Divalent platinum or palladium metal complex phosphorescent material based on dibenzothiophene coordination and application thereof

Abstract

The invention provides a divalent platinum or palladium metal complex phosphorescent material based on dibenzothiophene coordination and application of the divalent platinum or palladium metal complex phosphorescent material. The phosphorescent material has a general formula structure as shown in a formula (I): # imgabs0. The complex disclosed by the invention is based on a novel tetradentate ligand of 4-phenyl dibenzothiophene, pyridine phenoxy anions and derivatives thereof, and is coordinated with central metal ions to form a 6 / 5 / 6 type tetradentate ring metal complex phosphorescent material; due to the existence of the Pt-S coordinate bond, the material has an obvious temperature response characteristic. The luminescent intensity of the material is increased along with the reduction of the temperature, the emission wavelength is subjected to blue shift along with the reduction of the temperature, and the material shows dark green light emission at 77K, but shows yellow light emission along with the temperature rising to 289K, which indicates that the material has potential application value in optical thermometers.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of metal-organic optoelectronic functional materials, and particularly relates to a divalent platinum or palladium metal complex phosphorescent material coordinated by dibenzothiophene and its application. Background Art

[0002] In the past few decades, tetradentate Pt(II) complexes have attracted great attention, thanks to the strong spin-orbit coupling of Pt atoms and the square-planar rigid structure formed by tetradentate cyclometalated ligands that can inhibit non-radiative decay. Moreover, by using ligands with different coordination sites, coordination bonds, and connection modes of the coordination moieties, the photophysical properties of Pt(II) complexes can be adjusted. So far, most studies have focused on the coordination of carbon (carbene), oxygen (O), and nitrogen (N) atoms with Pt(II) metal to form a strong-field ligand, resulting in stronger coordination bonds. According to the hard–soft acid–base (HSAB) theory, compared with coordination bonds of O and N, the soft metals Pt / Pd can better match with the soft base sulfur (S) atom to form S coordination bonds. And different from the sp 2 hybridization of coordinated N atoms, the coordinated S in Pt(II) complexes is mainly sp 3 hybridization, which can distort the planar configuration and avoid molecular packing. However, the previously reported Pt(II) luminescent complexes containing Pt-S coordination bonds are mainly bidentate and tridentate complexes, and there are almost no tetradentate complexes. Bidentate and tridentate Pt(II) complexes mainly suffer from poor electrochemical and thermal stabilities and low phosphorescence efficiency. Compared with bidentate and tridentate complexes, tetradentate Pt(II) complexes have a planar structure and stronger ligand rigidity, which can reduce the configurational change of material molecules in the excited state, thereby reducing non-radiative decay caused by molecular vibration and rotation, improving the quantum efficiency, and at the same time improving the molecular chemical stability and thermal stability. Although divalent platinum or palladium complex phosphorescent materials have been reported, most of them are applied in the OLED field. It is still of great significance to explore the application of tetradentate Pt(II)-based phosphorescent materials in other fields by taking advantage of their advantages. Summary of the Invention

[0003] Aiming at the deficiencies in the prior art, the purpose of the present invention is to provide a divalent platinum or palladium metal complex phosphorescent material coordinated by dibenzothiophene. The provided material has temperature response characteristics, and the corresponding relationship between temperature and fluorescence intensity can be obtained without additional reference or calibration. The luminescent colors exhibited at different temperatures are significantly different, and the temperature at which the material is located can be estimated with the naked eye. It has extremely high application prospects in temperature response fields such as optical thermometers.

[0004] To achieve the above purpose, the technical solution of the present invention is as follows:

[0005] The present invention provides a phosphorescent material based on a divalent platinum or palladium metal complex coordinated with dibenzothiophene, and the phosphorescent material has a general formula structure shown in the following formula (I):

[0006]

[0007] Wherein: M is Pt or Pd;

[0008] Y 1 -Y 17 Each independently represents an N or C atom;

[0009] R 1 、R 2 、R 3 、R 4 and R 5 Each independently may be mono-substituted, di-substituted, tri-substituted, tetra-substituted or unsubstituted; R 1 、R 2 Each independently represents any one or a combination of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C1-C24 alkoxy, substituted or unsubstituted C1-C24 silyl, substituted or unsubstituted C6-C36 aryl;

[0010] R 3 Represents any one or a combination of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C1-C24 cycloalkyl, substituted or unsubstituted C3-C24 heterocycloalkyl, substituted or unsubstituted C1-C24 alkoxy, substituted or unsubstituted C6-C36 aryl, C6-C36 heteroaryl, substituted or unsubstituted C6-C36 arylamino, substituted or unsubstituted C6-C36 heteroarylamino, substituted or unsubstituted C1-C24 alkylamino; the heteroatoms in the heterocycloalkyl and heteroaryl may be selected from N, O, S or Si; the heteroatoms in the heteroarylamino may be selected from O, S or Si;

[0011] R 4 and R 5 Each independently represents any one or a combination of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C1-C24 cycloalkyl, substituted or unsubstituted C3-C24 heterocycloalkyl, substituted or unsubstituted C1-C24 alkoxy, substituted or unsubstituted C6-C36 aryl; when the above groups have substituents, the substituents each independently are selected from any one or a combination of deuterium, halogen, -CN, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C30 aryl.

[0012] All hydrogen atoms in formula (I) can be replaced by deuterium atoms.

[0013] Any two substituents in formula (I) can be joined or fused together to form a ring.

[0014] Preferably, two or more adjacent R 1 , R 2 , R 3 , R 4 and R 5 can be selectively linked to form a ring.

[0015] Furthermore, the R 1 , R 2 each independently represents any one or a combination of hydrogen, deuterium, F, -CN, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, methoxy, trimethylsilane.

[0016] The R 3 represents any one or a combination of hydrogen, deuterium, F, -CN, methyl, ethyl, propyl, isopropyl, tert-butyl, heptyl, cyclopentane, pyridyl, carbazolyl, diphenylamino, phenothiazinyl, phenoxazinyl, phenyl, methoxy, trimethylsilyl, benzofuranyl, benzothiophenyl, pyrrolidinyl, 1,1-dimethylindenyl.

[0017] The R 4 and R 5 each independently represents any one or a combination of hydrogen, deuterium, F, -CN, methyl, ethyl, propyl, isopropyl, tert-butyl, heptyl, cyclopentyl, cyclopentenyl, phenyl, methoxy, trimethylsilyl, benzofuranyl, benzothiophenyl, pyrrolidinyl, 1,1-dimethylindenyl.

[0018] Furthermore, the present invention provides a divalent platinum or palladium metal complex phosphorescent material based on dibenzothiophene coordination, and the phosphorescent material is selected from one of the following structures:

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] The present invention also provides the application of the divalent platinum or palladium metal complex phosphorescent material based on dibenzothiophene coordination in the preparation of organic light-emitting devices.

[0025] Preferably, the organic light-emitting element is an organic light-emitting diode, a light-emitting diode, or a light-emitting electrochemical cell.

[0026] The present invention also provides the use of the divalent platinum or palladium metal complex phosphorescent material coordinated with dibenzothiophene as a temperature-responsive luminescent material.

[0027] Furthermore, the present invention also provides the application of the divalent platinum or palladium metal complex phosphorescent material coordinated with dibenzothiophene in the preparation of an optical thermometer.

[0028] The present invention also provides an organic light-emitting diode, which includes

[0029] an anode;

[0030] a cathode; and

[0031] an organic layer disposed between the anode and the cathode, wherein the organic layer contains the divalent platinum or palladium metal complex phosphorescent material coordinated with dibenzothiophene as described above.

[0032] The present invention also provides a consumer product, which includes an organic light-emitting diode, and the organic light-emitting diode includes

[0033] an anode;

[0034] a cathode; and

[0035] an organic layer disposed between the anode and the cathode, wherein the organic layer contains the divalent platinum or palladium metal complex phosphorescent material coordinated with dibenzothiophene as described above.

