Metal complex, organic electroluminescence device and application

Abstract

The invention relates to a metal complex, an organic electroluminescence device and application. The metal complex disclosed by the invention has a structure as shown in a formula (I), contains ptycene groups, and shows enhanced phosphorescence quantum yield, good luminescence stability and high luminescence efficiency when being applied to an OLED (Organic Light Emitting Diode), especially used in a blue light emission region. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and relates to a metal coordination compound, an organic electroluminescent device, and the application of the metal coordination compound. Background Art

[0002] OLED (organic light-emitting diode) utilizes an organic thin film, which emits light when a voltage is applied to the device. OLED is becoming an increasingly concerned technology for applications such as flat panel displays, lighting, and backlighting.

[0003] One application of phosphorescent emission molecules is full-color displays. Industry standards for such displays require pixels suitable for emitting specific colors. Specifically, these standards require saturated red, green, and blue pixels. Currently, red and green phosphorescent materials with a luminous efficiency of 100% are used in OLEDs of various sizes. So far, no blue phosphorescent material has been commercialized, but the luminous efficiency of blue fluorescent materials is only 25%. Although a variety of blue light materials have been widely researched and developed, such as inorganic fluorescent powders, metal complexes, and thermally activated delayed fluorescence materials, etc. However, there are many dissipation pathways for triplet excitons of phosphorescent materials, such as non-radiative transitions, delayed fluorescence, triplet-triplet annihilation, quenching by oxygen and water vapor, etc., which seriously affect the improvement of phosphorescent performance. As people have discovered that crystal engineering can utilize strong intermolecular interactions to effectively inhibit non-radiative transitions of triplet excitons, and because of its dense molecular packing, it can reduce the quenching of triplet excitons by oxygen, water vapor, etc., which is an effective way to achieve high-efficiency room-temperature phosphorescence. However, in the crystal aggregate state, intermolecular π-π stacking easily leads to triplet-triplet annihilation, dissipating a large amount of triplet excitons and affecting the improvement of phosphorescent efficiency; and π-π stacking will increase the intermolecular conjugation degree and cause a red shift in luminescence, making it difficult to achieve blue phosphorescence. Therefore, how to construct long-lived and high-efficiency blue phosphorescence remains one of the challenges in the field of organic phosphorescent materials. Summary of the Invention

[0004] To solve the above problems existing in the prior art, the present invention provides a metal complex, which exhibits enhanced phosphorescence quantum yield when used in an OLED, especially in the blue light emission region, and is suitable as an emitter material in OLED applications. In addition, the present invention also provides an organic electroluminescent device comprising the above metal complex.

[0005] The first object of the present invention is to provide a metal complex, which has good electroluminescent stability and excellent luminous efficiency.

[0006] The second object of the present invention is to provide an application of the metal complex in an organic electroluminescent device.

[0007] The third object of the present invention provides an organic electroluminescent device including the metal complex.

[0008] The fourth object of the present invention provides a consumer product including the metal complex.

[0009] In order to achieve the above objects, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a metal complex having a structure represented by formula (I):

[0011]

[0012] Wherein, ring A, ring B, ring C and ring D are each independently selected from a monocyclic or polycyclic fused ring system, and each ring of the monocyclic and polycyclic fused ring systems is independently a 5-membered or 6-membered carbocyclic ring, a 5-membered or 6-membered heterocyclic ring, and in the rings A, B, C, D, R a , R b , R c and R d at least one contains or is selected from the structures represented by formula (2), formula (3) or formula (4):

[0013]

[0014] Metal M represents a metal element with a relative atomic mass greater than 40;

[0015] X 1 ~X 6 are each independently selected from C, B or N;

[0016] Z 1 ~Z 4 are each independently selected from C or N;

[0017] X 7 ~X 18 are each independently selected from CR 5 , or N;

[0018] L 1 , L 2 , L 3 are each independently selected from a single bond, O, S, S=O, SO 2 , Se, NR 6 , PR 6 , R 6 P=O, CR 6 R 7 , C=O, SiR 6 R 7 , GeR 6 R 7or BR 6 ;

[0019] R a , R b , R c and R d Each independently represents mono- or poly-substituted to saturated substitution, or unsubstituted;

[0020] R a , R b , R c , R d Each is independently selected from the group consisting of formula (2), formula (3), formula (4), hydrogen, or a group consisting of deuterium, a halogen atom, a cyano group, an acyl group, a carboxyl group, an ether group, an ester group, an isocyano group, a sulfide group, a selenoalkyl group, a sulfinyl group, a sulfonyl group, a phosphine group, a substituted or unsubstituted C 1 ~C 40 Straight chain alkyl, substituted or unsubstituted C 1 ~C 40 Straight chain heteroalkyl, substituted or unsubstituted C 3 ~C 40 Branched or cyclic alkyl, substituted or unsubstituted C 1 ~C 40 Alkoxy, substituted or unsubstituted C 6 ~C 60 Arylalkyl, substituted or unsubstituted C 6 ~C 60 Aryloxy, substituted or unsubstituted C 6 ~C 60 Arylamine, substituted or unsubstituted C 3 ~C 40 Silane, substituted or unsubstituted C 2 ~C 40 Alkenyl, substituted or unsubstituted C 4 ~C 40 Cycloalkenyl, substituted or unsubstituted C 2 ~C 40 Heteroalkenyl, substituted or unsubstituted C 2 ~C 40 Alkynyl, substituted or unsubstituted C 6 ~C 60 Aryl, substituted or unsubstituted C 2 ~C 60 Heteroaryl and combinations thereof, any adjacent two or more R a , R b , R c , R d They may be arbitrarily joined or fused to form a substituted or unsubstituted ring;

[0021] R 1 ~R7 Each independently selected from hydrogen, or selected from the group consisting of: deuterium, a halogen atom, a cyano group, an acyl group, a carboxyl group, an ether group, an ester group, an isocyano group, a sulfide group, a selenoalkyl group, a sulfinyl group, a sulfonyl group, a phosphino group, a substituted or unsubstituted C 1 ~C 40 linear alkyl, a substituted or unsubstituted C 1 ~C 40 linear heteroalkyl, a substituted or unsubstituted C 3 ~C 40 branched or cyclic alkyl, a substituted or unsubstituted C 1 ~C 40 alkoxy, a substituted or unsubstituted C 6 ~C 60 arylalkyl, a substituted or unsubstituted C 6 ~C 60 aryloxy, a substituted or unsubstituted C 6 ~C 60 arylamino, a substituted or unsubstituted C 3 ~C 40 silyl, a substituted or unsubstituted C 2 ~C 40 alkenyl, a substituted or unsubstituted C 4 ~C 40 cycloalkenyl, a substituted or unsubstituted C 2 ~C 40 heteroalkenyl, a substituted or unsubstituted C 2 ~C 40 alkynyl, a substituted or unsubstituted C 6 ~C 60 aryl, a substituted or unsubstituted C 2 ~C 60 heteroaryl and combinations thereof, any two or more adjacent R 1 ~R 7 may optionally be joined or fused to form a substituted or unsubstituted ring;

[0022] R a 、R b 、R c 、R d 、R 1 ~R 7 The substituents in are each independently selected from the group consisting of: deuterium, a halogen atom, a cyano group, an acyl group, a carboxyl group, an ether group, an ester group, an isocyano group, a sulfide group, a selenoalkyl group, a sulfinyl group, a sulfonyl group, a phosphino group, C 1 ~C 40 linear alkyl, C 1 ~C 40 linear heteroalkyl, C 3 ~C 40 branched or cyclic alkyl, C1 ~C 40 haloalkyl, C 1 ~C 40 deuterated alkyl, C 1 ~C 40 alkoxy, C 6 ~C 60 arylalkyl, C 6 ~C 60 aryloxy, C 6 ~C 60 arylamino, C 3 ~C 40 silyl, C 2 ~C 40 alkenyl, C 4 ~C 40 cycloalkenyl, C 2 ~C 40 heteroalkenyl, C 2 ~C 40 alkynyl, C 6 ~C 60 aryl, C 2 ~C 60 heteroaryl and combinations thereof.

