Patent Application
20250122422
The application claims priority to Chinese patent application No. 2023111997268, filed on Sep. 18, 2023, the entire contents of which are incorporated herein by reference.
The present invention relates to a phosphorescent material and the use thereof, and more particularly to a cyclic tetradentate metal platinum (II) complex phosphorescent material and the use thereof.
For organic light-emitting diode (OLED), electrons and holes are injected from the cathode and anode, respectively, during the application of the device, and are recombined through hopping transport into the light-emitting layer. The transition of the excited state to the ground state undergoes a radiative transition. Compared with the traditional LCD, OLED has more advanced brightness, low energy consumption, fast response, and other excellent performance. It can be used to make displays and is widely used in demonstration, lighting, military, space, and other fields.
In electroluminescence, 25% singlet excitons and 75% triplet excitons are formed according to spin statistics. At the beginning of the development, the main fluorescent materials were used, and theoretically only 25% of the single-line state excitons could be applied, resulting in extremely low external quantum efficiency, which severely limited the development of OLEDs. Phosphorescent materials break the transition forbidden and achieve 100% exciton utilization by introducing heavy metal atoms to induce a self-selective orbital coupling effect. In general, a cyclic metal platinum (II) complex phosphorescent material is formed by coordinating a ligand and a metal platinum atom, and modifying the chemical structure of the ligand can change the luminescent properties of the metal complex. Compared with bidentate and tridentate ligand structures, tetradentate complexes can suppress vibrational coupling, reduce nonradiative transitions, improve the luminescence quantum efficiency, and achieve efficient phosphorescent emission. Although many structures of cyclic tetradentate metal platinum (II) complexes have been reported, efficient, stable, and high-brightness platinum (II) complexes need to be developed. Therefore, the development of novel cyclic tetradentate metal platinum (II) complexes is still the top priority in the field of OLED.
In order to develop a wider variety of phosphorescent materials with higher performance, it is an object of the present invention to provide a cyclic tetradentate metal platinum (II) complex phosphorescent material and uses thereof. The present invention develops a new 6/6/6 metal fused-ring structure based on a tetradentate ligand of 8-phenylquinoline, benzoxazole, and phenoxy groups, resulting in a novel tetradentate platinum (II) complex containing the 6/6/6 metal fused-ring structure. The complex provided can be prepared as an organic electroluminescent device as a light-emitting layer so that the device has excellent properties. It can increase the external quantum efficiency and reduce the start-up voltage in organic electroluminescent devices.
In order to achieve the technical objectives above, the technical solution of the present invention is as follows.
The present invention provides a cyclic tetradentate metal platinum (II) complex phosphorescent material having the general structure shown in formula (I):
Optionally, R′ is selected from hydrogen, F, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 azaaryl, and combination thereof.
Optionally, R′ is selected from hydrogen, F, methyl, ethyl, propyl, isopropyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, triaryl, naphthyl, pyridyl, and combination thereof.
Optionally, R1-R16 are each independently selected from hydrogen, F, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C1-C30 N heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C12-C18 arylamine, substituted or unsubstituted C18 arylsilyl, and combination thereof.
Optionally, R1-R16 are each independently selected from hydrogen, F, methyl, ethyl, propyl, isopropyl, t-butyl, heptyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, triaryl, naphthyl, pyridyl, quinolinyl, benzofuranyl, dibenzofuranyl, triarylsilane, diphenylamine, diphenylamine oxide, and combination thereof.
Optionally, two or more adjacent R1-R16 are each independently or selectively linked to form a condensed ring.
Optionally, at least one of R′ and R1-R16 is hydrogen.
Preferably, the cyclic tetradentate metal platinum (II) complex phosphorescent material is any one of the following structural formulae:
Further, the present invention also provides the use of the cyclic tetradentate metal platinum (II) complex phosphorescent material having the structure shown in formula (I) above in an electronic device.
Further, the electronic device includes an organic electroluminescent device (OLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), a light-emitting electrochemical cell (LEC), and an organic laser diode (O-laser).
In another aspect, the present invention also provides an organic electroluminescent device including the cyclic tetradentate metal platinum (II) complex phosphorescent material having the structure shown in formula (I) as described above.
Further, the organic electroluminescent device includes a cathode, an anode, and an organic functional layer therebetween; the organic functional layer includes the cyclic tetradentate metal platinum (II) complex phosphorescent material having the structure shown in formula (I) as described above.
Preferably, the organic functional layer includes a light-emitting layer including the cyclic tetradentate metal platinum (II) complex phosphorescent material having the structure shown in formula (I) as described above.
Further, the light-emitting layer also includes a host material, and the mass percentage of the cyclic tetradentate metal platinum (II) complex phosphorescent material is between 1% and 50%. The host material is not limited.
In another aspect, the present invention also provides an organic photovoltaic device including: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; a second electrode on the organic light-emitting functional layer; wherein the organic light-emitting functional layer includes the cyclic tetradentate metal platinum (II) complex phosphorescent material having the structure shown in formula (I) as described above. For example, the cyclic tetradentate metal platinum (II) complex phosphorescent material may be included as a light-emitting material in the organic light-emitting functional layer.