[0036] The beneficial effects of the present invention are as follows:

[0037] 1. In the molecular structure design of the materials of the present invention, a new dibenzothiophene unit and a central metal ion are coordinated to form a six-membered metal ring, and at the same time, an ortho-pyridylphenolate anion and its derivatives are combined to form a novel tetradentate ligand. The tetradentate ligand coordinates with the central metal ion to form a 6 / 5 / 6-type tetradentate cyclometalated complex phosphorescent material. The presence of the Pt-S coordination bond endows such materials with obvious temperature-responsive characteristics. The luminescence intensity of the material increases with the decrease of temperature, and the emission wavelength blue-shifts with the decrease of temperature. At 77K, it shows cyan-green light emission, but when the temperature rises to 289K, it shows yellow light emission;

[0038] 2. The present invention reports for the first time a tetradentate platinum / palladium complex phosphorescent material containing an S-M coordination bond. According to the hard–soft acid–base (HSAB) theory, compared with the O and N coordination bonds, the soft metals Pt / Pd can better match with the soft base sulfur (S) atoms to form S coordination bonds. Compared with the sp of the coordinated N atoms 2Due to different hybridization, the coordinated S in the Pt(II) complex is mainly sp 3 hybridized, which can distort the planar configuration, avoid molecular packing, and effectively inhibit the Pt…Pt interaction between molecules that causes luminescence quenching.

[0039] 3. The complex phosphorescent material provided by the present invention has temperature-responsive characteristics in the solution state. Without the need for an external reference or calibration, the relationship between temperature and fluorescence intensity can be obtained. At the same time, there are also obvious differences in the luminescence colors shown at different temperatures, and the temperature of the material can be estimated with the naked eye. It overcomes the defect that the application field of traditional tetradentate Pt complexes is relatively limited, can be used in temperature-responsive fields such as optical thermometers, and expands the application scenarios. Description of the Drawings

[0040] Figure 1 are the spectrograms of complexes Pt-1 (PtSZ) and Pt-20 (PtSZtBu) and their ligands LSZ and LSZtBu; among them, (a) is the absorption spectrum in dichloromethane, (b) is the PL spectrum in 2-methyltetrahydrofuran (2-MeTHF) at 77K and toluene solution at RT; (c) is the frontier orbital distribution and energy level of theoretical calculation;

[0041] Figure 2 are the single crystal structures of complexes Pt-1 and Pt-20;

[0042] Figure 3 is the spectrogram of complex Pt-20 in tetrahydrofuran solution; in the figure, (a) is the variable-temperature photoluminescence spectrogram, (b) and (c) are transient spectrograms, and (d) is the change in luminescence color during the heating process in toluene solution;

[0043] Figure 4 is the theoretical calculation diagram of complex Pt-20; in the figure, (a) is the energy diagram of the excited triplet state, (b) is the localized molecular orbital of the Pipek–Mezey localization of the Pt–S bond, (c) is the potential energy curve and optical transition of the triplet emission state (T1), and (d) is the spin density distribution of T1-MIN1 / T1-TS / T1-MIN2. Detailed Embodiments

[0044] The content of the present invention will be described in detail below. 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.

[0045] Unless otherwise specified, the following terms used herein are defined as follows:

[0046] As used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" can actually be quite large. In some cases, small molecules can include repeating units. For example, the use of a long-chain alkyl group as a substituent does not remove a molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, such as as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also serve as the core part of a dendrimer, which consists of a series of chemical shells built on the core part. The core part of a dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules", and all dendrimers currently used in the OLED field are considered small molecules.

[0047] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. In cases where a first layer is described as being "disposed over" a second layer, the first layer is disposed further from the substrate. Unless it is specified that the first layer "contacts" the second layer, there can be other layers between the first and second layers. For example, even if there are various organic layers between the cathode and the anode, the cathode can still be described as being "disposed over" the anode.

[0048] The terms "halo", "halogen", and "halo group" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine. The term "acyl" refers to a substituted carbonyl group (C(O)-Rs). The term "ester" refers to a substituted oxycarbonyl group (-O-C(O)-Rs or -C(O)-O-Rs). The term "ether" refers to an -ORs group. The terms "thio" or "thioether" are used interchangeably and refer to an -SRs group. The term "sulfinyl" refers to an -S(O)-Rs group. The term "sulfonyl" refers to an -SO2-Rs group. Where each Rs can be the same or different. The term "silyl" refers to a -Si(Rs)3 group, where each Rs can be the same or different.

[0049] In each of the above, Rs can be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred Rs are selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0050] The term "alkyl" means and includes straight-chain and branched-chain alkyl groups. Preferred alkyl groups are those containing from one to fifteen carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.

[0051] The term "cycloalkyl" means and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing from 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.

[0052] The terms "heteroalkyl" or "heterocycloalkyl" refer to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocycloalkyl group may be optionally substituted. The term "alkenyl" means and includes straight-chain and branched-chain alkenyl groups. An alkenyl group is essentially an alkyl group that includes at least one carbon-carbon double bond in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group that includes at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing from two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.

[0053] The term "alkynyl" means and includes straight-chain and branched-chain alkynyl groups. An alkynyl group is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing from two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted. The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted by an aryl group. Additionally, the aralkyl group may be optionally substituted.

[0054] The term "heterocyclic group" means and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. An aromatic heterocyclic group may be used interchangeably with a heteroaryl group. Preferred non-aromatic heterocyclic groups are those containing from 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, and the like, and cyclic ethers / sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.

[0055] The term "aryl" means and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. The polycycle can have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), where at least one of the rings is an aromatic hydrocarbon group, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl. Preferred aryl groups are aryl groups containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, fluorene, phenanthrene, fluorene, pyrene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group can be optionally substituted.

[0056] The term "heteroaryl" means and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many cases, O, S, or N are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring can have one to six heteroatoms. The heteropolycyclic system can have two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), where at least one of the rings is a heteroaryl, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl. The heteropolycyclic aromatic ring system can have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are heteroaryl groups containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazene, and their nitrogen analogs. Additionally, the heteroaryl group can be optionally substituted.

[0057] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and their respective nitrogen analogs are of particular interest.

[0058] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl are independently unsubstituted or independently substituted with one or more general substituents.

[0059] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, borono, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0060] In some cases, the preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, borono, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0061] In some cases, the preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, borono, aryl, heteroaryl, thio, and combinations thereof.

[0062] In other cases, the more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0063] The terms "substituted" and "substitution" mean that a substituent other than H is bonded to the relevant position, such as carbon or nitrogen. For example, when R1 represents monosubstitution, one R1 must not be H (i.e., substituted). Similarly, when R1 represents disubstitution, two R1s must not be H. Similarly, when R1 represents zero or no substitution, R1 can be, for example, hydrogen at the available valences of the ring atoms, such as the carbon atoms of benzene and the nitrogen atom in pyrrole, or can only represent nothing for a ring atom with a fully saturated valence, such as the nitrogen atom in pyridine. The maximum possible number of substitutions in a ring structure will depend on the total number of available valences in the ring atoms.

[0064] As used herein, "a combination thereof" means that one or more members of an applicable list are combined to form a known or chemically stable arrangement that can be envisioned by one of ordinary skill in the art from the applicable list. For example, an alkyl and deuterium can be combined to form a partially or fully deuterated alkyl; a halogen and an alkyl can be combined to form a haloalkyl substituent; and a halogen, an alkyl, and an aryl can be combined to form a haloarylalkyl. In one instance, the term substituted includes combinations of two to four of the listed groups. In another instance, the term substituted includes combinations of two to three groups. In yet another instance, the term substituted includes combinations of two groups. Preferred combinations of substituents are combinations that contain up to fifty atoms that are not hydrogen or deuterium, or combinations that include up to forty atoms that are not hydrogen or deuterium, or combinations that include up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0065] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art.