[0023] The metal complex of the present invention introduces a triptycene structure into the ligand. During the metal-to-ligand charge transfer process of C^Pt^N, by utilizing the steric hindrance characteristics of the triptycene group, the steric hindrance and polarity in the metal polarization direction are enhanced, the stability and quantum efficiency of the ligand are improved. When used in organic electroluminescent materials, especially in the blue light emission region, it exhibits enhanced phosphorescence quantum yield, good luminescence stability, and high luminescence efficiency.

[0024] In some embodiments, the ring A is selected from heteroaryl of C 2 ~C 60 In some embodiments, the ring A is selected from heteroaryl of C 2 ~C 40 In some embodiments, the ring A is selected from heteroaryl of C 2 ~C 30 In some embodiments, the ring A is selected from heteroaryl of C 2 ~C 20 In some embodiments, the ring A is selected from heteroaryl of C 2 ~C 10Heteroaryl. In some embodiments, the heteroatom in the heteroaryl related to Ring A is one or more (e.g., 1, 2, or 3). In some embodiments, the heteroatom in the heteroaryl related to Ring A is an N atom. In some examples, Ring A is a benzimidazolyl group. In some examples, Ring A is a benzimidazolyl group substituted with any one of the structures of Formula (2), Formula (3), or Formula (4). In some examples, Ring A is an imidazolyl group fused to any one of the structures of Formula (2), Formula (3), or Formula (4).

[0025] In some embodiments, Ring B is selected from aryl of C 6 ~C 60 or heteroaryl of C 2 ~C 60 In some embodiments, Ring B is selected from aryl of C 6 ~C 640 or heteroaryl of C 2 ~C 40 In some embodiments, Ring B is selected from aryl of C 6 ~C 30 or heteroaryl of C 2 ~C 30 In some embodiments, Ring B is selected from aryl of C 6 ~C 20 or heteroaryl of C 2 ~C 20 In some embodiments, Ring B is selected from aryl of C 6 ~C 10 or heteroaryl of C 2 ~C 10 In some embodiments, the heteroatom in the heteroaryl related to Ring B is one or more (e.g., 1, 2, or 3). In some embodiments, the heteroatom in the heteroaryl related to Ring B is an N atom. In some examples, Ring B is a benzene ring. In some examples, Ring B is a benzene ring substituted with any one of the structures of Formula (2), Formula (3), or Formula (4). In some examples, Ring B is any one of the structures of Formula (2), Formula (3), or Formula (4).

[0026] In some embodiments, Ring C is selected from heteroaryl of C 2 ~C 60 In some embodiments, Ring C is selected from heteroaryl of C 2 ~C 40 In some embodiments, Ring C is selected from heteroaryl of C 2 ~C 30 In some embodiments, Ring C is selected from heteroaryl of C 2 ~C 20 In some embodiments, Ring C is selected from heteroaryl of C2 ~C 10 heteroaryl groups. In some embodiments, the heteroatom in the heteroaryl group related to Ring C is one or more (e.g., 1, 2, or 3). In some embodiments, the heteroatom in the heteroaryl group related to Ring C is an N atom. In some embodiments, Ring C is a carbazolyl group. In some embodiments, Ring C is a carbazolyl group substituted with any one of the structures of formula (2), formula (3), or formula (4). In some embodiments, Ring C is a benzopyrrolyl group fused to any one of the structures of formula (2), formula (3), or formula (4).

[0027] In some embodiments, Ring D is selected from C 2 ~C 60 heteroaryl groups. In some embodiments, Ring D is selected from C 2 ~C 40 heteroaryl groups. In some embodiments, Ring D is selected from C 2 ~C 30 heteroaryl groups. In some embodiments, Ring D is selected from C 2 ~C 20 heteroaryl groups. In some embodiments, Ring D is selected from C 2 ~C 10 heteroaryl groups. In some embodiments, the heteroatom in the heteroaryl group related to Ring D is one or more (e.g., 1, 2, or 3). In some embodiments, the heteroatom in the heteroaryl group related to Ring D is an N atom. In some embodiments, Ring D is a pyridyl group. In some embodiments, Ring D is a pyridyl group substituted with any one of the structures of formula (2), formula (3), or formula (4). In some embodiments, Ring D is selected from any one of the structures of formula (2), formula (3), or formula (4). In some embodiments, Ring D is selected from any one of the structures of formula (2), formula (3), or formula (4), and the ring atom Z 4 connected to metal M

[0028] In some embodiments, metal M is selected from Ir, Pt, Pd, Ru, Rh, Os, Au, Cu, Ni, Co, Ga, or Ge; preferably, metal M is selected from Pt or Pd. According to one embodiment of the present invention, metal M is Pt.

[0029] In some embodiments, the L 1 、L 2 、L 3 each independently selected from a single bond, O, S, Se, NR 6 、PR 6 、BR 6 、CR 6 R 7 or SiR 6 R7 。In some embodiments, L 1 is selected from O, S, or Se. In some embodiments, L 2 is selected from a single bond, NR 6 , PR 6 , or BR 6 。In some embodiments, L 3 is selected from a single bond, O, S, or Se. According to one embodiment of the present invention, the L 2 is selected from NR 6 , PR 6 , or BR 6 。

[0030] In some embodiments, the substituents in R a , R b , R c , R d , R 1 ~R 7 are each independently selected from the group consisting of: deuterium, a halogen atom, a cyano group, an acyl group, a carboxyl group, an ether group, an ester group, an isocyano group, a sulfide group, a selenoalkyl group, a sulfinyl group, a sulfonyl group, a phosphino group, C 1 ~C 20 linear alkyl, C 1 ~C 20 linear heteroalkyl, C 3 ~C 20 branched or cyclic alkyl, C 1 ~C 20 haloalkyl, C 1 ~C 20 deuterated alkyl, C 1 ~C 20 alkoxy, C 6 ~C 30 arylalkyl, C 6 ~C 30 aryloxy, C 6 ~C 30 arylamino, C 3 ~C 20 silyl, C 2 ~C 20 alkenyl, C 4 ~C 20 cycloalkenyl, C 2 ~C 20 heteroalkenyl, C 2 ~C 20 alkynyl, C 6 ~C 30 aryl, C 2 ~C 30 heteroaryl, and combinations thereof.

[0031] In some embodiments, Ra , R b , R c , R d , R 1 ~R 7 The substituents in are each independently selected from the group consisting of the following groups: deuterium, halogen atom, cyano group, acyl group, carboxyl group, ether group, ester group, isocyano group, sulfhydryl group, selenoalkyl group, sulfinyl group, sulfonyl group, phosphino group, C 1 ~C 10 linear alkyl, C 1 ~C 10 linear heteroalkyl, C 3 ~C 12 branched or cyclic alkyl, C 1 ~C 10 haloalkyl, C 1 ~C 10 deuterated alkyl, C 1 ~C 10 alkoxy, C 6 ~C 20 arylalkyl, C 6 ~C 20 aryloxy, C 6 ~C 20 arylamino, C 3 ~C 12 silyl, C 2 ~C 10 alkenyl, C 4 ~C 12 cycloalkenyl, C 2 ~C 10 heteroalkenyl, C 2 ~C 10 alkynyl, C 6 ~C 20 aryl, C 2 ~C 20 heteroaryl and combinations thereof.