Further, the organic light-emitting functional layer includes a host material, and the mass percentage of the cyclic tetradentate metal platinum (II) complex phosphorescent material is between 1% and 50%. The host material is not limited.
In the present invention, the organic optoelectronic device can be prepared by utilizing methods such as sputter coating, electron beam evaporation, vacuum evaporation, etc. to evaporate metal or oxides having electrical conductivity and alloys thereof on a substrate to form an anode; evaporating a hole-injection layer, a hole-transporting layer, a light-emitting layer, an air-blocking layer, and an electron transporting layer on the surface of the anode obtained by the preparation in sequential order, and then evaporating a cathode at a later time. In addition to the above method, an organic electroluminescent device is fabricated on a substrate by evaporation in the order of a cathode, an organic layer, and an anode. The organic layer may also include a multilayer structure such as a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, and an electron transport layer. In the present invention, the organic layer is prepared by solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, ink-jet printing, or thermal-imaging) using a high molecular material instead of the evaporation method, reducing the number of device layers.
The present invention also provides a composition including the cyclic tetradentate metal platinum (II) complex phosphorescent material having the structure shown in formula (I). Preferably, the composition further includes a fluorescent doping material, and the fluorescent doping materials are preferably boron-containing organic molecular light-emitting materials, and preferably phosphorescent sensitizable boron-containing compounds.
The present invention also provides a formulation including the cyclic tetradentate metal platinum (II) complex phosphorescent material having the structure shown in formula (I) or a composition as described above and at least one solvent.
The solvent is not particularly limited, and an unsaturated hydrocarbon solvent such as toluene, xylene, mesitylene, tetrahydronaphthalene, decahydronaphthalene, dicyclohexane, n-butylbenzene, sec-butylbenzene, t-butylbenzene and other unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, methylene chloride, ethylene chloride, butyl chloride, butyl bromide, pentyl chloride, pentyl bromide, hexyl chloride, hexyl bromide, cyclohexyl chloride, cyclohexyl bromide, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran and tetrahydropyran, and other halogenated solvents known to those skilled in the art, can be used.
The present invention also provides a display or lighting device including one or more of the organic photoelectric devices described above.
The present invention provides a cyclic tetradentate metal platinum (II) complex phosphorescent material based on 8-phenylquinoline, benzoxazole, and phenoxy groups. It is a novel tetradentate platinum (II) complex with a 6/6/6 metal fused ring structure. The phosphorescent materials of the tetradentate fused ring structure system of the present invention have the characteristics of easy modulation of HOMO and LUMO orbital energy levels and strong luminescence. It has good chemical stability and thermal stability and is easy to fabricate evaporation-type OLED devices. The organic electroluminescent device fabricated using the compound of the present invention as a light-emitting layer can reduce the start-up voltage and remarkably improve the external quantum efficiency.
Hereinafter, the present invention will be described in detail. The description of the constituent elements recorded below is 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.
As used herein, the term “substituted” is intended to encompass all permissible substituents of organic compounds. In broad aspects, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of the organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents may be one or more and the same or different for appropriate organic compounds. For purposes of this invention, a heteroatom (e.g. nitrogen) can have a hydrogen substituent and/or any permissible substituent of the organic compound described herein that satisfies the valences of the heteroatom. The present invention is not intended to be limited in any manner by the permissible substituents of organic compounds. Likewise, the term “substituted” or “substituted with” includes the implicit proviso that such substitution is in accordance with a 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 transformation such as by rearrangement, cyclization, elimination, etc.). It is also contemplated that, in certain aspects, unless expressly stated to the contrary, individual substituents can be further optionally substituted (i.e. further substituted or unsubstituted).
In defining various terms, “R1-R16” are used herein as a general symbol to represent various specific substituents. These symbols can be any substituents, not limited to those disclosed herein, and when they are limited in one instance to certain substituents, they can be limited in other instances to some other substituents.
As used herein, “R′, R1 . . . . R16” can independently have one or more of the groups listed above. For example, if R1 is a straight chain alkyl group, one hydrogen atom of the alkyl group may be optionally substituted with hydroxyl, alkoxy, alkyl, halogen, and the like. Depending on the group selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendant, i.e. attached, to the second group. For example, for the phrase “amino-containing alkyl”, the amino group can be incorporated within the backbone of the alkyl group. Optionally, the amino group may be attached to the backbone 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.
The term “alkyl” as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 60 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, hemi-, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group is substitutable or unsubstituted. For example, the alkyl group is substitutable with one or more groups including, but not limited to, an optionally substituted alkyl, cycloalkyl, alkoxy, amino, halo, hydroxy, nitro, silyl, sulfo-oxo, or mercapto group as described herein.
The term “aryl” as used herein is a radical of any carbon-based aromatic group containing from 6 to 60 carbon atoms including, but not limited to, phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, and the like. The term “aryl” also includes “heteroaryl”, which is defined as a group containing an aromatic group having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term “non-heteroaryl” (which is also encompassed by the term “aryl”) defines groups that contain aromatic groups that are free of a heteroatom. The aryl group is substitutable or unsubstituted. The aryl group is substitutable 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 thiol as described herein.
The compounds of the invention may contain “optionally substituted” moieties. In general, the term “substituted” (whether preceded by the term “optionally” or not) means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure is substitutable with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds. In certain aspects, unless expressly stated to the contrary, it is encompassed that individual substituents can be further optionally substituted (i.e. further substituted or unsubstituted).