[0066] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name can be written as if it were the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0067] In some cases, a pair of adjacent substituents can optionally join or fuse to form a ring. Preferred rings are five-, six-, or seven-membered carbocyclic or heterocyclic rings, including cases where part of the ring formed by the pair of substituents is saturated and part of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved can be adjacent to each other on the same ring, or on two adjacent rings having the two closest available substitutable positions (such as the 2,2'-positions in biphenyl or the 1,8-positions in naphthalene), provided that they can form a stable fused ring system.

[0068] In some embodiments, the consumer product can be one of the following products: a flat panel display, a computer monitor, a medical monitor, a television, a sign, a lamp for internal or external lighting and / or signaling, a head-up display, a fully transparent or partially transparent display, a flexible display, a laser printer, a telephone, a cellular phone, a tablet computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay having a diagonal less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising a plurality of tiled together displays, a theater or stadium screen, a light therapy device, and a signpost.

[0069] Specific examples of the divalent platinum metal complex (phosphorescent material) of the present invention represented by the following general formula (1) are exemplified below, however, it is not to be construed as limiting the present invention.

[0070] Examples

[0071] Unless otherwise specified, all commercially available reagents involved in the following examples were used directly after purchase without further purification. 1H NMR spectra were measured in deuterated chloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO-d6) solutions, and the 1H NMR spectra were measured using a 400 or 500 MHz nuclear magnetic resonance spectrometer. If CDCl3 was used as the solvent, the 1H NMR spectra were referenced to CDCl3 (δ = 7.26 ppm) as the internal standard. If DMSO-d6 was used as the solvent, the 1H NMR spectra were referenced to DMSO-d6 (δ = 2.50 ppm) as the internal standard. The following abbreviations (or combinations) were used to interpret 1H NMR peaks: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad peak. In theoretical calculations, the geometric structures of the ground state (S0) molecules of the metal complexes were optimized using density functional theory (DFT); DFT calculations were performed using the B3LYP functional, where C, H, O, S, and N atoms used the 6-31G(d) basis set, and Pt and Pd atoms used the LANL2DZ basis set.

[0072] Example 1: The synthetic route of the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-1 is as follows:

[0073]

[0074] Synthesis of intermediate (SZ-Bpin): Add SZ-Br (2.00 g, 5.90 mmol, 1.00 equivalent), bis(pinacolato)diboron (2.25 g, 8.84 mmol, 1.50 equivalents), Pd(dppf)Cl2 (130 mg, 0.18 mmol, 3 mmol%) and anhydrous potassium acetate (1.74 g, 17.70 mmol, 3.0 equivalents) to a dry flask, evacuate and backfill with nitrogen three times using an oil pump, and inject dimethyl sulfoxide (30 mL). React at 85 °C for 48 hours, cool naturally to room temperature, add ethyl acetate, wash with deionized water, concentrate by rotary evaporation, and further purify using a silica gel column chromatography. The eluent used was petroleum ether / ethyl acetate = 100:1. After concentration, 2.18 g of a white solid product was obtained with a yield of 96%. 11H NMR (500 MHz, CDCl3) δ (ppm): 1.37 (s, 12H), 7.43–7.49 (m, 2H), 7.50–7.57 (m, 3H), 7.81–7.85 (m, 1H), 7.86–7.91 (m, 2H), 8.10–8.14 (m, 1H), 8.15 (dd, J = 7.5, 1.5 Hz, 1H), 8.17–8.21 (m, 1H). 13 13C NMR (125 MHz, CDCl3) δ (ppm): 24.87, 83.88, 120.34, 121.67, 122.58, 124.27, 124.97, 126.66, 127.03, 128.04, 130.87, 134.34, 134.80, 135.79, 136.07, 136.97, 138.63, 139.60, 139.96。

[0075] Synthesis of intermediate (Py-Br): Add o-methoxyphenylboronic acid (3.74 g, 24.62 mmol, 1.0 equiv), 2,6-dibromopyridine (7.0 g, 29.55 mmol, 1.2 equiv), tetrakis(triphenylphosphine)palladium (284 mg, 0.25 mmol, 1 mmol%) and anhydrous potassium carbonate (6.80 g, 49.24 mmol, 2.0 equiv) into a dry flask. Evacuate and refill with nitrogen three times using an oil pump, and then inject deionized water (20 mL) and redistilled 1,4-dioxane (100 mL). Stir at 70 °C for 72 h, rotary evaporate under reduced pressure to remove low-boiling solvents, and further purify by silica gel column chromatography using petroleum ether / ethyl acetate = 200:1 - 100:1 as the eluent. After concentration, 4.12 g of a colorless liquid is obtained with a yield of 63%. 1 1H NMR (500 MHz, CDCl3) δ (ppm): 3.87 (s, 3H), 6.99 (d, J = 8.5 Hz, 1H), 7.08 (td, J = 7.5, 1.0 Hz, 1H), 7.36–7.40 (m, 2H), 7.54 (t, J = 7.5 Hz, 1H), 7.85 (dd, J = 7.5, 1.5 Hz, 2H). 13 13C NMR (125 MHz, CDCl3) δ (ppm): 55.50, 111.32, 121.02, 123.79, 125.74, 127.16, 130.47, 131.23, 137.93, 141.31, 156.84, 156.97。

[0076] Synthesis of Intermediate (LSZ-OMe): Add SZ-Bpin (500 mg, 1.29 mmol, 1.0 equiv), Py-Br (340 mg, 1.29 mmol, 1.0 equiv), tetrakis(triphenylphosphine)palladium (45 mg, 0.039 mmol, 3 mmol%) and anhydrous potassium carbonate (357 mg, 2.58 mmol, 2.0 equiv) into a dry Schlenk tube. Pump and replace nitrogen three times, and then inject deionized water (1 mL) and redistilled 1,4-dioxane (4 mL). React at 85 °C for 48 hours, rotary evaporate under reduced pressure to remove low-boiling solvents, and further purify with a silica gel chromatography column. The eluent used is petroleum ether / ethyl acetate = 100:1 - 20:1. After concentration, 526 mg of white solid product is obtained with a yield of 92%. 1 H NMR (500 MHz, CDCl3) δ (ppm): 3.90 (s, 3H), 7.02 (dd, J = 8.0, 1.0 Hz, 1H), 7.11 (td, J = 7.5, 1.0 Hz, 1H), 7.38 (ddd, J = 8.0, 7.5, 2.0 Hz, 1H), 7.45–7.50 (m, 2H), 7.58 (s, 1H), 7.59 (d, J = 1.5 Hz, 1H), 7.64 (td, J = 7.5, 0.5 Hz, 1H), 7.75 (dd, J = 7.5, 1.0 Hz, 1H), 7.77–7.82 (m, 2H), 7.83–7.86 (m, 1H), 7.88 (dd, J = 7.5, 1.0 Hz, 1H), 8.06 (dd, J = 7.5, 2.0 Hz, 1H), 8.17–8.23 (m, 3H), 8.48 (t, J = 1.5 Hz, 1H). 13 C NMR (125 MHz, CDCl3) δ (ppm): 55.60, 111.45, 118.45, 120.48, 121.06, 121.70, 122.59, 123.69, 124.32, 125.09, 126.68, 126.74, 126.92, 126.94, 128.54, 129.14, 129.90, 131.52, 135.80, 136.21, 136.39, 136.99, 138.69, 139.63, 140.37, 140.88, 155.51, 156.46, 157.23。

