarbene part. The introduction of fluorine atoms at the appropriate position of the ligand can improve the charge distribution of its excited state, so that the excited state of the material has more metal to pyridocarbene charge transfer states ( 3 MLCT) component; and because there is both a coordination bond and a feedback π bond between carbene and platinum (II), its stability is higher than the coordination bond between pyridine and platinum (II); the above results are conducive to improving its radiation rate, thereby extending the life of the device.

[0166] Fabrication of OLED devices:

[0167] As a reference preparation method for a device embodiment, the present invention deposits a p-type dopant material on the surface of an ITO glass or anode with a luminescent area of 2mm×2mm, or co-evaporates the p-type dopant material with a hole injection material at a concentration of 1% to 50%, to form a 5-100nm hole injection layer (HIL) and a 5-200nm hole transport layer (HTL). Subsequently, a 10-100nm light-emitting layer (EML) (which may contain the compound described herein) is formed on the hole transport layer, followed by a 20-200nm electron transport layer (ETL) and a 50-200nm 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 cathode to produce an OLED device. The OLED device is then tested using standard methods. Unless otherwise specified, the device materials involved in this invention can be obtained by known synthesis methods.

[0168] In a preferred embodiment, the structure of device example 1 provided by the present invention is: ITO / P-4 (10 nm) / NPD (60 nm) / HTH-85 (5 nm) / platinum (II) complex: HTH-85:ETH-45 (25 nm) (Pt-169:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0169] Device Examples 2 through 15 and Comparative Example 1 were prepared using structures similar to those of Device Example 1, differing only in that Pt-169 in Device Example 1 was replaced with Pt-170, Pt-172, Pt-4, Pt-52, Pt-86, Pt-144, Pt-171, Pt-394, Pt-312, Pt-338, Pt-394, Pt-422, Pt-478, Pt-646, and R1, respectively. Luminescence characteristics of the comparative examples and each device example prepared above were tested using standard methods and are shown in Table 2. The device structures are as follows: where P-4 represents HATCN and ET-14 represents BPyTP.

[0170]

[0171] Table 2. Device luminescence characteristics data table

[0172]

[0173] As can be seen from Table 2, compared with Comparative Example 1, Device Examples 1 to 15 prepared in this application all demonstrated good device performance in terms of driving voltage, current efficiency, and device life. The improvement in the performance of each device example is based on the specific compound material of the present invention having better electron transport capability. It can be seen that when it is used as a light-emitting layer material to prepare an electronic device, it has higher current efficiency and device life while reducing the driving voltage. This shows that the compound provided by the present invention has certain commercial application value.

[0174] In a preferred specific embodiment, the structure of device example 16 provided by the present invention is: ITO / P-4 (10nm) / NPD (60nm) / HTH-85 (5nm) / platinum (II) complex: boron-containing compound: HTH-85:ETH-45 (25nm) (Pt169:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0175] Device Examples 17 to 30 were prepared using structures similar to those of Device Example 16, with the only difference being that the fluorine-containing tetradentate platinum (II) complex and the boron-containing compound in Device Example 16 were replaced with the compounds listed in Table 3. The device structures and luminescence characteristics are shown in Table 3.

[0176] Table 3. Device structure and luminescence characteristics data

[0177]

[0178] As shown in Table 3, the performance of each device is significantly improved when the compound of the present invention is used as a sensitizer together with a boron-containing compound as a luminescent material, further demonstrating that the compound provided by the present invention has certain commercial application value.

[0179] Furthermore, the devices prepared in this invention all emit deep blue light, with CIEy values less than 0.20. Adding boron-containing compounds to sensitize the device structure can further reduce the CIEy value, thereby improving the color purity of the device's luminescence.

[0180] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A fluorine-containing tetradentate platinum (II) complex, characterized in that The fluorine-containing tetradentate platinum (II) complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

2. Use of the fluorine-containing tetradentate platinum (II) complex according to claim 1 in electronic devices.

3. The use according to claim 2, characterized in that The electronic devices include organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells and organic laser diodes.

4. An organic electroluminescent device, characterized in that The organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the fluorine-containing tetradentate platinum (II) complex according to claim 1.

5. The organic electroluminescent device according to claim 4, characterized in that: The light-emitting layer further comprises a fluorescent doping material; the fluorescent doping material is selected from a compound represented by formula (BN2): Wherein, X is O, S or Se, X1 is Se or N; R a -R d Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R a -R d Each is independently selected from the group consisting of hydrogen, deuterium, methyl, isopropyl, tert-butyl, and phenyl; R5 is selected from substituted diphenylamino groups, substituted or unsubstituted carbazolyl groups; when containing substituents, the substituents are selected from deuterium, methyl, isopropyl, tert-butyl, and phenyl groups.

6. The organic electroluminescent device according to claim 4, characterized in that: The light-emitting layer further comprises a fluorescent doping material, and the fluorescent doping material is selected from any one of the following chemical structures, wherein Ph represents a phenyl group:

7. An organic optoelectronic device, characterized in that: The organic photoelectric device includes: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; and a second electrode, which is on the organic light-emitting functional layer; wherein the organic light-emitting functional layer contains the fluorine-containing tetradentate platinum (II) complex according to claim 1.

8. The organic optoelectronic device according to claim 7, characterized in that: The organic light-emitting functional layer further comprises a fluorescent doping material; the fluorescent doping material is selected from a compound represented by formula (BN2): Wherein, X is O, S or Se, X1 is Se or N; R a -R d Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R a -R d Each is independently selected from the group consisting of hydrogen, deuterium, methyl, isopropyl, tert-butyl, and phenyl; R5 is selected from substituted diphenylamino groups, substituted or unsubstituted carbazolyl groups; when containing substituents, the substituents are selected from deuterium, methyl, isopropyl, tert-butyl, and phenyl groups.

9. A composition, characterized in that The composition comprises the fluorine-containing tetradentate platinum (II) complex according to claim 1.

10. A preparation, characterized in that The preparation contains the fluorine-containing tetradentate platinum (II) complex according to claim 1.

11. A display or lighting device, characterized in that: The device comprises one or more organic electroluminescent devices according to any one of claims 4 to 6.

Images