[0032] In some embodiments, the metal complex has a group of compounds of the formula M(LA)(LB):

[0033]

[0034] wherein, LA-LB is selected from the group consisting of:

[0035]

[0036]

[0037]

[0038] and / or LA-LB are selected from the group consisting of:

[0039]

[0040]

[0041]

[0042]

[0043]

[0044] wherein, ring A1, ring B1, ring C1, ring C2 and ring D are each independently selected from any one of the structures of formula (2), formula (3) or formula (4);

[0045] W is selected from O, S, CR 8 R 9 , SiR 8 R 9 , CR 8 R 9 CR 10 R 11 or NR x ;

[0046] Y is selected from O, S or NR x ;

[0047] The R in LA1 to LA24 x are each independently selected from formula (2), formula (3) or formula (4), and in formula (2), formula (3) and formula (4), X 7 ~X 18 at least one is C and is connected to R x ;

[0048] The R in LA25 to LA60, LB1 to LB140 x in each occurrence, are each independently selected from formula (2), formula (3), formula (4), or selected from the group consisting of: substituted or unsubstituted C 1 ~C 40 linear alkyl, substituted or unsubstituted C 3 ~C 40 branched or cyclic alkyl, substituted or unsubstituted C 6 ~C 60 arylalkyl, substituted or unsubstituted C 2 ~C 40 alkenyl, substituted or unsubstituted C 4 ~C 40 cycloalkenyl, substituted or unsubstituted C 6 ~C 60Aryl, substituted or unsubstituted C 2 ~C 60 Heteroaryl, and combinations thereof, R x may be joined or fused to adjacent R a , R 5 , R c or R d optionally to form a substituted or unsubstituted ring;

[0049] R Y each occurrence is independently selected from formula (2), formula (3), formula (4), or selected from the group consisting of: substituted or unsubstituted C 1 ~C 40 linear alkyl, substituted or unsubstituted C 3 ~C 40 branched or cyclic alkyl, substituted or unsubstituted C 6 ~C 60 arylalkyl, substituted or unsubstituted C 2 ~C 40 alkenyl, substituted or unsubstituted C 4 ~C 40 cycloalkenyl, substituted or unsubstituted C 6 ~C 60 aryl, substituted or unsubstituted C 2 ~C 60 heteroaryl, and combinations thereof;

[0050] R 8 ~R 11 each is independently selected from hydrogen, or selected from the group consisting of: deuterium, halogen atom, cyano group, acyl group, carboxyl group, ether group, ester group, isocyano group, sulfhydryl group, selenoalkyl group, sulfinyl group, sulfonyl group, phosphino group, substituted or unsubstituted C 1 ~C 40 linear alkyl, substituted or unsubstituted C 1 ~C 40 linear heteroalkyl, substituted or unsubstituted C 3 ~C 40 branched or cyclic alkyl, substituted or unsubstituted C 1 ~C 40 alkoxy, substituted or unsubstituted C 6 ~C 60 arylalkyl, substituted or unsubstituted C 6 ~C 60 aryloxy, substituted or unsubstituted C 6 ~C 60 arylamino, substituted or unsubstituted C 3 ~C 40 silyl, substituted or unsubstituted C 2 ~C40 Alkenyl, substituted or unsubstituted C 4 -C 40 Cycloalkenyl, substituted or unsubstituted C 2 -C 40 Heteroalkenyl, substituted or unsubstituted C 2 -C 40 Alkynyl, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 2 -C 60 Heteroaryl and combinations thereof, any two or more adjacent R 8 -R 11 may optionally be joined or fused to form a substituted or unsubstituted ring;

[0051] R x 、R Y and R 8 -R 11 The substituents in are each independently selected from the group consisting of: deuterium, halogen atom, cyano group, acyl group, carboxyl group, ether group, ester group, isocyano group, sulfide group, selenoalkyl group, sulfinyl group, sulfonyl group, phosphino group, C 1 -C 40 linear alkyl, C 1 -C 40 linear heteroalkyl, C 3 -C 40 branched or cyclic alkyl, C 1 -C 40 haloalkyl, C 1 -C 40 deuterated alkyl, C 1 -C 40 alkoxy, C 6 -C 60 arylalkyl, C 6 -C 60 aryloxy, C 6 -C 60 arylamino, C 3 -C 40 silyl, C 2 -C 40 alkenyl, C 4 -C 40 cycloalkenyl, C 2 -C 40 heteroalkenyl, C 2 -C 40 alkynyl, C 6 -C 60 aryl, C 2 -C 60 heteroaryl and combinations thereof.

[0052] According to an embodiment of the present invention, the metal complex is selected from the group consisting of Pt(LAi)(LBj), where i is an integer from 1 to 60, j is an integer from 1 to 140, LA is selected from the structures shown by LA1 to LA60 or the structure in which some or all of the hydrogen atoms in the structures shown by LA1 to LA60 are replaced by deuterium atoms; LB is selected from the structures shown by LB1 to LB140 or the structure in which some or all of the hydrogen atoms in the structures shown by LB1 to LB140 are replaced by deuterium atoms.

[0053] In some embodiments, each Y is independently selected from S or NR x According to an embodiment of the present invention, each Y is NR x 。

[0054] In some embodiments, R 8 ~R 11 are each independently selected from hydrogen or the group consisting of: deuterium, a halogen atom, a substituted or unsubstituted C 1 ~C 20 linear alkyl, a substituted or unsubstituted C 1 ~C 20 linear heteroalkyl, a substituted or unsubstituted C 3 ~C 20 branched or cyclic alkyl, a substituted or unsubstituted C 1 ~C 20 alkoxy, a substituted or unsubstituted C 6 ~C 30 arylalkyl, a substituted or unsubstituted C 6 ~C 30 aryloxy, a substituted or unsubstituted C 6 ~C 30 arylamino, a substituted or unsubstituted C 3 ~C 20 silyl, a substituted or unsubstituted C 2 ~C 20 alkenyl, a substituted or unsubstituted C 4 ~C 20 cycloalkenyl, a substituted or unsubstituted C 2 ~C 20 heteroalkenyl, a substituted or unsubstituted C 2 ~C 20 alkynyl, a substituted or unsubstituted C 6 ~C 30 aryl, a substituted or unsubstituted C 2 ~C 30 heteroaryl and combinations thereof, any two or more adjacent R 8 ~R 11Optionally joined or fused to form a substituted or unsubstituted ring.

[0055] In some embodiments, R 8 ~R 11 Each independently selected from hydrogen, or a group consisting of: deuterium, a halogen atom, a substituted or unsubstituted C 1 ~C 10 linear alkyl, a substituted or unsubstituted C 3 ~C 10 branched or cyclic alkyl, a substituted or unsubstituted C 6 ~C 20 aryl.

[0056] In some embodiments, R 8 ~R 11 Each independently selected from hydrogen, or a group consisting of: deuterium, fluorine, chlorine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl.

[0057] In some embodiments, the W is selected from O, S, C(CH 3 ) 2 , C(C 6 H 5 ) 2 , Si(CH 3 ) 2 , Si(C 6 H 5 ) 2 or NR x . According to one embodiment of the present invention, the W is selected from O, S, C(CH 3 ) 2 , C(C 6 H 5 ) 2 , Si(CH 3 ) 2 or Si(C 6 H 5 ) 2 .

[0058] In some embodiments, the substituents of R x , R Y and R 8 ~R 11 are each independently selected from the group consisting of: deuterium, a halogen atom, a cyano group, an acyl group, a carboxyl group, an ether group, an ester group, an isocyano group, a thio group, a selenoalkyl group, a sulfinyl group, a sulfonyl group, a phosphino group, a C 1 ~C 20 linear alkyl, a C 1 ~C 20 linear heteroalkyl, a C3 ~C 20 branched or cyclic alkyl, C 1 ~C 20 haloalkyl, C 1 ~C 20 deuterated alkyl, C 1 ~C 20 alkoxy, C 6 ~C 30 arylalkyl, C 6 ~C 30 aryloxy, C 6 ~C 30 arylamino, C 3 ~C 20 silyl, C 2 ~C 20 alkenyl, C 4 ~C 20 cycloalkenyl, C 2 ~C 20 heteroalkenyl, C 2 ~C 20 alkynyl, C 6 ~C 30 aryl, C 2 ~C 30 heteroaryl and combinations thereof.

[0059] In some embodiments, the substituents in R x , R Y and R 8 ~R 11 are each independently selected from the group consisting of: deuterium, halogen atom, cyano group, acyl group, carboxyl group, ether group, ester group, isocyano group, sulfide group, selenyl group, sulfinyl group, sulfonyl group, phosphino group, C 1 ~C 10 linear alkyl, C 1 ~C 10 linear heteroalkyl, C 3 ~C 12 branched or cyclic alkyl, C 1 ~C 10 haloalkyl, C 1 ~C 10 deuterated alkyl, C 1 ~C 10 alkoxy, C 6 ~C 20 arylalkyl, C 6 ~C 20 aryloxy, C 6 ~C 20 arylamino, C 3 ~C 12 silyl, C 2 ~C 10Alkenyl, C 4 ~C 12 Cycloalkenyl, C 2 ~C 10 Heteroalkenyl, C 2 ~C 10 Alkynyl, C 6 ~C 20 Aryl, C 2 ~C 20 Heteroaryl and combinations thereof.