[0077] Synthesis of Ligand (L1): Add LSZ-OMe (500 mg, 1.13 mmol, 1.0 equiv) and pyridine hydrochloride (1.30 g, 11.27 mmol, 10 equiv) to a dry Schlenk tube. Pump and replace with nitrogen three times, and inject anhydrous 1,3-dimethyl-2-imidazolidinone (4 mL). React at 180 °C for 17 hours, add ethyl acetate (100 mL), wash with deionized water, and concentrate by rotary evaporation. Further purify by silica gel column chromatography, using petroleum ether / dichloromethane = 100:1 - 10:1 as the eluent. After concentration, 455 mg of white solid product is obtained, with a yield of 94%. 1 H NMR (500 MHz, DMSO-d6) δ (ppm): 6.91–6.97 (m, 2H), 7.33 (ddd, J = 8.5, 7.0, 1.5 Hz, 1H), 7.60 (dd, J = 8.0, 4.0 Hz, 1H), 7.70 (t, J = 7.5 Hz, 1H), 7.75 (dd, J = 8.0, 7.0 Hz, 1H), 7.81 (dt, J = 7.5, 1.5 Hz, 1H), 7.90 (dd, J = 7.0, 1.5 Hz, 1H), 8.02–8.04 (m, 2H), 8.08 (ddd, J = 10.0, 8.0, 1.5 Hz, 2H), 8.13 (t, J = 8.0 Hz, 1H), 8.18–8.25 (m, 1H), 8.28 (t, J = 1.5 Hz, 1H), 8.48 (dd, J = 8.0, 1.5 Hz, 1H), 8.94 (dd, J = 4.0, 2.0 Hz, 1H), 14.41 (s, 1H). 13 C NMR (125 MHz, CDCl3) δ (ppm): 117.64, 118.46, 118.78, 118.86, 118.88, 120.70, 121.70, 122.57, 124.38, 125.18, 126.37, 126.41, 126.69, 126.79, 126.90, 129.32, 129.63, 131.52, 135.70, 136.26, 136.32, 138.49, 138.58, 139.41, 141.29, 154.41, 157.75, 159.94. HRMS (ESI): for C 29 H 20 NOS [M+H] + calcd 430.1260, found 430.1263。

[0078] Synthesis of Pt-1: Add L1 (200 mg, 0.47 mmol, 1.00 equivalent) and platinum(II) chloride (130 mg, 0.49 mmol, 1.05 equivalent) into a dry flask. Pump and replace nitrogen three times with an oil pump, and then inject benzonitrile (20 mL). Bubble nitrogen for 30 min to remove oxygen. Stir at 180 °C for 64 h, rotary evaporate under reduced pressure (80 °C) to remove the solvent, and further purify with a silica gel chromatography column. The eluent used is petroleum ether / dichloromethane = 5:1 - 1:1. After concentration, 95 mg of yellow solid product is obtained with a yield of 32%. 1 H NMR (500 MHz, CD2Cl2) δ (ppm): 6.66 (ddd, J = 8.0, 6.5, 1.5 Hz, 1H), 7.09 (dd, J = 8.5, 1.5 Hz, 1H), 7.26 (ddd, J = 8.5, 6.5, 1.5 Hz, 1H), 7.37 (t, J = 7.5 Hz, 1H), 7.65 (t, J = 7.5 Hz, 1H), 7.68 (td, J = 7.5, 1.5 Hz, 1H), 7.71–7.77 (m, 4H), 7.80 (dd, J = 8.0, 1.5 Hz, 1H), 7.99–8.03 (m, 3H), 8.07 (t, J = 7.5 Hz, 1H), 8.22 (ddd, J = 8.0, 1.5, 0.5 Hz, 1H), 8.58 (ddd, J = 8.0, 1.5, 0.5 Hz, 1H). HRMS (ESI): for C 29 H 18 NOPtS [M + H] + calcd 623.0751, found 623.0764。

[0079] Example 2: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-20

[0080] The synthesis route is as follows:

[0081]

[0082] Synthesis of intermediate (tBu-Bpin): Add tBu-OMe (20.0 g, 66.83 mmol, 1.0 equiv) into a dry flask, evacuate and backfill with nitrogen three times using an oil pump, and inject freshly distilled tetrahydrofuran (250 mL). Place the reaction flask in an ethanol cold bath, cool it to -80 °C with liquid nitrogen, then slowly add n-butyllithium (54.30 mL, 86.88 mmol, 1.3 equiv, 1.60 M in hexane) dropwise. After reacting for 1.5 h, inject isopropyl alcohol pinacol borate (18.65 g, 100 mmol, 1.5 equiv). Stir the reaction at room temperature for 19 h. Quench the reaction by adding aqueous ammonium chloride solution, and extract with ethyl acetate three times. Concentrate by rotary evaporation. Further purify using a silica gel column chromatography, with the eluent being petroleum ether / ethyl acetate = 100:1 - 10:1. Concentrate to obtain 19.68 g of a white solid product with a yield of 85%. 1 H NMR (500 MHz, CDCl3) δ (ppm): 1.31 (s, 9H), 1.37 (s, 12H), 1.39 (s, 9H), 3.84 (s, 3H), 7.44 (d, J = 2.5 Hz, 1H), 7.58 (d, J = 2.5 Hz, 1H). 13 C NMR (125 MHz, CDCl3) δ (ppm): 24.78, 30.95, 31.53, 34.39, 35.10, 63.03, 83.49, 127.49, 131.35, 140.87, 144.43, 163.30。

[0083] Synthesis of intermediate (tBuPy-Cl): Add tBu-Bpin (19.68 g, 56.83 mmol, 1.0 equiv), 2-bromo-6-chloropyridine (13.68 g, 71.07 mmol, 1.2 equiv), tetrakis(triphenylphosphine)palladium (1.37 g, 1.18 mmol, 2 mmol%) and anhydrous potassium carbonate (16.37 g, 118.44 mmol, 2.0 equiv) into a dry flask. Evacuate and backfill with nitrogen three times using an oil pump, and inject deionized water (40 mL) and freshly distilled 1,4-dioxane (220 mL). React at 65 °C for 43 h. Rotavap to remove low-boiling solvents under reduced pressure. Further purify using a silica gel column chromatography, with the eluent being petroleum ether / dichloromethane = 200:1 - 100:1. After concentration, separate the excess 2-bromo-6-chloropyridine under reduced pressure at 150 °C under vacuum to obtain 13.69 g of a white solid product with a yield of 73%. 1HNMR(500MHz, CDCl3) δ (ppm): 1.33 (s, 9H), 1.43 (s, 9H), 3.35 (s, 3H), 7.26–7.27 (m, 1H), 7.40 (d, J = 2.5 Hz, 1H), 7.46 (d, J = 2.5 Hz, 1H), 7.66 (t, J = 7.5 Hz, 1H), 7.71 (dd, J = 7.5, 1.0 Hz, 1H). 13 C NMR(125MHz, CDCl3) δ (ppm): 30.90, 31.47, 34.61, 35.31, 61.50, 122.02, 123.24, 125.15, 126.50, 131.79, 138.56, 142.07, 145.72, 151.11, 155.58, 158.82。