The compound disclosed herein can exhibit desirable properties and have emission and/or absorption spectra that can be modulated by the selection of appropriate ligands. In another aspect, the invention may exclude any one or more compounds, structures, or portions thereof specifically recited herein.
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.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.
The present application can be understood more readily by reference to the following detailed description and examples contained therein.
Before the present compounds, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods (as otherwise indicated), or to specific reagents (as otherwise indicated), as such can, of course, vary. It is also to be understood that the terminology used in the invention is for the purpose of describing only the particular aspect and is 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 starting materials and solvents of synthesis examples were purchased commercially unless otherwise specified, and the solvents were used as they are without further treatment.
The substrate of the present invention may be any substrate typically used in organic optoelectronic devices. It may be a glass or transparent plastic substrate, it may be a substrate of an opaque material such as silicon or stainless steel, and it may be a flexible PI film. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, and water resistance. The application direction is different according to the properties of the substrates. As the materials for the hole-injecting layer, the hole-transporting layer, and the electron injecting layer, any material can be selected and used from known related materials for OLED devices, and the present invention is not particularly limited thereto.
The following examples of compound syntheses, compositions, devices, or methods are provided merely to provide a general approach to the industry and are not intended to limit the scope of the patent. For the data mentioned in the patent (quantities, temperatures, etc.) are guaranteed to be as accurate as possible, but there may be some errors. Unless otherwise noted, the weighing is done separately, the temperature is ° C., or room temperature, and the pressure is near atmospheric.
Methods for the preparation of novel compounds are provided in the following examples, but the preparation of such compounds is not limited to this method. In this technical field, since the claimed compound of the present invention can be easily prepared by modification, the methods listed below or other methods can be used. The following examples are given by way of example only and are not intended to limit the scope of this patent. The temperature, catalyst, concentration, reactants, and course of reaction may be varied to select different conditions for different reactants to produce the compound.
1H NMR (500 MHz), 1H NMR (400 MHz), and 13C NMR (126 MHz) spectra were measured on an ANANCE III (500M) NMR spectrometer. Unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR. TMS (δ=0.00 ppm) was used as an internal standard when CDCl3 was used as a solvent for 1H NMR spectrum. TMS (δ=0.00 ppm), residual DMSO peak (δ=2.50 ppm) or residual water peak (δ=3.33 ppm) was used as the internal standard when DMSO-d6 was used as the solvent. In 13C NMR spectra, CDCl3 (δ=77.00 ppm) or DMSO-d6 (δ=39.52 ppm) was used as the internal standard. Determination was done on the HPLC-MS Agilent 6210 TOF LC/MS. HRMS spectra were determined on the Agilent 6210 TOF LC/MS type liquid chromatography-time-of-flight mass spectrometer. 1H NMR spectral data: s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, m=multiplet, br=broad.
(1) Synthesis of ligand Ligand1: to a schlenk tube with a magnetic stirrer were added 1-Bpin (200 mg, 0.52 mmoL, 1.0 eq.), 1-Br (150 mg, 0.52 mmol, 1.0 eq.), tetra (triphenylphosphine) palladium (18 mg, 0.015 mmoL, 3 mol %), and potassium carbonate (214 mg, 1.55 mmoL, 3.0 eq.) successively. Nitrogen was pumped three times before injecting 1,4-dioxane (4 mL) and water (1 mL). The reaction lasted 12 h at 85° C. under stirring, and the starting material was substantially completely reacted as determined by TLC. The heating was stopped and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/ethyl acetate=15/1-12/1 was used as gradient elution to obtain 237 mg of product, a white foam solid, 97% yield. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 1.46 (s, 9H), 7.07-7.12 (m, 2H), 7.51-7.56 (m, 2H), 7.59 (t, J=8.0 Hz, 1H), 7.68 (t, J=7.5 Hz, 1H), 7.72-7.77 (m, 2H), 7.86 (dd, J=8.0, 1.0 Hz, 1H), 7.93-7.99 (m, 3H), 8.06 (dd, J=8.0, 1.5 Hz, 1H), 8.19 (t, J=1.5 Hz, 1H), 8.43 (dd, J=8.5, 2.0 Hz, 1H), 8.86 (dd, J=4.0, 2.0 Hz, 1H), 11.38 (s, 1H).