[0060] According to one embodiment of the present invention, the R a , R b , R c , R d are each independently selected from the group consisting of the structure represented by formula (2), the structure represented by formula (3), the structure represented by formula (4), a hydrogen atom, a deuterium atom, fluorine, a cyano group, an isocyano group, R A1 ~R A30 , R B1 ~R B195 , R C1 ~R C80 , R A1 ~R A30 substituted with one or more deuterium atoms, R B1 ~R B195 substituted with one or more deuterium atoms, R C1 ~R C80 substituted with one or more deuterium atoms.

[0061] According to one embodiment of the present invention, the R 1 ~R 11 are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a cyano group, R A1 ~R A30 , R B1 ~R B195 , R C1 ~R C80 , R A1 ~R A30 substituted with one or more deuterium atoms, R B1 ~R B195 substituted with one or more deuterium atoms, R C1 ~R C80 substituted with one or more deuterium atoms.

[0062] According to one embodiment of the present invention, the R x , R Y are each independently selected from formula (2), formula (3), formula (4), or selected from the group consisting of R A1 ~R A25 , R B1 ~RB185 , R C1 to R C79 , R substituted with one or more deuterium atoms A1 to R A25 , R substituted with one or more deuterium atoms B1 to R B185 , R substituted with one or more deuterium atoms C1 to R C79 and the group consisting of

[0063] R as described in the present invention A1 to R A30 has the structural formula shown below:

[0064]

[0065]

[0066] R as described in the present invention B1 to R B195 has the structure shown below:

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] R as described in the present invention C1 to R C80 has the structure shown below:

[0073]

[0074]

[0075] In some embodiments, formula (2) has a structure shown in any one of formulae (2-1) to (2-3), formula (3) has a structure shown in any one of formulae (3-1) to (3-8), and formula (4) has a structure shown in any one of formulae (4-1) to (4-3):

[0076]

[0077]

[0078] wherein, R 1 to R 4is defined as in the foregoing definition of the present invention. In some embodiments, R 1 to R 4 are independently selected from hydrogen, deuterium, a halogen atom, C 1 to C 10 linear or branched alkyl, C 3 to C 12 cyclic alkyl. In some embodiments, R 1 to R 4 are independently selected from hydrogen, deuterium, fluorine, methyl, ethyl, propyl, isopropyl, tert-butyl.

[0079] In some embodiments, the metal complex is selected from compounds represented by any one of the structures of formula (I-1) to formula (I-6) below:

[0080]

[0081] Wherein, R a to R d are defined as in the foregoing of the present invention, and in formula (I-1), at least 1, preferably 1 to 2 of R a to R d are structures represented by formula (2), formula (3) or formula (4);

[0082] In formula (I-2), (I-3), (I-4) and (I-5), ring B, ring C1, ring C2 and ring D are each independently selected from any one of the structures of formula (2), formula (3) or formula (4);

[0083] In formula (I-6), is fused to any one of the structures of formula (2), formula (3) or formula (4), preferably fused to an adjacent ring atom on the aromatic ring in any one of the structures of formula (2), formula (3) or formula (4).

[0084] In some embodiments, in formula (I-1) to formula (I-6), R a to R d are independently selected from the structures represented by formula (2), formula (3) or formula (4), or hydrogen, or the group consisting of: deuterium, a halogen atom, substituted or unsubstituted C 1 to C 10 linear alkyl, substituted or unsubstituted C 3 to C 12 branched or cyclic alkyl, substituted or unsubstituted C 6 to C 20 arylalkyl, substituted or unsubstituted C 6 to C 20 aryl and combinations thereof.

[0085] In some embodiments, in formula (I-1) to formula (I-6), Ra to R d are independently selected from the structures represented by formula (2), formula (3) or formula (4), or hydrogen, or the group consisting of the following groups: deuterium, a halogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, phenyl substituted by a C 1 ~C 6 linear or branched alkyl-substituted phenyl.

[0086] In some embodiments, when R a to R d are independently selected from the structures represented by formula (2), formula (3) or formula (4), the structures represented by formula (2), formula (3) or formula (4) are connected to any one of the structures of formula (I-1) to formula (I-6) through the ring atoms on their aromatic rings.

[0087] According to some embodiments of the present invention, the metal complex is selected from the group consisting of the compounds shown in Table 1 below or the compounds in which some or all of the hydrogen atoms in the compounds shown in Table 1 are replaced by deuterium atoms:

[0088] Table 1

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] In a second aspect, the present invention provides the use of the above metal complex in the preparation of an organic electroluminescent device.

[0096] In some embodiments, the metal complex is used as a doping material in the organic light-emitting layer of the organic electroluminescent device.

[0097] In some embodiments, the organic light-emitting layer includes a host material and a doping material, and the doping amount of the metal complex in the organic light-emitting layer is: 1 to 50% of the mass of the host material, such as 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or any value between them, preferably 1 to 20%, more preferably 5 to 15%.

[0098] In a third aspect, the present invention provides an organic electroluminescent device, which includes an organic layer, and the organic layer includes the metal complex of the present invention as described above.

[0099] In some embodiments, the organic electroluminescent device further includes an anode and a cathode, and the organic layer is disposed between the anode and the cathode. In some embodiments, the organic layer is one or more layers, and at least one layer of the organic layer contains the metal complex of the present invention as described above.

[0100] In some embodiments, the organic electroluminescent device of the present invention includes a light-emitting layer, and the light-emitting layer contains the metal complex of the present invention as described above.

[0101] According to an embodiment of the present invention, the light-emitting layer in the organic electroluminescent device emits blue light.

[0102] In some embodiments, the light-emitting layer contains the metal complex of the present invention as described above, and may further contain other compounds, such as fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

[0103] In some embodiments, the light-emitting layer includes a host compound and a dopant compound, and the dopant compound includes the metal complex of the present invention; the host compound may include one or more; when the host compound is a combination of multiple types, it includes at least one n-type host compound and at least one p-type host compound.

[0104] According to an embodiment of the present invention, the light-emitting layer in the organic electroluminescent device contains an organic electroluminescent material, and further, the organic electroluminescent material contains the metal complex disclosed by the present invention.

[0105] According to an embodiment of the present invention, at least one of the host compounds is selected from the group consisting of phenyl, naphthyl, pyridyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phenanthryl, azaphenanthryl, pyrimidinyl, triazine, triphenylene, carbazolyl, indolocarbazolyl, dibenzothiophenyl, dibenzofuranyl, fluorenyl, silafluorenyl, dibenzoselenophenyl, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracenyl, aza-triphenylene, aza-carbazolyl, aza-indolocarbazolyl, aza-dibenzothiophenyl, aza-dibenzofuranyl, aza-dibenzoselenophenyl, and aza-(5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene) group or a combination derived from these systems.

[0106] The organic layer described in the present invention may be a light-emitting layer and the metal complex as described herein may be an emissive dopant compound or a non-emissive dopant compound. Further, the dopant compound is 0.1% to 100% by mass of the host compound in the light-emitting layer. Further, the dopant compound is 1% to 50% by mass of the host compound in the light-emitting layer, such as 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or any value therebetween, preferably 1 to 20%, more preferably 5 to 15%. Further, the dopant compound is 1% to 30% by mass of the host compound in the light-emitting layer. Further, the dopant compound is 1% to 20% by mass of the host compound in the light-emitting layer. Further, the dopant compound is 5% to 15% by mass of the host compound in the light-emitting layer. In some embodiments, the dopant compound is 12% by mass of the host compound in the light-emitting layer.