[0084] Synthesis of Intermediate (LSZtBu-OMe): Add SZ-Bpin (600 mg, 1.55 mmol, 1.0 equiv), tBuPy-Cl (567 mg, 1.71 mmol, 1.1 equiv), tetrakis(triphenylphosphine)palladium (54 mg, 0.047 mmol, 3 mmol%) and anhydrous potassium carbonate (429 mg, 3.11 mmol, 2.0 equiv) into a dry Schlenk tube. Pump and replace with nitrogen three times, and then inject deionized water (1 mL) and redistilled 1,4-dioxane (5 mL). React at 100 °C for 21 h, rotary evaporate under reduced pressure to remove low-boiling solvents, and further purify by silica gel column chromatography. The eluent used is petroleum ether / ethyl acetate = 1:0 - 50:1. After concentration, 820 mg of white solid product is obtained with a yield of 95%. 1 H NMR(500MHz, DMSO-d6) δ (ppm): 1.25 (s, 9H), 1.40 (s, 9H), 3.31 (s, 3H), 7.34 (d, J = 2.5 Hz, 1H), 7.54–7.56 (m, 2H), 7.60 (d, J = 2.5 Hz, 1H), 7.67 (d, J = 2.0 Hz, 1H), 7.68 (s, 1H), 7.71–7.76 (m, 2H), 7.81–7.84 (m, 1H), 7.97–8.01 (m, 2H), 8.07 (dd, J = 8.0, 1.0 Hz, 1H), 8.26 (dt, J = 8.0, 1.5 Hz, 1H), 8.41–8.45 (m, 2H), 8.67 (t, J = 2.0 Hz, 1H). 1313C NMR (125 MHz, CDCl3) δ (ppm): 30.96, 31.52, 34.62, 35.35, 61.39, 118.28, 120.52, 121.71, 122.65, 123.35, 124.35, 124.60, 125.10, 126.58, 126.74, 126.91, 126.97, 128.68, 129.24, 133.29, 135.82, 136.26, 136.82, 136.97, 138.65, 139.61, 140.07, 140.95, 141.97, 145.52, 155.74, 156.61, 157.88。

[0085] Synthesis of ligand (L20): Add LSZtBu-OMe (800 mg, 1.44 mmol, 1.0 equiv) and pyridine hydrochloride (1.66 g, 14.39 mmol, 10 equiv) to a dry Schlenk tube. Pump and replace with nitrogen three times, and inject anhydrous 1,3-dimethyl-2-imidazolidinone (2 mL). React at 180 °C for 18 hours, add ethyl acetate (100 mL), wash with pure water, and concentrate by rotary evaporation. Further purify using a silica gel column chromatography, with the eluent being petroleum ether / ethyl acetate = 100:1 - 50:1. After concentration, a yellow solid product of 660 mg is obtained with a yield of 85%. 1 1H NMR (500 MHz, DMSO-d6) δ (ppm): 1.33 (s, 9H), 1.41 (s, 9H), 7.34 (d, J = 2.0 Hz, 1H), 7.53–7.57 (m, 2H), 7.66–7.71 (m, 2H), 7.81–7.84 (m, 2H), 7.90 (ddd, J = 7.5, 2.0, 1.0 Hz, 1H), 7.97–8.01 (m, 1H), 8.05 (dd, J = 7.5, 0.5 Hz, 1H), 8.10 (ddd, J = 7.5, 2.0, 1.0 Hz, 1H), 8.14 (t, J = 7.5 Hz, 1H), 8.26 (d, J = 8.0 Hz, 1H), 8.40 (t, J = 2.0 Hz, 1H), 8.41–8.47 (m, 2H), 15.00 (s, 1H). 1313C NMR (125 MHz, CDCl3) δ (ppm): 29.68, 31.64, 34.35, 35.38, 118.06, 118.40, 118.46, 120.69, 121.04, 121.69, 122.71, 124.38, 125.15, 126.27, 126.53, 126.77, 126.84, 127.00, 129.26, 129.69, 135.73, 136.33, 136.45, 137.65, 138.35, 138.56, 138.86, 139.53, 139.81, 141.27, 154.18, 156.86, 159.09. HRMS (ESI): for C 37 H 36 NOS [M+H] + calcd 542.2512, found 542.2511。

[0086] Synthesis of Pt-20: Add L20 (300 mg, 0.55 mmol, 1.0 equiv) and platinum(II) dichloride (147 mg, 0.55 mmol, 1.0 equiv) to a dry flask. Pump and replace nitrogen three times with an oil pump, and then inject benzonitrile (25 mL). Bubble nitrogen for 30 min to remove oxygen. React at 180 °C for 65 h. Rotavaporize the solvent under reduced pressure at 80 °C, and then further purify with a silica gel chromatography column. The eluent used is petroleum ether / dichloromethane = 5:1 - 1:1. After concentration, 70 mg of a yellow solid product is obtained, with a yield of 19%. 1 1H NMR (500 MHz, CD2Cl2) δ (ppm): 1.32 (s, 9H), 7.05 (d, J = 8.5 Hz, 1H), 7.33–7.37 (m, 2H), 7.63 (t, J = 7.5 Hz, 1H), 7.66–7.74 (m, 5H), 7.78 (dd, J = 7.5, 1.5 Hz, 1H), 7.98–8.01 (m, 3H), 8.06 (t, J = 8.0 Hz, 1H), 8.20 (dd, J = 7.5, 1.0 Hz, 1H), 8.59 (ddd, J = 7.5, 1.5, 0.5 Hz, 1H). HRMS (ESI): for C 33 H 26 NOPtS [M+H] + calcd 679.1378, found 679.1350。

[0087] Example 3: The synthetic route of the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-3 is as follows:

[0088]

[0089]

[0090] Synthesis of Intermediate (LSZ-3): Add 2a (1.0 equiv), Py-Br (1.0 equiv), tetrakis(triphenylphosphine)palladium (3 mmol%), and anhydrous potassium carbonate (2.0 equiv) to a dry Schlenk tube. Evacuate and backfill with nitrogen three times using an oil pump, and then inject deionized water (1 mL) and freshly distilled 1,4-dioxane (4 mL). React at 85 °C for 48 h, rotary evaporate under reduced pressure to remove low-boiling solvents, and further purify by silica gel column chromatography using a eluent of petroleum ether / ethyl acetate = 100:1 - 20:1 to obtain a white solid product with a yield of 90%.

[0091] Synthesis of Ligand (L3): Add LSZ-3 (1.0 equiv) and pyridine hydrochloride (10 equiv) to a dry Schlenk tube. Evacuate and backfill with nitrogen three times using an oil pump, and then inject anhydrous 1,3-dimethyl-2-imidazolidinone (4 mL). React at 180 °C for 15 h, add ethyl acetate (100 mL), wash with deionized water, and rotary evaporate to concentrate. Further purify by silica gel column chromatography using a eluent of petroleum ether / dichloromethane = 100:1 - 10:1 to obtain a white solid product with a yield of approximately 94%.

[0092] Synthesis of Pt-3: Add L3 (1.00 equiv) and platinum(II) dichloride (1.05 equiv) to a dry flask. Evacuate and backfill with nitrogen three times using an oil pump, and then inject benzonitrile (20 mL). Bubble nitrogen through the solution for 30 min to remove oxygen. Stir at 180 °C for 61 h, rotary evaporate under reduced pressure to remove the solvent, and further purify by silica gel column chromatography using a eluent of petroleum ether / dichloromethane = 5:1 - 1:1 to obtain a yellow solid product with a yield of approximately 21%. MS: m / z 735.19 (M+H) + 。

[0093] Example 4: The synthetic route of the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-131 is as follows:

[0094]

[0095] Synthesis of Intermediate (L-131-OMe): Add 3a (1.0 equiv), Py-Br (1.3 equiv), tetrakis(triphenylphosphine)palladium (3 mol%), and potassium carbonate (2.0 equiv) to a Schlenk tube equipped with a magnetic stir bar. Then evacuate and backfill with nitrogen three times, and add 1,4-dioxane (8 mL) and water (2 mL) under nitrogen protection. React in an oil bath at 100 °C for 30 h, then cool to room temperature. After rotary evaporating under reduced pressure to remove the solvent, separate the crude product by silica gel column chromatography using a eluent of petroleum ether / ethyl acetate = 20:1 - 10:1 to obtain a yellow solid with a yield of approximately 81%.

[0096] Synthesis of ligand L-131: Add L-131 (1.0 equivalent) and pyridine hydrochloride (10.0 equivalents) into a Schlenk tube equipped with a magnetic stirrer. Then evacuate and refill with nitrogen three times, and add 1,3-dimethyl-2-imidazolidinone (3 mL) under nitrogen protection. After reacting in an oil bath at 180 °C for 17 hours, cool to room temperature, dilute with ethyl acetate, wash the organic phase with water, separate the layers, dry over anhydrous sodium sulfate, filter, and distill off the solvent under reduced pressure. The obtained crude product is separated by silica gel column chromatography, and the eluent is petroleum ether / ethyl acetate = 20:1 - 5:1, to obtain a white solid with a yield of about 85%.