(2) Synthesis of Pt1: to a 50 mL three-neck flask equipped with a magnetic stirrer were added Ligand1 (200 mg, 0.43 mmoL, 1.0 eq.), potassium chloroplatinite (185 mg, 0.45 mmoL, 1.05 eq.), and tetra-n-butylammonium bromide (14 mg, 0.043 mmoL, 10 mol %) successively. A condenser tube was connected. Nitrogen was pumped three times before injecting 26 mL of acetic acid with a syringe. The reaction solution was bubbled with nitrogen for 30 minutes. After 12 hours of stirring at room temperature, the temperature was raised to 120° C., and stirring was continued for 48 hours. The reaction solution was cooled, and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/dichloromethane=2/1-1/1 was used as gradient elution to obtain 140 mg of product, light yellow solid, 49% yield. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 1.49 (s, 9H), 6.76 (ddd, J=8.0, 7.0, 1.0 Hz, 1H), 6.91-6.96 (m, 1H), 7.43 (t, J=7.5 Hz, 1H), 7.47 (ddd, J=8.5, 7.0, 2.0 Hz, 1H), 7.57 (d, J=7.0 Hz, 1H), 7.65 (t, J=8.0 Hz, 1H), 7.79-7.86 (m, 2H), 8.07 (td, J=4.0, 3.5, 2.0 Hz, 2H), 8.21 (d, J=2.0 Hz, 1H), 8.36 (d, J=7.0 Hz, 1H), 8.41 (d, J=8.0 Hz, 1H), 8.83 (dd, J=8.5, 1.5 Hz, 1H), 9.51 (dd, J=5.5, 1.5 Hz, 1H).
(1) Synthesis of ligand Ligand2: to a schlenk tube with a magnetic stirrer were added 2-Bpin (200 mg, 0.49 mmoL, 1.0 eq.), 1-Br (142 mg, 0.49 mmoL, 1.0 eq.), tetra (triphenylphosphine) palladium (17 mg, 0.015 mmoL, 3 mol %), and potassium carbonate (204 mg, 1.47 mmoL, 3.0 eq.) successively. Nitrogen was pumped three times before injecting 1,4-dioxane (4 mL) and water (1 mL). The reaction lasted 12 h at 85° C. under stirring, and the starting material was substantially completely reacted as determined by TLC. The heating was stopped and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/ethyl acetate=15/1-12/1 was used as gradient elution to obtain of 215 mg of product, white foam solid, 90% yield. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 7.05-7.13 (m, 2H), 7.45 (t, J=7.5 Hz, 1H), 7.51-7.64 (m, 5H), 7.70 (t, J=7.5 Hz, 1H), 7.77 (dd, J=7.5, 0.5 Hz, 1H), 7.86 (td, J=7.5, 7.0, 1.0 Hz, 2H), 7.95-7.98 (m, 2H), 8.00 (dt, J=8.0, 1.0 Hz, 1H), 8.05 (dd, J=8.0, 1.5 Hz, 1H), 8.21 (d, J=2.0 Hz, 1H), 8.29 (t, J=1.5 Hz, 1H), 8.36 (d, J=2.0 Hz, 1H), 8.53 (dd, J=8.5, 1.5 Hz, 1H), 8.94 (dd, J=4.0, 2.0 Hz, 1H), 11.39 (s, 1H).
(2) Synthesis of Pt2: to a 50 mL dried three-neck flask equipped with a magnetic stirrer were added Ligand2 (165 mg, 0.34 mmoL, 1.0 eq.), potassium chloroplatinite (147 mg, 0.35 mmoL, 1.05 eq.), and tetra-n-butylammonium bromide (11 mg, 0.034 mmoL, 10 mol %) successively. A condenser tube was connected. Nitrogen was pumped three times before injecting 20 mL of acetic acid with a syringe. The reaction solution was bubbled with nitrogen for 30 minutes. After 12 hours of stirring at room temperature, the temperature was raised to 120° C., and stirring was continued for 48 hours. The reaction solution was cooled, and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/dichloromethane=2/1-1/1 was used as gradient elution to obtain 163 mg of product, light yellow solid, 70% yield. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 6.77 (ddd, J=8.0, 7.0, 1.0 Hz, 1H), 6.95-6.99 (m, 1H), 7.42 (t, J=7.5 Hz, 1H), 7.46-7.50 (m, 2H), 7.58 (t, J=7.5 Hz, 2H), 7.66 (t, J=8.0 Hz, 1H), 7.74 (d, J=7.0 Hz, 1H), 7.85 (d, J=8.0 Hz, 1H), 7.88 (dd, J=8.0, 5.5 Hz, 1H), 7.97-8.01 (m, 2H), 8.08 (dd, J=8.0, 1.5 Hz, 1H), 8.37 (d, J=7.5 Hz, 1H), 8.41 (dd, J=5.0, 3.0 Hz, 2H), 8.45 (d, J=2.0 Hz, 1H), 8.90 (dd, J=8.5, 1.5 Hz, 1H), 9.58 (dd, J=5.5, 1.5 Hz, 1H).
(1) Synthesis of ligand Ligand3: to a schlenk tube with a magnetic stirrer were added 3-Bpin (300 mg, 0.68 mmoL, 1.0 eq.), 1-Br (196 mg, 0.68 mmoL, 1.0 eq.), tetra (triphenylphosphine) palladium (23 mg, 0.020 mmoL, 3 mol %), and potassium carbonate (281 mg, 2.03 mmoL, 3.0 eq.) successively. Nitrogen was pumped three times before injecting 1,4-dioxane (4 mL) and water (1 mL). The reaction lasted 12 h at 85° C. under stirring, and the starting material was substantially completely reacted as determined by TLC. The heating was stopped and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/ethyl acetate=15/1-12/1 was used as gradient elution to obtain 297 mg of product, white foam solid, 83% yield. 1H NMR (400 MHz, DMSO-d6): δ (ppm) 1.44 (s, 9H), 1.46 (s, 9H), 7.07-7.20 (m, 2H), 7.49-7.63 (m, 3H), 7.75 (d, J=6.8 Hz, 2H), 7.85 (d, J=8.0 Hz, 1H), 7.89-7.99 (m, 3H), 8.07 (d, J=6.4 Hz, 2H), 8.35-8.47 (m, 1H), 8.78-8.93 (m, 1H), 11.49 (s, 1H).