[0107] In some embodiments, the host compound is selected from the group consisting of the following structures:

[0108]

[0109]

[0110] According to one embodiment of the present invention, the organic electroluminescent device further comprises a hole injection layer, which may be a single-material functional layer or a functional layer comprising a plurality of materials, and the most common of the plurality of materials is a hole transport material doped with a certain proportion of a p-type conductive dopant material. Common p-type dopant materials include:

[0111]

[0112]

[0113] According to another embodiment of the present invention, a composition is also disclosed, which comprises a metal complex, and the specific structure of the metal complex is as shown in any of the foregoing embodiments.

[0114] The materials described herein as suitable for use in a particular layer of an organic light-emitting device may be used in combination with a variety of other materials present in the device. For example, the emissive dopant compounds disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that may be used in combination.

[0115] These methods are generally known to those of ordinary skill in the art, and they can be applied to organic electroluminescent elements containing the compounds according to the present invention without creative efforts.

[0116] According to one embodiment, novel ligands of metal complexes are disclosed. The inventors have found that the introduction of these ligands unexpectedly narrows the emission spectrum, reduces the sublimation temperature, and improves the luminous efficiency of the device.

[0117] As a method for preparing the organic electroluminescent device of the present invention, the following preparation methods can be listed, but are not limited thereto, and those skilled in the art can make various changes based on the common general knowledge in the art. The foregoing preparation method includes the following steps:

[0118] Cleaning step: Cleaning a glass substrate with ITO using a cleaning agent, deionized water, an organic solvent, etc.;

[0119] Step of forming a hole injection layer: Evaporating a hole injection layer forming material containing the organic electroluminescent material of the present invention on the foregoing anode layer by vacuum evaporation to form a hole injection layer containing the organic electroluminescent material of the present invention on the foregoing substrate;

[0120] Step of forming a hole transport layer: Forming a hole transport layer on the foregoing hole injection layer by vacuum evaporation;

[0121] Step of forming an organic light-emitting layer: Evaporating an organic light-emitting layer forming material containing the material of the present invention on the foregoing hole transport layer by vacuum evaporation to form an organic light-emitting layer containing the organic electroluminescent material of the present invention on the foregoing hole transport layer;

[0122] Step of forming an electron transport layer: Evaporating an electron transport layer forming material containing the organic electroluminescent material of the present invention on the foregoing organic light-emitting layer by vacuum evaporation to form an electron transport layer containing the organic electroluminescent material of the present invention on the foregoing organic light-emitting layer;

[0123] Step of forming a cathode layer: Evaporating, sputtering, or spin-coating a cathode forming material on the foregoing electron transport layer to form a cathode layer.

[0124] Fourth aspect, the present invention provides a consumer product including the organic electroluminescent device described above.

[0125] The consumer product of the present invention includes but is not limited to: a display device, a lighting device.

[0126] The consumer product of the present invention can be any one of the following products: flat panel display, computer monitor, medical monitor, television, billboard, lamp for internal or external lighting and / or signaling, head-up display, fully transparent or partially transparent display, flexible display, laser printer, telephone, cellular phone, tablet computer, phablet, personal digital assistant (PDA), wearable device, laptop computer, digital camera, video camera, viewfinder, microdisplay with a diagonal less than 2 inches, 3-D display, virtual reality or augmented reality display, vehicle, video wall comprising a plurality of tiled together displays, theater or stadium screen, light therapy device, and signboard.

[0127] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0128] (1) The metal complex of the present invention regulates its photophysical properties by adjusting the structure of the ligands around the metal center and controlling the structure of the substituents on the ligands, and has the advantages of narrow emission spectrum, high stability and high efficiency, and has broad application prospects in many fields such as OLED display and lighting.

[0129] (2) When the metal complex of the present invention is applied in an OLED, especially in the blue emission region, it exhibits enhanced phosphorescence quantum yield, good luminescence stability, high luminescence efficiency, and is suitable as an emissive dopant (doping material) in OLED applications.

[0130] (3) The metal complex of the present invention can obtain an organic electroluminescent device with blue phosphorescent electroluminescence and improved luminescence efficiency, and the luminescent device has good thermal stability. The consumer product of the organic light-emitting device of the present invention can obtain an electronic device with blue phosphorescent electroluminescence and improved luminescence efficiency by containing the organic electroluminescent device of the present invention. Description of the Drawings

[0131] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0132] Figure 1 It is a schematic diagram of an organic electroluminescent device 100 according to a specific embodiment of the present invention.

[0133] Figure 2 It is a schematic diagram of an organic electroluminescent device 200 according to a specific embodiment of the present invention.

[0134] The reference numerals are as follows:

[0135] 101: Substrate, 102: Anode, 103: Hole injection layer, 104: Hole transport layer, 105: Electron blocking layer, 106: Light emitting layer, 107: Hole blocking layer, 108: Electron transport layer, 109: Electron injection layer, 110: Cathode, 111: Capping layer (CPL);

[0136] 201: Substrate, 202: Anode, 203: Hole injection layer, 204: Hole transport layer, 205: First light emitting layer, 206: Electron transport layer, 207: Charge generation layer, 208: Hole injection layer, 209: Hole transport layer, 210: Second light emitting layer, 211: Electron transport layer, 212: Electron injection layer, 213: Cathode. Detailed implementation manners

[0137] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation manners obtained by those of ordinary skill in the art without creative efforts fall within the scope protected by the present invention.

[0138] In the substituted or unsubstituted ring formed by the adjacent groups binding to each other in the present invention, the "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring. The term "bonding" to form a ring is referred to as a fused ring, and a fused ring refers to a fused aliphatic ring, a fused aromatic ring, a fused aliphatic heterocyclic ring, a fused aromatic heterocyclic ring or a form formed by their combination. The term "fused" ring means that two aromatic rings are joined together through a shared single bond or double bond. As non-limiting examples, for instance, two benzene rings are fused into a naphthalene ring, a benzene ring and a furan ring are fused into benzofuran, two benzene rings and a furan ring are fused into dibenzofuran, etc.

[0139] The "aryl" or "aromatic ring" according to the present invention means and includes a monocyclic aromatic hydrocarbon group and a polycyclic aromatic ring system. 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, heterocyclic and / or heteroaryl. Preferred aryl or aromatic rings are aryls containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Particularly preferred are aryls having six carbons, ten carbons or twelve carbons. Suitable aryls include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, anthryl, phenanthryl, fluoranthenyl, pyrenyl, perylenyl, indenyl and azulyl, preferably phenyl, biphenyl, terphenyl, triphenylene, fluoranthenyl and naphthyl. Additionally, the aryl can be optionally substituted.

[0140] "Heteroaryl" or "heteroaromatic ring" in the sense of the present invention refers to a monocyclic aromatic group and a polycyclic aromatic ring system comprising at least one heteroatom. Heteroatoms include, but are not limited to, oxygen, sulfur, nitrogen, phosphorus, boron, silicon or selenium. In many cases, oxygen, sulfur or nitrogen are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The hetero polycyclic system may 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 heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic and / or heteroaryl. The hetero polycyclic aromatic ring system may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryl is heteroaryl containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl includes dibenzothienyl, dibenzofuranyl, dibenzoselenophenyl, furyl, thienyl, benzofuranyl, benzothienyl, benzoselenophenyl, carbazolyl, indolocarbazolyl, pyridylindolyl, pyrrolodipyridyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, oxatriazolyl, dioxazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, oxathiazinyl, oxadiazinyl, indolyl, benzimidazolyl, indazolyl, indoxazinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, phthalazinyl, pteridinyl, xanthenyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, benzofuranopyridyl, furanodipyridyl, benzothiophenopyridyl, thiophenodipyridyl, benzoselenophenopyridyl, selenophenodipyridyl, 1,2-azaborolyl, 1,3-azaborolyl, 1,4-azaborolyl, borazynyl and its nitrogen analogs, preferably dibenzothienyl, dibenzofuranyl, dibenzoselenophenyl, carbazolyl, indolocarbazolyl, imidazolyl, pyridyl, triazinyl, benzimidazolyl, 1,2-azaborolyl, 1,3-azaborolyl, 1,4-azaborolyl, borazynyl and its nitrogen analogs. Additionally, the heteroaryl may be optionally substituted.