[0097] Synthesis of Pt-131: Add L-131 (1.0 equivalent) and platinum(II) chloride (1.05 equivalents) into a three-necked flask equipped with a magnetic stirrer. Evacuate and refill with nitrogen three times using an oil pump, and inject benzonitrile (20 mL). Bubble nitrogen for 30 min to remove oxygen. Stir at 180 °C for 64 hours, rotary evaporate under reduced pressure to remove the solvent, and further purify by silica gel column chromatography. The eluent used is petroleum ether / dichloromethane = 5:1 - 1:1, to obtain a yellow solid product with a yield of about 32%. MS: m / z 788.13 (M+H) + 。

[0098] Example 5: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-2

[0099] Synthesize Pt-2 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 is replaced to synthesize the target compound Pt-2, a yellow solid. MS: m / z 651.10 (M+H) + 。

[0100] Example 6: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-4

[0101] Synthesize Pt-4 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 is replaced to synthesize the target compound Pt-4, a yellow solid. MS: m / z 775.13 (M+H) + 。

[0102] Example 7: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-15

[0103] Synthesize Pt-15 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 is replaced to synthesize the target compound Pt-15, a yellow solid. MS: m / z 785.18 (M+H) + 。

[0104] Example 8: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-22

[0105] Pt-22 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-22 can be synthesized only by replacing the ligand raw materials of the corresponding fragments in Example 1. Yellow solid. MS: m / z 792.15 (M+H) + 。

[0106] Example 9: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-26

[0107] Pt-26 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-26 can be synthesized only by replacing the ligand raw materials of the corresponding fragments in Example 1. Yellow solid. MS: m / z 755.16 (M+H) + 。

[0108] Example 10: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-29

[0109] Pt-29 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-29 can be synthesized only by replacing the ligand raw materials of the corresponding fragments in Example 1. Yellow solid. MS: m / z 711.13 (M+H) + 。

[0110] Example 11: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-30

[0111] Pt-30 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-30 can be synthesized only by replacing the ligand raw materials of the corresponding fragments in Example 1. Yellow solid. MS: m / z 699.10 (M+H) + 。

[0112] Example 12: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-31

[0113] Pt-31 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-31 can be synthesized only by replacing the ligand raw materials of the corresponding fragments in Example 1. Yellow solid. MS: m / z 673.08 (M+H) + 。

[0114] Example 13: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-49

[0115] Synthesize Pt-49 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material corresponding to the fragment in Example 1 is replaced to synthesize the target compound Pt-49, a yellow solid. MS: m / z 831.19 (M+H) + 。

[0116] Example 14: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-55

[0117] Synthesize Pt-55 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material corresponding to the fragment in Example 1 is replaced to synthesize the target compound Pt-55. A yellow solid. MS: m / z 750.09 (M+H) + 。

[0118] Example 15: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-58

[0119] Synthesize Pt-58 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material corresponding to the fragment in Example 1 is replaced to synthesize the target compound Pt-58. A yellow solid. MS: m / z 733.18 (M+H) + 。

[0120] Example 16: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-60

[0121] Synthesize Pt-60 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material corresponding to the fragment in Example 1 is replaced to synthesize the target compound Pt-60. A yellow solid. MS: m / z 841.21 (M+H) + 。

[0122] Example 17: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-63

[0123] Synthesize Pt-63 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material corresponding to the fragment in Example 1 is replaced to synthesize the target compound Pt-63. A yellow solid. MS: m / z 681.14 (M+H) + 。

[0124] Example 18: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-67

[0125] Synthesize Pt-67 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material corresponding to the fragment in Example 1 is replaced to synthesize the target compound Pt-67. A yellow solid. MS: m / z 757.18 (M+H) + 。

[0126] Example 19: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-71

[0127] Synthesize Pt-71 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw materials of the corresponding fragments in Example 1 are replaced to synthesize the target compound Pt-71. Yellow solid. MS: m / z 719.17 (M+H) + .

[0128] Example 20: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-73

[0129] Synthesize Pt-73 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw materials of the corresponding fragments in Example 1 are replaced to synthesize the target compound Pt-73. Yellow solid. MS: m / z 857.31 (M+H) + .

[0130] Example 21: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-77

[0131] Synthesize Pt-77 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw materials of the corresponding fragments in Example 1 are replaced to synthesize the target compound Pt-77. Yellow solid. MS: m / z 768.15 (M+H) + .

[0132] Example 22: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-80

[0133] Synthesize Pt-80 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw materials of the corresponding fragments in Example 1 are replaced to synthesize the target compound Pt-80. Yellow solid. MS: m / z 737.19 (M+H) + .

[0134] Example 23: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-82

[0135] Synthesize Pt-82 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw materials of the corresponding fragments in Example 1 are replaced to synthesize the target compound Pt-82. Yellow solid. MS: m / z 831.20 (M+H) + .

[0136] Example 24: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-93

[0137] Synthesize Pt-93 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-93, a yellow solid, can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. MS: m / z 791.93 (M+H) + 。

[0138] Example 25: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-94

[0139] Synthesize Pt-94 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-94, a yellow solid, can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. MS: m / z 811.22 (M+H) + 。

[0140] Example 26: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-98

[0141] Synthesize Pt-98 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-98, a yellow solid, can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. MS: m / z 769.79 (M+H) + 。

[0142] Example 27: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-103

[0143] Synthesize Pt-103 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-103 can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z 713.08 (M+H) + 。

[0144] Example 28: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-108

[0145] Synthesize Pt-108 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-108, a yellow solid, can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. MS: m / z 795.19 (M+H) + 。

[0146] Example 29: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-114

[0147] Synthesize Pt-114 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-114 can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z 851.26 (M+H)+ .

[0148] Example 30: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-122

[0149] Pt-122 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 was replaced to synthesize the target compound Pt-122, a yellow solid. MS: m / z 920.22 (M+H) + .

[0150] Example 31: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-123

[0151] Pt-123 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 was replaced to synthesize the target compound Pt-123, a yellow solid. MS: m / z 920.22 (M+H) + .

[0152] Example 32: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-125

[0153] Pt-125 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 was replaced to synthesize the target compound Pt-125, a yellow solid. MS: m / z 952.19 (M+H) + .

[0154] Example 33: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-129

[0155] Pt-129 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 was replaced to synthesize the target compound Pt-129. A yellow solid. MS: m / z 922.24 (M+H) + .

[0156] Example 34: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-130

[0157] Pt-130 was synthesized by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 was replaced to synthesize the target compound Pt-130, a yellow solid. MS: m / z 962.27 (M+H) + .