(2) Synthesis of Pt3: to a 50 mL three-neck flask equipped with a magnetic stirrer were added Ligand3 (230 mg, 0.44 mmoL, 1.0 eq.), potassium chloroplatinite (190 mg, 0.46 mmoL, 1.05 eq.), and tetra-n-butylammonium bromide (14 mg, 0.044 mmoL, 10 mol %) successively. A condenser tube was connected. Nitrogen was pumped three times before injecting 26 mL of acetic acid with a syringe. The reaction solution was bubbled with nitrogen for 30 minutes. After 12 hours of stirring at room temperature, the temperature was raised to 120° C. and stirring was continued for 48 hours. The reaction solution was cooled, and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/dichloromethane=2/1-1/1 was used as gradient elution to obtain 200 mg of product, light yellow solid, 63% yield. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 1.45 (s, 9H), 1.50 (s, 9H), 6.76 (ddd, J=8.0, 7.0, 1.0 Hz, 1H), 6.94 (d, J=8.0 Hz, 1H), 7.47 (ddd, J=8.5, 7.0, 2.0 Hz, 1H), 7.51 (d, J=2.0 Hz, 1H), 7.66 (t, J=8.0 Hz, 1H), 7.77-7.86 (m, 2H), 8.07 (dd, J=6.5, 2.0 Hz, 2H), 8.19 (d, J=2.0 Hz, 1H), 8.33 (d, J=2.0 Hz, 1H), 8.46 (d, J=8.5 Hz, 1H), 8.83 (dd, J=8.5, 1.5 Hz, 1H), 9.53 (dd, J=5.5, 1.5 Hz, 1H).
(1) Synthesis of ligand Ligand4: to a schlenk tube with a magnetic stirrer were added 1-Bpin (145 mg, 0.37 mmoL, 1.0 eq.), 2-Br (200 mg, 0.37 mmoL, 1.0 eq.), tetra (triphenylphosphine) palladium (13 mg, 0.011 mmoL, 3 mol %), and potassium carbonate (155 mg, 1.10 mmoL, 3.0 eq.) successively. Nitrogen was pumped three times before injecting 1,4-dioxane (4 mL) and water (1 mL). The reaction lasted 12 h at 85° C. under stirring, and the starting material was substantially completely reacted as determined by TLC. The heating was stopped and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/ethyl acetate=15/1-12/1 was used as gradient elution to obtain 233 mg of product, white foam solid, 87% yield. 1H NMR (400 MHz, CDCl3): δ (ppm) 0.93 (s, 9H), 1.41 (s, 9H), 1.42 (s, 9H), 1.47 (s, 9H), 6.89 (d, J=2.4 Hz, 1H), 7.10 (dd, J=8.0, 0.8 Hz, 1H), 7.32 (t, J=7.6 Hz, 1H), 7.35-7.43 (m, 3H), 7.56 (dd, J=7.6, 0.8 Hz, 1H), 7.59-7.66 (m, 2H), 7.68-7.79 (m, 3H), 7.93 (d, J=2.0 Hz, 1H), 8.15 (t, J=1.6 Hz, 1H), 8.16-8.24 (m, 2H), 8.92 (dd, J=4.2, 1.6 Hz, 1H), 13.59 (s, 1H).
(2) Synthesis of Pt4: to a 50 mL dried three-neck flask equipped with a magnetic stirrer were added Ligand4 (200 mg, 0.28 mmoL, 1.0 eq.), potassium chloroplatinite (122 mg, 0.29 mmoL, 1.05 eq.), and tetra-n-butylammonium bromide (9 mg, 0.028 mmoL, 10 mol %) successively. A condenser tube was connected. Nitrogen was pumped three times before injecting 17 mL of acetic acid with a syringe. The reaction solution was bubbled with nitrogen for 30 minutes. After 12 hours of stirring at room temperature, the temperature was raised to 120° C., and stirring was continued for 48 hours. The reaction solution was cooled, and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/dichloromethane=2/1-1/1 was used as gradient elution to obtain 211 mg of product, light yellow solid, 83% yield. 1H NMR (400 MHz, DMSO-d6): δ (ppm) 0.82 (s, 9H), 1.20 (s, 9H), 1.36 (s, 9H), 1.49 (s, 9H), 6.74 (d, J=2.4 Hz, 1H), 7.11 (d, J=2.4 Hz, 1H), 7.18 (d, J=8.0 Hz, 1H), 7.37 (t, J=7.6 Hz, 1H), 7.43-7.61 (m, 4H), 7.69 (d, J=8.8 Hz, 2H), 7.75 (dd, J=8.0, 5.2 Hz, 1H), 8.03 (d, J=2.0 Hz, 1H), 8.20 (d, J=7.6 Hz, 1H), 8.27 (d, J=8.0 Hz, 1H), 8.34 (d, J=2.0 Hz, 1H), 8.79 (dd, J=8.4, 1.2 Hz, 1H), 9.56 (dd, J=5.2, 1.2 Hz, 1H).