[0141] The aryl or heteroaryl according to the present invention particularly refers to a group derived from the following substances: phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, pyrenyl, a group selected from the group consisting of a base, a perylene group, a fluoranthene group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an azobenzene group, a terphenyl group, a triphenylphenyl group, a quaterphenyl group, a fluorenyl group, a spirobifluorenyl group, a dihydrophenanthrenyl group, a triphenylene group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis- or trans-indeno[1,2-b]fluorene group, a cis- or trans-indeno[1,2-b]carbazole group, a cis- or trans-indolo[2,3-b]carbazole group, a trindene group, an isotrindene group, a spirotrindene group, a spiroisotrindene group, a furyl group, a benzofuryl group, an isobenzofuryl group, a dibenzofuryl group, a thienyl group, a benzothienyl group, an isobenzothienyl group, a dibenzothienyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, a carbazolyl group, a pyridyl group, a quinolinyl group, an isoquinolinyl group, an acridinyl group, a phenanthridinyl group, a benzo[5,6]quinolinyl group, a benzo[6,7]quinolinyl group, a benzo[7,8]quinolinyl group, a phenothiazinyl group, a phenoxazinyl group, a pyrazolyl group, a benzopyrazolyl group, an indazolyl group, an imidazolyl group, a benzimidazolyl group, a naphthimidazolyl group, a phenanthrimidazolyl group, a pyridinimidazolyl group, a pyrazinimidazolyl group, a quinoxalinimidazolyl group, an oxazolyl group, a benzoxazolyl group, a naphthoxazolyl group, an anthroxazolyl group, a phenanthroxazolyl group, an isoxazolyl group, a 1,2-thiazolyl group, a 1,3-thiazolyl group, a benzothiazolyl group, a pyridazinyl group, a hexaazatriphenylene group, a benzopyridazinyl group, a pyrimidinyl group, a benzopyrimidinyl group, a quinoxalinyl group, a 1,5-diazaanthracenyl group, a 2,7-diazapyrenyl group, a 2,3-diazapyrenyl group, a 1,6-diazapyrenyl group, a 1,8-diazapyrenyl group, a 4,5-diazapyrenyl group, a 4,5,9,10-tetraazaperylene group, a pyrazinyl group, a phenazinyl group, a phenoxazinyl group, a phenothiazinyl group, a fluoranthene ring group, a naphthyridinyl group, an azacarbazolyl group, a benzocarbazolyl group, a carbazolyl group, a phenanthrolinyl group, a 1,2,3-triazolyl group, a 1,2,4-triazolyl group, a benzotriazolyl group, a 1,2,3-oxadiazolyl group, a 1,2,4-oxadiazolyl group, a 1,2,5-oxadiazolyl group, a 1,3,4-oxadiazolyl group, a 1,2,3-thiadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,2,5-thiadiazolyl group, a 1,3,4-thiadiazolyl group, a 1,3,5-triazinyl group, a 1,2,4-triazinyl group, a 1,2,3-triazinyl group, a tetrazolyl group, a 1,2,4,5-tetrazinyl group, a 1,2,3,4-tetrazinyl group, a 1,2,3,5-tetrazinyl group, a purinyl group, a pteridinyl group, an indolizinyl group, a quinazolinyl group, a benzothiadiazolyl group, a 1,3,2-diazaborolyl group, a 1,3,2-benzo[d]diazaborolyl group, or a group derived from a combination of these systems

[0142] "Alkyl" in the sense of the present invention includes straight-chain and branched-chain alkyl groups. The alkyl group can be an alkyl group having 1 to 40 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. Additionally, the alkyl group can be optionally substituted.

[0143] "Cycloalkyl" refers to a cyclic alkyl group, including monocyclic, polycyclic and spiroalkyl groups. The cycloalkyl group can be a cycloalkyl group having 3 to 40 ring carbon atoms, preferably a cycloalkyl group having 4 to 20 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl are preferred. Additionally, the cycloalkyl group can be optionally substituted.

[0144] "Heterocycloalkyl" in the sense of the present invention refers to a cycloalkyl group in which a single hydrogen atom or -CH 2 - group can be substituted by an oxygen, sulfur, halogen atom, nitrogen, phosphorus, boron, silicon or selenium atom, preferably a group substituted by oxygen, sulfur or nitrogen. Additionally, the heteroalkyl or heterocycloalkyl group can be optionally substituted.

[0145] "Alkenyl" encompasses straight-chain, branched-chain and cyclic olefin groups. The alkenyl group can be an alkenyl group containing 2 to 40 carbon atoms, preferably an alkenyl group having 2 to 20 carbon atoms. Examples of alkenyl groups include vinyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylethenyl, styryl, 2,2-diphenylethenyl, 1,2-diphenylethenyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl and norbornenyl. Additionally, the alkenyl group can be optionally substituted.

[0146] "Alkynyl" encompasses straight-chain alkynyl groups. The alkynyl group can be an alkynyl group containing 2 to 40 carbon atoms, preferably an alkynyl group having 2 to 20 carbon atoms. Examples of the alkynyl group include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3,3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3,3-diisopropyl-1-pentynyl, phenyl ethynyl, phenyl propynyl, etc. Among the above, ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and phenyl ethynyl are preferred. Additionally, the alkynyl group can be optionally substituted.

[0147] "Cycloalkenyl" refers to a cyclic olefin group, including monocyclic, polycyclic, and spiro cycloalkenyl groups. The preferred cycloalkenyl group is a cycloalkenyl group containing 3 to 15 ring carbon atoms, which can be cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc.; in addition, one or more hydrogen atoms can also be replaced by deuterium atoms, halogen atoms, or cyano groups.

[0148] "Heteroalkenyl" or "heterocycloalkenyl" in the sense of the present invention refers to an alkenyl or cycloalkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, the at least one heteroatom is selected from oxygen, sulfur, nitrogen, phosphorus, boron, silicon, or selenium, preferably oxygen, sulfur, or nitrogen. The preferred alkenyl and cycloalkenyl groups are those containing 3 to 15 carbon atoms. Additionally, the heteroalkenyl and heterocycloalkenyl groups can be optionally substituted.

[0149] "Heteroalkyl" is formed by replacing one or more carbons in an alkyl chain with a heteroatom selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, phosphorus atoms, silicon atoms, germanium atoms, and boron atoms. The heteroalkyl can be a heteroalkyl having 1 to 40 carbon atoms, preferably a heteroalkyl having 1 to 20 carbon atoms, and more preferably a heteroalkyl having 1 to 12 carbon atoms. Examples of the heteroalkyl include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermylmethyl, trimethylgermylethyl, trimethylgermylisopropyl, dimethylethylgermylmethyl, dimethylisopropylgermylmethyl, tert-butyldimethylgermylmethyl, triethylgermylmethyl, triethylgermylethyl, triisopropylgermylmethyl, triisopropylgermylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl, triisopropylsilylethyl. Additionally, the heteroalkyl can be optionally substituted.

[0150] "Alkoxy" in the sense of the present invention is represented by -O-alkyl, -O-cycloalkyl, -O-heteroalkyl or -O-heteroalkenyl. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl and heteroalkenyl are the same as those described above. The alkoxy may be an alkoxy having 1 to 40 carbon atoms, preferably an alkoxy having 1 to 20 carbon atoms. Examples of alkoxy include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuryloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. Additionally, the alkoxy may be optionally substituted.

[0151] "Selenoalkyl" is represented by -Se-alkyl, -Se-cycloalkyl, -Se-heteroalkyl or -Se-heteroalkenyl. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl and heteroalkenyl are the same as those described above. The selenoalkyl may be a selenoalkyl having 1 to 40 carbon atoms, preferably a selenoalkyl having 1 to 20 carbon atoms. Examples of selenoalkyl include methylseleno, ethylseleno, propylseleno, butylseleno, pentylseleno, hexylseleno, cyclopropylseleno, cyclobutylseleno, cyclopentylseleno, cyclohexylseleno, tetrahydrofurylseleno, tetrahydropyranylseleno, methoxypropylseleno, ethoxyethylseleno, methoxymethylseleno and ethoxymethylseleno, etc. Additionally, the selenoalkyl may be optionally substituted.