[0158] Example 35: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-131

[0159] Synthesize Pt-131 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-131 can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z 788.13 (M+H) + 。

[0160] Example 36: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-135

[0161] Synthesize Pt-135 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-135 can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z 799.19 (M+H) + 。

[0162] Example 37: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-139

[0163] Synthesize Pt-139 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-139 can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z 881.16 (M+H) + 。

[0164] Example 38: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-145

[0165] Synthesize Pt-145 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-145 can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z 1015.21 (M+H) + 。

[0166] Example 39: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-151

[0167] Synthesize Pt-151 by referring to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-151 can be synthesized only by replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z828.27 (M+H) + 。

[0168] Example 40: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt-153

[0169] Synthesize Pt-153 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-153 can be synthesized by only replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z 875.36 (M+H) + 。

[0170] Example 41: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-155

[0171] Synthesize Pt-155 according to the synthesis method of Reference Example 1. The difference from Example 1 is that the target compound Pt-155 can be synthesized by only replacing the ligand raw material of the corresponding fragment in Example 1. Yellow solid. MS: m / z 941.47 (M+H) + 。

[0172] Example 42: Synthesis route of tetradentate cyclometalated palladium(II) complex phosphorescent luminescent material Pd-156 is as follows:

[0173]

[0174] Synthesis of Pd-156: Add L-1 (1.0 equivalent), palladium acetate (1.05 equivalents) and tetrabutylammonium bromide (0.1 equivalent) to a three-necked flask equipped with a magnetic stir bar. Evacuate and replace with nitrogen three times. Under nitrogen protection, add acetic acid (20 mL), and deoxygenate by nitrogen bubbling for 30 min. Place the three-necked flask in an oil bath equipped with magnetic stirring, heat to 120 °C and react for 72 hours. After the reaction is cooled to room temperature, distill off the solvent under reduced pressure. The obtained crude product is separated by silica gel column chromatography. Eluent: petroleum ether / dichloromethane = 5:1 - 1:1, to obtain a yellow solid with a yield of 26%. MS: m / z 534.01 (M+H) + 。

[0175] Example 43: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-165

[0176] Synthesize Pt-165 according to the synthesis methods of Reference Example 1 and Example 42. The difference from Example 1 is that the ligand raw material of the corresponding fragment in Example 1 is replaced, and after metallization with reference to the example, the target compound Pt-165 can be synthesized. Yellow solid. MS: m / z 590.07 (M+H) + 。

[0177] Example 44: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-166

[0178] Synthesize Pt-166 by referring to the synthesis methods of Reference Example 1 and the Examples. The difference from Example 1 is only that the ligand raw materials for the corresponding fragments in Example 1 are replaced. After metallization with reference to the Examples, the target compound Pt-166 can be synthesized. Yellow solid. MS: m / z 693.12 (M+H) + 。

[0179] Example 45: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-171

[0180] Synthesize Pt-171 by referring to the synthesis methods of Reference Example 1 and the Examples. The difference from Example 1 is only that the ligand raw materials for the corresponding fragments in Example 1 are replaced. After metallization with reference to the Examples, the target compound Pd-171 can be synthesized. Yellow solid. MS: m / z 590.07 (M+H) + 。

[0181] Example 46: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-184

[0182] Synthesize Pt-184 by referring to the synthesis methods of Reference Example 1 and the Examples. The difference from Example 1 is only that the ligand raw materials for the corresponding fragments in Example 1 are replaced. After metallization with reference to the Examples, the target compound Pt-184 can be synthesized. Yellow solid. MS: m / z 847.16 (M+H) + 。

[0183] Example 47: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-188

[0184] Synthesize Pt-188 by referring to the synthesis methods of Reference Example 1 and the Examples. The difference from Example 1 is only that the ligand raw materials for the corresponding fragments in Example 1 are replaced. After metallization with reference to the Examples, the target compound Pt-188 can be synthesized. Yellow solid. MS: m / z 861.21 (M+H) + 。

[0185] Example 48: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-193

[0186] Synthesize Pt-193 by referring to the synthesis methods of Reference Example 1 and the Examples. The difference from Example 1 is only that the ligand raw materials for the corresponding fragments in Example 1 are replaced. After metallization with reference to the Examples, the target compound Pd-193 can be synthesized. Yellow solid. MS: m / z 584.02 (M+H) + 。

[0187] Example 49: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt-195

[0188] Synthesize Pt-195 by referring to the synthesis method of Reference Example 1 and the Examples. The difference from Example 1 is only that the ligand raw material corresponding to the fragment in Example 1 is replaced. After metallization by referring to the Examples, the target compound Pd-195, a yellow solid, can be synthesized. MS: m / z 665.10 (M+H) + 。

[0189] Example 50: Preparation of Temperature-Responsive Doping Solution

[0190] Place 1 mg of the complex Pt-20 in a glass tube, add 10 mL of toluene solution, dissolve it evenly by ultrasonic treatment, deoxygenate it by bubbling with nitrogen for 20 min, and then seal it to isolate oxygen to obtain the temperature-responsive doping solution.

[0191] Example 51: Device Example. All materials were purified by gradient heating sublimation under high vacuum (10 -5 -10 -6 Torr) before use. The indium tin oxide (ITO) substrates used for the devices were ultrasonically treated in deionized water, acetone, and isopropyl alcohol in sequence. The devices were prepared by vacuum thermal evaporation under a pressure of less than 10 -7 Torr. The anode electrode was indium tin oxide (ITO) with a thickness of The cathode was composed of Li2CO3 with a thickness of and Al. After all the devices were prepared, they were encapsulated with a glass cover and epoxy resin in a nitrogen glove box, and a moisture absorbent was added to the package. Taking the luminescent materials Pt-1 and Pt-20 as representative examples, device structures were prepared with them as the luminescent bodies under different host materials and transport materials. The devices and their electroluminescent properties are shown in Table 1.

[0192] Device 1: ITO / HATCN(10 nm) / TAPC(60 nm) / mCBP:PPT:Pt-1(1:1, 5%, 30 nm) / PPT(2 nm) / Bepp2:Li2CO3(5%, 35 nm) / Li2CO3(1 nm) / Al;

[0193] Device 2: ITO / HATCN(10 nm) / TAPC(60 nm) / mCBP:PPT:Pt-1(1:2, 5%, 30 nm) / PPT(2 nm) / Bepp2:Li2CO3(5%, 35 nm) / Li2CO3(1 nm) / Al;

[0194] Device 3: ITO / HATCN(10 nm) / TAPC(60 nm) / DPEPO:Pt-1(5%, 30 nm) / PPT(2 nm) / PPT:Li2CO3(5%, 35 nm) / Li2CO3(1 nm) / Al;

[0195] Device 4: ITO / HATCN (10 nm) / TAPC (60 nm) / mCBP:PPT:Pt-20 (1:1, 5%, 30 nm) / PPT (2 nm) / Bepp2:Li2CO3 (5%, 35 nm) / Li2CO3 (1 nm) / Al;

[0196] Device 5: ITO / HATCN (10 nm) / TAPC (60 nm) / mCBP:Pt-20 (5%, 30 nm) / PPT (2 nm) / Bepp2:Li2CO3 (5%, 35 nm) / Li2CO3 (1 nm) / Al;

[0197] Device 6: ITO / HATCN (10 nm) / TAPC (60 nm) / DPEPO:Pt-20 (1:1, 10%, 30 nm) / PPT (2 nm) / PPT:Li2CO3 (5%, 35 nm) / Li2CO3 (1 nm) / Al;

[0198] The molecular structures of the materials used in the above devices are as follows:

[0199]

[0200] Table 1. Table of Devices and Electroluminescence Characteristics

[0201]

[0202]

[0203] It can be seen from Table 1 that the compounds disclosed in the present invention can be used as luminescent materials in the preparation of organic electroluminescent devices, which has certain commercial application value.

[0204] Figure 1 are the spectrograms of the complexes Pt-1 (PtSZ) and Pt-20 (PtSZtBu) and their ligands LSZ and LSZtBu; among them, (a) is the absorption spectrum in dichloromethane, (b) is the PL spectrum in 2-methyltetrahydrofuran (2-MeTHF) at 77 K and toluene solution at RT (room temperature); (c) is the frontier orbital distribution and energy levels calculated theoretically. By Figure 1 It can be seen that in the emission spectra at 77 K and 298 K, both Pt-1 (PtSZ) and Pt-20 (PtSZtBu) show the same three emission bands, and these complexes show different emission behaviors in two different temperature ranges.

[0205] Figure 2 are the single crystal structure diagrams of the complexes Pt-1 and Pt-20; by Figure 2As can be seen, the structures of Pt-1 and Pt-20 were confirmed by single-crystal X-ray diffraction analysis. Pt-1 and Pt-20 exhibit highly distorted molecular structures, as evidenced by the dihedral angles between the dibenzothiophene plane and the phenol plane of 61.39° and 57.84°, respectively. However, the tetradentate ligand provides rigidity to maintain the square-planar coordination of the Pt(II) metal center, with the sum of its four bond angles approaching 360°. It is worth noting that Pt-1 and Pt-20 show S-Pt bond lengths similar to those in the literature and significantly longer than previously reported N-Pt (2.040 - ), due to the larger atomic radius of the S atom.