(1) Synthesis of ligand Ligand5: to a schlenk tube with a magnetic stirrer were added 1-Bpin (76 mg, 0.20 mmoL, 1.0 eq.), 3-Br (120 mg, 0.20 mmol, 1.0 eq.), tetra (triphenylphosphine) palladium (7 mg, 0.0059 mmoL, 3 mol %), and potassium carbonate (81 mg, 0.59 mmoL, 3.0 eq.) successively. Nitrogen was pumped three times before injecting 1,4-dioxane (4 mL) and water (1 mL). The reaction lasted 12 h at 85° C. under stirring, and the starting material was substantially completely reacted as determined by TLC. The heating was stopped and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/ethyl acetate=15/1-12/1 was used as gradient elution to obtain 147 mg of product, white foam solid, 92% yield. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 0.92 (s, 9H), 1.21 (s, 9H), 1.40 (s, 9H), 1.43 (s, 9H), 6.88 (d, J=2.5 Hz, 1H), 7.12-7.17 (m, 2H), 7.39 (t, J=8.0 Hz, 1H), 7.50 (dd, J=8.5, 4.0 Hz, 1H), 7.58 (dd, J=7.0, 1.5 Hz, 2H), 7.67 (td, J=4.5, 1.5 Hz, 2H), 7.71 (d, J=8.5 Hz, 1H), 7.77 (dd, J=8.5, 2.5 Hz, 1H), 7.92 (q, J=2.0 Hz, 2H), 7.93-7.97 (m, 1H), 8.16 (s, 1H), 8.39 (dd, J=8.5, 1.5 Hz, 1H), 8.81 (dd, J=4.0, 2.0 Hz, 1H), 12.97 (s, 1H).
(2) Synthesis of Pt5: to a 50 mL dried three-neck flask equipped with a magnetic stirrer were added Ligand5 (127 mg, 0.16 mmoL, 1.0 eq.), potassium chloroplatinite (67 mg, 0.17 mmoL, 1.05 eq.), and tetra-n-butylammonium bromide (5 mg, 0.016 mmoL, 10 mol %) successively. A condenser tube was connected. Nitrogen was pumped three times before injecting 10 mL of acetic acid with a syringe. The reaction solution was bubbled with nitrogen for 30 minutes. After 12 hours of stirring at room temperature, the temperature was raised to 120° C., and stirring was continued for 48 hours. The reaction solution was cooled, and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/dichloromethane=2/1-1/1 was used as gradient elution to obtain 125 mg of product, light yellow solid, 79% yield. 1H NMR (500 MHz, CDCl3): δ (ppm) 0.88 (s, 9H), 1.20 (s, 9H), 1.42 (s, 9H), 1.49 (s, 9H), 6.89 (d, J=2.5 Hz, 1H), 7.02 (d, J=8.0 Hz, 1H), 7.13 (d, J=2.5 Hz, 1H), 7.29 (t, J=8.0 Hz, 1H), 7.34 (t, J=7.5 Hz, 1H), 7.45 (dd, J=8.0, 5.0 Hz, 1H), 7.51-7.60 (m, 4H), 7.68 (d, J=2.0 Hz, 1H), 8.06 (d, J=8.0 Hz, 1H), 8.09-8.13 (m, 1H), 8.25 (d, J=2.0 Hz, 1H), 8.35 (dd, J=8.5, 1.5 Hz, 1H), 9.55 (dd, J=5.0, 1.5 Hz, 1H).
(1) Synthesis of ligand Ligand6: to a schlenk tube with a magnetic stirrer were added 2-Bpin (81 mg, 0.20 mmoL, 1.0 eq.), 3-Br (120 mg, 0.20 mmoL, 1.0 eq.), tetra (triphenylphosphine) palladium (7 mg, 0.0059 mmoL, 3 mol %), and potassium carbonate (81 mg, 0.59 mmoL, 3.0 eq.) successively. Nitrogen was pumped three times before injecting 1,4-dioxane (4 mL) and water (1 mL). The reaction lasted 12 h at 85° C. under stirring, and the starting material was substantially completely reacted as determined by TLC. The heating was stopped and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/ethyl acetate=15/1-12/1 was used as gradient elution to obtain 137 mg of product, white foam solid, 84% yield. 1H NMR (500 MHz, DMSO-d6): δ (ppm) 0.94 (s, 9H), 1.20 (s, 9H), 1.41 (s, 9H), 6.91 (d, J=2.5 Hz, 1H), 7.15 (dd, J=8.0, 1.0 Hz, 1H), 7.16 (d, J=2.5 Hz, 1H), 7.36-7.40 (m, 1H), 7.40-7.44 (m, 1H), 7.50 (t, J=7.5 Hz, 2H), 7.57-7.64 (m, 3H), 7.69 (t, J=7.5 Hz, 1H), 7.73 (d, J=8.5 Hz, 1H), 7.76-7.82 (m, 2H), 7.88-7.93 (m, 2H), 8.01 (dt, J=8.0, 1.0 Hz, 1H), 8.18 (d, J=2.0 Hz, 1H), 8.27 (t, J=1.5 Hz, 1H), 8.33 (d, J=2.0 Hz, 1H), 8.51 (dd, J=8.5, 2.0 Hz, 1H), 8.91 (dd, J=4.0, 2.0 Hz, 1H), 13.08 (s, 1H).