[0152] "Acyl" in the sense of the present invention refers to a substituted carbonyl (COR x ).

[0153] "Carboxyl" or "carboxylic acid group" in the sense of the present invention refers to a substituted carboxyl (R x COOH).

[0154] "Ester group" in the sense of the present invention refers to a substituted oxycarbonyl (-OCOR x or CO 2 R x ).

[0155] "Ether group" in the sense of the present invention refers to the -OR x group.

[0156] "Thio group" or "thioether" as described herein are used interchangeably and refer to the -SR x group.

[0157] "Sulfinyl" in the sense of the present invention refers to the -SOR x group.

[0158] "Sulfonyl" in the sense of the present invention refers to the -SO 2 R x group.

[0159] "Phosphino" in the sense of the present invention means -PR x 3 group, where each R x can be the same or different.

[0160] Each of the above R x , preferably selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl.

[0161] Aryloxy is represented by -O-aryl or -O-heteroaryl. Examples and preferred examples of aryl and heteroaryl are the same as those described above. Aryloxy can be aryloxy having 6 to 60 carbon atoms, preferably aryloxy having 6 to 20 carbon atoms. Examples of aryloxy include phenoxy and biphenyloxy. Additionally, aryloxy can be optionally substituted.

[0162] The arylphosphino used in the present invention means diarylphosphino substituted by an aryl having 6 to 60 carbon atoms. As non-limiting examples of arylphosphino, there are diphenylphosphino, bis(4-trimethylsilylbenzene)phosphino, etc. Arylphosphinyloxy is the phosphorus atom of diarylphosphino oxidized to the highest valence state.

[0163] The arylamino or arylamino group used in the present invention means an amino group substituted by an aryl having 6 to 60 carbon atoms. As non-limiting examples of arylamino, there are diphenylamino, carbazolyl, etc.

[0164] "Halogen", "halogen atom", "halo group" in the sense of the present invention are used interchangeably and mean fluorine, chlorine, bromine, or iodine.

[0165] Aralkyl or arylalkyl are used interchangeably to encompass aryl-substituted alkyl groups. Aralkyl groups may be aralkyl groups having 7 to 60 carbon atoms, preferably aralkyl groups having 7 to 40 carbon atoms, and more preferably aralkyl groups having 7 to 20 carbon atoms. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthyl-ethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthyl-ethyl, 2-β-naphthyl-ethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, Aralkyl can be substituted with 1-hydroxy-2-phenylisopropyl or 1-chloro-2-phenylisopropyl. Among the above, benzyl, 1-hydroxy-2-phenylisopropyl or 1-chloro-2-phenylisopropyl are preferred. In the above, benzyl, 1-hydroxy-2-phenylisopropyl or 1-chloro-2-phenylisopropyl are preferred. In addition, aralkyl can be substituted with 1-hydroxy-2-phenylisopropyl or 1-chloro-2-phenylisopropyl.

[0166] Alkylsilyl or silyl encompasses alkyl-substituted silicon groups. It may be an alkylsilyl having 3 to 40 carbon atoms, preferably an alkylsilyl having 3 to 20 carbon atoms. Examples of alkylsilyl include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-tert-butylsilyl, triisobutylsilyl, dimethyltert-butylsilyl, methylditert-butylsilyl. In addition, the alkylsilyl may be optionally substituted.

[0167] The arylsilyl group encompasses at least one aryl-substituted silicon group. The arylsilyl group can be an arylsilyl group having 6 to 60 carbon atoms, preferably an arylsilyl group having 8 to 40 carbon atoms. Examples of the arylsilyl group include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, and diphenyltert-butylsilyl. In addition, the arylsilyl group can be optionally substituted.

[0168] Alkylgermyl groups encompass alkyl-substituted germyl groups. The alkylgermyl group can be an alkylgermyl group having 3 to 40 carbon atoms, preferably an alkylgermyl group having 3 to 20 carbon atoms. Examples of the alkylgermyl group include trimethylgermyl, triethylgermyl, methyldiethylgermyl, ethyldimethylgermyl, tripropylgermyl, tributylgermyl, triisopropylgermyl, methyldiisopropylgermyl, dimethylisopropylgermyl, tritert-butylgermyl, triisobutylgermyl, dimethyltert-butylgermyl, methylditert-butylgermyl. Additionally, the alkylgermyl group can be optionally substituted.

[0169] Arylgermyl groups encompass germyl groups substituted with at least one aryl or heteroaryl group. The arylgermyl group can be an arylgermyl group having 6 to 60 carbon atoms, preferably an arylgermyl group having 8 to 40 carbon atoms. Examples of the arylgermyl group include triphenylgermyl, phenyldibiphenylgermyl, diphenylbiphenylgermyl, phenyldiethylgermyl, diphenylethylgermyl, phenyldimethylgermyl, diphenylmethylgermyl, phenyldiisopropylgermyl, diphenylisopropylgermyl, diphenylbutylgermyl, diphenylisobutylgermyl, diphenyltert-butylgermyl. Additionally, the arylgermyl group can be optionally substituted.

[0170] In the present disclosure, the term "aza" in azadibenzofuran, azadibenzothiophene, etc. means that one or at least two C-H groups in the corresponding aromatic fragment are replaced by nitrogen atoms. For example, azatriphenylene includes dibenzo[f,h]quinoxaline, dibenzo[f,h]quinoline, and other similar compounds having two or more nitrogens in the ring system. Those of ordinary skill in the art can readily envision other nitrogen analogs of the above-mentioned aza derivatives, and all such analogs are determined to be included in the terms described herein.

[0171] In many cases, common substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxyl, ether, ester, cyano, isocyano, thio, sulfinyl, sulfonyl, and phosphino.

[0172] In this document, the term "substituted or unsubstituted" means being selected from hydrogen, deuterium, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazino group, hydrazono group, carboxyl group or its carboxylate, sulfonic acid group or its sulfonate, phosphoric acid group or its phosphate, C 1 -C 40 alkyl, C 2 -C 40 alkenyl, C 2 -C 40 alkynyl, C 1 -C 40 alkoxy, C 3 -C 40 cycloalkyl, C3 -C 40 cycloalkenyl, C 6 -C 60 aryl, C 6 -C 60 aryloxy, C 6 -C 60 arylthioether group and C 2 -C 60 substituted or unsubstituted with one or more substituents selected from cycloalkenyl, C

[0173] As used herein, "a combination thereof" or "a group" 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 group and deuterium can be combined to form a partially or fully deuterated alkyl group; a halogen and an alkyl group can be combined to form a haloalkyl substituent, such as difluoromethyl, trifluoromethyl, etc.; and a halogen, an alkyl group, and an aryl group can be combined to form a haloaryalkyl group.

[0174] In one example, the term "substituted" includes combinations of two to four of the listed groups.

[0175] In another example, the term "substituted" includes combinations of two to three groups. In yet another example, the term "substituted" includes combinations of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations including up to forty atoms that are not hydrogen or deuterium, or combinations including up to thirty atoms that are not hydrogen or deuterium. In many cases, the preferred combinations of substituents will include combinations of up to twenty atoms that are not hydrogen or deuterium.

[0176] In the complexes mentioned in this disclosure, unless explicitly defined, such as adjacent substituents can optionally be linked to form a ring, adjacent substituents in the complexes cannot be linked to form a ring. In the complexes mentioned in this disclosure, adjacent substituents can optionally be linked to form a ring, which includes both the case where adjacent substituents can be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be linked to form a ring, the resulting ring can be a monocyclic or polycyclic ring (including spiro rings, bridged rings, fused rings, etc.), and an alicyclic ring, a heteroalicyclic ring, an aromatic ring, or a heteroaromatic ring. In this expression, adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further apart. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0177] "EQE" in the present invention refers to the external quantum efficiency of a device, that is, the ratio of the number of photons emitted by the device to the number of electrons injected into the device.