[0206] Figure 3 is the spectral diagram of complex Pt-20 in a tetrahydrofuran solution; in the figure, (a) is the variable-temperature photoluminescence spectral diagram, (b) and (c) are transient spectra, and (d) is the change in luminescence color during the heating process in a toluene solution. As Figure 3 can be seen, at 77 K, the main emission peak is quite intense compared to the second and third emission bands, showing cyan-green luminescence. However, as the temperature rises to 289 K, the main emission peak at 77 K (487 nm) gradually weakens and redshifts to 509 nm. At the same time, the emission sideband at 524 nm is significantly enhanced and begins to dominate the emission, reaching a peak of 539 nm at 298 K, showing yellow luminescence. Compared with the 77 K spectrum, the peak of each corresponding emission band at 298 K redshifts regularly by approximately 10 - 12 nm. From 77 to 200 K, the transient decay spectrum of PtSZtBu in a dilute 2-MeTHF solution shows single-exponential decay, with the excited-state lifetime (τ) gradually decreasing from 46 μs to 0.39 μs. However, at 250 and 298 K, PtSZtBu shows double-exponential decay, with a short τ of 45 ns and a relatively long τ of 1.2 μs at 250 K. This phenomenon is caused by different structural deformations of the excited state at different temperatures. The significant changes in the emission peaks and excited-state lifetimes at different temperatures indicate that the tetradentate Pt(II) / Pd(II) complexes based on dibenzothiophene coordination possess temperature-responsive properties and can be used in temperature-responsive luminescence fields such as biological labeling, imaging, anti-counterfeiting, and temperature sensing. From the change in luminescence color at different temperatures in Figure (d), it can be clearly seen that as the temperature rises, the luminescence color changes from cyan to green and then to yellow, indicating its temperature-responsive properties and its applicability in fields such as optical temperature sensing.

[0207] Figure 4It is the theoretical calculation diagram of complex Pt-20; in the diagram, (a) is the energy diagram of the excited triplet state, (b) is the localized molecular orbital of the Pipek–Mezey localization of the Pt–S bond, (c) is the potential energy curve and optical transition of the triplet emission state (T1), and (d) is the spin density distribution of T1-MIN1 / T1-TS / T1-MIN2. From Figure 4 It can be seen that the change in the emission light color of Pt-20 at different temperatures is caused by the change in the spatial structure due to the change in the nature of its S-Pt bond. Based on this, it can be inferred that complexes with the same parent nucleus and containing such S-Pt will have similar changes in luminescence color. Such complexes provided can be used for the preparation of temperature indicating devices.

[0208] Those of ordinary skill in the art can understand that the above embodiments are specific examples for implementing the present invention, and in practical applications, various changes can be made in form and details without departing from the spirit and scope of the present invention. For example, many substituent structures described here can be replaced by other structures without departing from the spirit of the present invention.

Claims

1. A phosphorescent material based on a divalent platinum or palladium metal complex coordinated with dibenzothiophene, characterized in that, The phosphorescent material has a general formula structure shown in formula (I): Wherein: M is Pt or Pd; Y 1 -Y 17 each independently selected from an N or C atom; R 1 、R 2 、R 3 、R 4 and R 5 each independently may be mono-substituted, di-substituted, tri-substituted, tetra-substituted or unsubstituted; R 1 、R 2 each independently represents any one or a combination of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C1-C24 alkoxy, substituted or unsubstituted C1-C24 silyl, substituted or unsubstituted C6-C36 aryl; R 3 is represented by any one or a combination thereof of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted C1-C24 alkyl, substituted or unsubstituted C1-C24 cycloalkyl, substituted or unsubstituted C3-C24 heterocycloalkyl, substituted or unsubstituted C1-C24 alkoxy, substituted or unsubstituted C6-C36 aryl, C6-C36 heteroaryl, substituted or unsubstituted C6-C36 arylamino, substituted or unsubstituted C6-C36 heteroarylamino, substituted or unsubstituted C1-C24 alkylamino; the heteroatoms in the heterocycloalkyl and heteroaryl may be selected from N, O, S or Si; the heteroatoms in the heteroarylamino may be selected from O, S or Si; R 4 and R 5 each independently represents hydrogen, deuterium, a halogen, -CN, a substituted or unsubstituted C1-C24 alkyl group, a substituted or unsubstituted C1-C24 cycloalkyl group, a substituted or unsubstituted C3-C24 heterocycloalkyl group, a substituted or unsubstituted C1-C24 alkoxy group, a substituted or unsubstituted C6-C36 aryl group, or a combination thereof; when the above groups have substituents, the substituents each independently are selected from deuterium, a halogen, -CN, a C1-C10 alkyl group, a C3-C10 cycloalkyl group, a C6-C30 aryl group, or a combination thereof.

2. The phosphorescent material according to claim 1, wherein All hydrogen atoms in formula (I) can be replaced by deuterium atoms.

3. The phosphorescent material according to claim 1, wherein Any two substituents in formula (I) can be joined or fused together to form a ring.

4. The phosphorescent material according to claim 1, wherein R in formula (I) 1 、R 2 、R 3 、R 4 and R 5 Two or more adjacent ones of them may optionally be linked to form a ring.

5. The phosphorescent material according to claim 1, characterized in that, R as described in formula (I) 1 and R 2 each independently represents any one or a combination thereof selected from hydrogen, deuterium, F, -CN, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, methoxy, and trimethylsilane.

6. The phosphorescent material according to claim 1, wherein R as described in formula (I) 3 represents any one or a combination thereof selected from hydrogen, deuterium, F, -CN, methyl, ethyl, propyl, isopropyl, tert-butyl, heptyl, cyclopentane, pyridyl, carbazolyl, diphenylamino, phenothiazinyl, phenoxazinyl, phenyl, methoxy, trimethylsilyl, benzofuranyl, benzothiophenyl, pyrrolidinyl, 1,1-dimethylindenyl.

7. The phosphorescent material according to claim 1, wherein R as described in formula (I) 4 and R 5 each independently represents any one or a combination of hydrogen, deuterium, F, -CN, methyl, ethyl, propyl, isopropyl, tert-butyl, heptyl, cyclopentyl, cyclopentenyl, phenyl, methoxy, trimethylsilyl, benzofuranyl, benzothiophenyl, pyrrolidinyl, 1,1-dimethylindenyl.

8. A phosphorescent material of divalent platinum or palladium metal complex coordinated by dibenzothiophene, characterized in that, The phosphorescent material is selected from one of the following structures:

9. Use of the divalent platinum or palladium metal complex phosphorescent material based on dibenzothiophene coordination according to any one of claims 1-8 as a temperature-responsive luminescent material.

10. An optical thermometer, characterized in that, The optical thermometer comprises the divalent platinum or palladium metal complex phosphorescent material based on dibenzothiophene coordination according to any one of claims 1-8.

11. Use of the divalent platinum or palladium metal complex phosphorescent material based on dibenzothiophene coordination according to any one of claims 1-8 in the preparation of an organic light-emitting device.

12. The application according to claim 11, wherein The organic light-emitting device is an organic light-emitting diode, a light-emitting diode or a light-emitting electrochemical cell.

13. An organic light-emitting diode, comprising: An anode; A cathode; And An organic layer disposed between the anode and the cathode, wherein the organic layer contains the divalent platinum or palladium metal complex phosphorescent material based on dibenzothiophene coordination according to any one of claims 1-8.

14. A consumer product, characterized in that, The consumer product comprises the organic light-emitting diode according to claim 12.

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