(2) Synthesis of Pt6: to a 50 mL dried three-neck flask equipped with a magnetic stirrer were added Ligand6 (117 mg, 0.14 mmoL, 1.0 eq.), potassium chloroplatinite (63 mg, 0.15 mmoL, 1.05 eq.), and tetra-n-butylammonium bromide (5 mg, 0.014 mmoL, 10 mol %) successively. A condenser tube was connected. Nitrogen was pumped three times before injecting 9 mL of acetic acid with a syringe. The reaction solution was bubbled with nitrogen for 30 minutes. After 12 hours of stirring at room temperature, the temperature was raised to 120° C., and stirring was continued for 48 hours. The reaction solution was cooled, and the solvent was removed under reduced pressure. The mixture was stirred with silica gel and separated by column chromatography. Petroleum ether/dichloromethane=2/1-1/1 was used as gradient elution to obtain 111 mg of product, light yellow solid, 79% yield. 1H NMR (500 MHz, CDCl3): δ (ppm) 0.89 (s, 9H), 1.21 (s, 9H), 1.43 (s, 9H), 6.91 (d, J=2.5 Hz, 1H), 7.03 (d, J=8.0 Hz, 1H), 7.15 (d, J=2.5 Hz, 1H), 7.30 (t, J=8.0 Hz, 1H), 7.34 (t, J=7.5 Hz, 1H), 7.43-7.46 (m, 1H), 7.49-7.63 (m, 8H), 7.77-7.80 (m, 2H), 7.96 (d, J=2.0 Hz, 1H), 8.07 (d, J=8.0 Hz, 1H), 8.12 (d, J=8.0 Hz, 1H), 8.42 (d, J=2.0 Hz, 1H), 8.45 (dd, J=8.0, 1.5 Hz, 1H), 9.61 (dd, J=5.0, 1.5 Hz, 1H).
Pt7 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 122 mg of yellow solid with a yield of 63%. Molecular weight [M+H]+: 738.73.
Pt33 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 201 mg of yellow solid with a yield of 79%. Molecular weight [M+H]+: 707.72.
Pt48 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 159 mg of yellow solid with a yield of 68%. Molecular weight [M+H]+: 831.83.
Pt67 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 186 mg of yellow solid with a yield of 69%. Molecular weight [M+H]+: 754.73.
Pt77 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 175 mg of yellow solid with a yield of 65%. Molecular weight [M+H]+: 859.87.
Pt79 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 210 mg of yellow solid with a yield of 80%. Molecular weight [M+H]+: 928.03.
Pt96 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 169 mg of yellow solid with a yield of 63%. Molecular weight [M+H]+: 755.76.
Pt107 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 163 mg of yellow solid with a yield of 58%. Molecular weight [M+H]+: 774.84.
Pt137 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 210 mg of yellow solid with a yield of 76%. Molecular weight [M+H]+: 861.93.
Pt150 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 182 mg of yellow solid with a yield of 68%. Molecular weight [M+H]+: 805.77.
Pt156 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 188 mg of yellow solid with a yield of 77%. Molecular weight [M+H]+: 763.82.
Pt178 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 178 mg of yellow solid with a yield of 78%. Molecular weight [M+H]+: 769.79.
Pt184 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 153 mg of yellow solid with a yield of 49%. Molecular weight [M+H]+: 797.84.
Pt192 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 190 mg of yellow solid with a yield of 76%. Molecular weight [M+H]+: 902.98.
Pt208 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 152 mg of yellow solid with a yield of 62%. Molecular weight [M+H]+: 924.00.
Pt239 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 167 mg of yellow solid with a yield of 68%. Molecular weight [M+H]+: 1012.18.
Pt246 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 182 mg of yellow solid with a yield of 73%. Molecular weight [M+H]+: 750.84.
Pt254 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 166 mg of yellow solid with a yield of 56%. Molecular weight [M+H]+: 945.12.
Pt269 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 190 mg of yellow solid with a yield of 74%. Molecular weight [M+H]+: 812.91.
Pt281 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 192 mg of yellow solid with a yield of 79%. Molecular weight [M+H]+: 694.74.
Pt305 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 173 mg of yellow solid with a yield of 68%. Molecular weight [M+H]+: 851.93.
Pt325 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 188 mg of yellow solid with a yield of 73%. Molecular weight [M+H]+: 809.90.
Pt349 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 180 mg of yellow solid with a yield of 68%. Molecular weight [M+H]+: 990.15.
Pt368 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 191 mg of yellow solid with a yield of 75%. Molecular weight [M+H]+: 999.11.
Pt382 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 143 mg of yellow solid with a yield of 65%. Molecular weight [M+H]+: 809.90.
Pt392 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 167 mg of yellow solid with a yield of 66%. Molecular weight [M+H]+: 908.09.
Pt409 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 178 mg of yellow solid with a yield of 73%. Molecular weight [M+H]+: 821.79.
Pt462 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 156 mg of yellow solid with a yield of 59%. Molecular weight [M+H]+: 829.89.
Pt476 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 170 mg of yellow solid with a yield of 68%. Molecular weight [M+H]+: 976.12.
Pt484 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 192 mg of yellow solid with a yield of 79%. Molecular weight [M+H]+: 948.07.
Pt516 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 167 mg of yellow solid with a yield of 68%. Molecular weight [M+H]+: 895.05.
Pt560 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 158 mg of yellow solid with a yield of 58%. Molecular weight [M+H]+: 1067.23.
Pt577 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 166 mg of yellow solid with a yield of 65%. Molecular weight [M+H]+: 829.89.
Pt578 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 178 mg of yellow solid with a yield of 72%. Molecular weight [M+H]+: 787.81.
Pt579 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 189 mg of yellow solid with a yield of 78%. Molecular weight [M+H]+: 740.62.
Pt580 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 177 mg of yellow solid with a yield of 71%. Molecular weight [M+H]+: 945.02.
Pt581 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 159 mg of yellow solid with a yield of 63%. Molecular weight [M+H]+: 760.77.
Pt582 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 183 mg of yellow solid with a yield of 74%. Molecular weight [M+H]+: 883.93.
Pt583 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 202 mg of yellow solid with a yield of 80%. Molecular weight [M+H]+: 993.93.
Pt584 was synthesized by referring to the synthesis procedure and reaction condition of compound Pt1. The desired product was obtained as 182 mg of yellow solid with a yield of 79%. Molecular weight [M+H]+: 900.92.
Steady state emission experiments and lifetime measurements were performed on a Horiba Jobin Yvon FluoroLog-3 spectrometer. Pt (II) complexes were theoretically calculated using the Titan software package, and the geometry of the ground state (So) molecule was optimized using density-functional theory (DFT). DFT calculations were performed using B3LYP functional where the 6-31G (d) basis set was used for C, H, O and S atoms and the LANL2DZ basis set was used for Pt atoms.
The following structures were calculated using density functional theory (DFT). Table 1 shows DFT theoretical calculation data,
It can be seen from
In a preferred embodiment of the present invention, the OLED device of the present invention includes a hole transport layer. The hole transport material may be selected from known or unknown materials and is particularly preferred from the following structures, but this does not mean that the present invention is limited to the following structures:
In a preferred embodiment of the invention, the hole transport layer contained in the OLED device of the invention includes one or more p-type dopants. Preferred p-type dopants of the present invention may be selected from the following structures, but this does not mean that the present invention is limited to the following structures:
In a preferred embodiment of the invention, the electron transport layer may be selected from at least one of the compounds ET-1 to ET-77, but this does not mean that the present invention is limited to the following structures:
The electron transport layer may be formed from an organic material together with one or more n-type dopants (e.g. LiQ, LiTHPh, etc.).
As a reference fabrication method for a device example, the method of the present invention includes: evaporating a p-doped material on the surface or an 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%-50% to form a hole injection layer (HIL) of 5-100 nm, a hole transport layer (HTL) of 5-200 nm, then forming a light-emitting layer (EML) of 10-100 nm (which may contain the compound described in the present invention) on the hole transport layer, and forming an electron transport layer (ETL) of 20-200 nm and a cathode of 50-200 nm. If necessary, an electron blocking layer (EBL) is added between the HTL and EML layers, and an electron injecting layer (EIL) is added between the ETL and the cathode to fabricate an OLED device. The OLED was tested by standard methods. The device materials referred to in the present invention may be obtained by known synthetic methods unless otherwise specified.
In a preferred embodiment, the structure of Device Example 1 provided by the present invention is ITO/P-4 (10 nm)/NPD (60 nm)/HT-85 (5 nm)/platinum (II) complex: H-1 (25 nm) (mass ration of Pt1:H-1 is 10:90)/ET-8 (5 nm)/ET-14 or BPyTP (40 nm)/LiQ (1 nm)/A1 (100 nm).
Device Examples 2 to 47 and Comparative Example 1 were prepared using a structure similar to Device Example 1, except that Pt1 in Device Example 1 was replaced with Pt2, Pt3, Pt4, Pt5, Pt6, Pt7, Pt33, Pt48, Pt67, Pt77, Pt79, Pt96, Pt107, Pt137, Pt150, Pt156, Pt178, Pt184, Pt192, Pt208, Pt239, Pt246, Pt254, Pt269, Pt281, Pt305, Pt325, Pt349, Pt368, Pt382, Pt392, Pt409, Pt462, Pt476, Pt484, Pt516, Pt560, Pt577, Pt578, Pt579, Pt580, Pt581, Pt582, Pt583, Pt584 and PtON11Me, respectively. The comparative example and each device example prepared above were tested for luminescent characteristics by standard methods, and the data are shown in Table 2. The structural formulas of the devices involved are as follows:
As can be seen from Table 2, Device Examples 1 to 46 prepared in the present application all have a lower start-up voltage and a higher external quantum efficiency compared with the comparative example 1, indicating that the phosphorescent material cyclic tetradentate metal platinum (II) complex provided in the present invention has a certain commercial application value.
It will be understood by those skilled in the art that the embodiments described above are specific examples for practicing the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention. For example, many of the substituent structures described herein can be replaced with other structures without departing from the spirit of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2023111997268 | Sep 2023 | CN | national |