[0178] The organic electroluminescent device described in the present invention includes at least one organic layer, which is disposed between the anode and the cathode and is electrically connected to the anode and the cathode. Figure 1 A schematic diagram of an organic light-emitting device 100 is shown. The illustration is not necessarily drawn to scale. The device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, a hole blocking layer 107, an electron transport layer 108, an electron injection layer 109, a cathode 110, and a capping layer (CPL) 111. The device 100 can be fabricated by sequentially depositing the described layers.

[0179] Figure 2 A schematic diagram of an organic light-emitting device 200 containing two light-emitting layers is shown. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 can be prepared by sequentially depositing the described layers. Since the most common OLED devices have a single monochromatic light-emitting layer or have three light-emitting layers of the three primary colors, while the device 200 has two light-emitting layers of the same light color. In the corresponding layers of the device 200, materials similar to those described with respect to the device 100 can be used. Figure 2 An example of how some layers can be added to the structure of the device 100 is provided.

[0180] Figure 1 and Figure 2The simple layered structure described is provided as a non-limiting example, and it should be understood that embodiments of the present invention can be used in combination with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be achieved by combining the described individual layers in different ways based on design, performance, and cost factors, or several layers can be completely omitted. Other layers not specifically described can also be included. Materials different from those specifically described can be used. Although many of the examples provided herein describe the various layers as including a single material, it will be understood that combinations of materials can be used, such as a mixture of a matrix and a dopant, or more generally, a mixture. Also, the layers can have various sub-layers. The names given to the individual layers herein are not intended to be strictly limiting. For example, in device 200, the hole transport layer 204 transports holes and injects the holes into the light-emitting layer 205, and can be described as a hole transport layer or an electron blocking layer. In one embodiment, an OLED can be described as having an organic layer disposed between a cathode and an anode. This organic layer can include a single layer or can further include multiple layers of different organic materials as described, for example, Figure 1 and Figure 2 described.

[0181] Structures and materials not specifically described can also be used, such as PLEDs that include polymer materials. As another example, an OLED with a single organic layer or multiple stacks can be used. The OLED structure can deviate from Figure 1 and Figure 2 the simple layered structure described. For example, the substrate can include an angled reflective surface to improve light coupling.

[0182] Unless otherwise specified, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, organic vapor deposition methods, or sublimation of one or more layers by means of a carrier gas, where the material is applied at a pressure between 10 -5 mbar and 1 bar. A particular example of this method is the organic vapor jet printing method, where the material is applied directly through a nozzle and is thus structured. Other suitable deposition methods include, for example, generating one or more layers by spin coating, or by means of any desired printing method such as screen printing, flexographic printing, lithographic printing, photo-thermal imaging, thermal transfer, inkjet printing, or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers, and polymers. Also feasible are hybrid methods, where, for example, one or more layers are applied from a solution and one or more additional layers are applied by vapor deposition.

[0183] The device fabricated according to an embodiment of the present invention may further optionally include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage due to exposure to harmful substances in the environment, including moisture, vapors, and / or gases, etc. The barrier layer may be deposited on the substrate, on the electrodes, under the substrate, beside the electrodes, or on any other part of the device, including the edges. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds or both. Preferably, the barrier layer includes a mixture of a polymeric material and a non-polymeric material. In order to be considered a mixture, the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited under the same conditions and / or simultaneously. The weight ratio of the polymeric material to the non-polymeric material may be in the range of 95 / 5 to 5 / 95. In one example, the mixture of the polymeric material and the non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

[0184] In any of the compounds mentioned above used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any specifically listed substituent, such as (but not limited to) methyl, ethyl, isopropyl, tert-butyl, phenyl, pyridyl, etc. may be in its non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (such as (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their non-deuterated, partially deuterated, and fully deuterated forms.

[0185] The materials and structures described herein may be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. Further, organic devices such as organic transistors may use the materials and structures.

[0186] In the embodiment of material synthesis, unless otherwise stated, all reactions are carried out under nitrogen protection. All reaction solvents are anhydrous and used as they are from commercial sources. The synthetic product uses one or more conventional equipment in the art (including but not limited to nuclear magnetic resonance, liquid chromatograph, liquid chromatography-mass spectrometer, gas chromatography-mass spectrometer, differential scanning calorimeter, fluorescence spectrophotometer, electrochemical workstation, sublimator, etc.), and the structure is confirmed and the characteristics are tested by methods well known to those skilled in the art. In the embodiment of the device, the characteristics of the device are also tested by methods well known to those skilled in the art using conventional equipment in the art (including but not limited to evaporation machine, optical test system, life test system, ellipsometer, etc.). Since those skilled in the art are aware of the relevant contents such as the use of the above-mentioned equipment and the test method, the inherent data of the sample can be obtained with certainty and without being affected, so the above-mentioned relevant contents will not be elaborated in this patent.

[0187] In order to explain the present invention more clearly, the technical solution of the present invention is described below in conjunction with some specific embodiments.

[0188] In the following examples of the present invention, conventional preparation methods are used unless otherwise specified. The raw materials used can be obtained from public commercial channels unless otherwise specified, and the percentages are by mass unless otherwise specified.

[0189] In the embodiments of the present invention, the performance testing conditions of the prepared electroluminescent device are as follows:

[0190] Chromaticity coordinates: tested using a spectrum scanner PhotoResearch PR-715;

[0191] Current-voltage: Tested using a digital source meter Keithley 2420;

[0192] Power efficiency: tested using NEWPORT 1931-C;

[0193] Brightness: Tested using a brightness meter Minolta CS-1000A.

[0194] Example 1 Preparation of Intermediates A1 to A6

[0195] 1. Preparation of intermediate A2:

[0196] Step 1: Preparation of Compound A2

[0197]

[0198] Under nitrogen protection, 0.28 mol of 9,10-dimethylanthracene and 0.67 mol of isoamyl nitrite were dissolved in 300 mL of THF, heated to reflux, and slowly added dropwise to a solution of 0.62 mol of 2-amino-5-bromobenzoic acid in 200 mL of THF. The mixture was stirred for 4 hours, concentrated to dryness under reduced pressure, 400 mL of xylene and 0.84 mol of maleic anhydride were added, heated to reflux for 2 hours, cooled to room temperature, concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain Intermediate A2, a white solid, with a yield of 80%.

[0199]

[0200] 2. Preparation of Intermediate A1: Referring to the above synthetic method of Intermediate A2, only replace 2-amino-5-bromobenzoic acid with 2-amino-3-bromobenzoic acid to obtain Compound A1, a white solid, with a yield of 78%.

[0201]

[0202] 3. Preparation of Intermediate A3: Referring to the above synthetic method of Intermediate A2, replace 2-amino-5-bromobenzoic acid with 2-amino-3-bromobenzoic acid and replace 9,10-dimethylanthracene with anthracene to obtain Compound A3, a white solid, with a yield of 82%.

[0203]

[0204] 4. Preparation of Intermediate A4: Referring to the above synthetic method of Intermediate A2, only replace 9,10-dimethylanthracene with anthracene to obtain Compound A4, a white solid, with a yield of 83%.

[0205]

[0206] 5. Preparation of Intermediate A5: Referring to the above synthetic method of Intermediate A2, only replace 2-amino-5-bromobenzoic acid with 2-amino-3-nitrobenzoic acid to obtain Compound A5, a yellow solid, with a yield of 64%.

[0207]

[0208] 6. Preparation of Intermediate A6: Referring to the above synthetic method of Intermediate A2, only replace 2-amino-5-bromobenzoic acid with 2-amino-5-nitrobenzoic acid to obtain Compound A6, a yellow solid, with a yield of 65%.

[0209] Example 2 Preparation of Intermediates A7 - A14

[0210] 1. Preparation of Intermediate A7

[0211] Step 1: Preparation of Compound Int-1

[0212]

[0213] Under nitrogen protection, 20.0 mmol of S1 was dissolved in 60 mL of dry THF, the temperature was lowered to -78 °C, 22.0 mmol of a 2.5 M n-butyllithium n-hexane solution was added dropwise, and the mixture was stirred for 10 minutes. Then, a solution of 22.0 mmol of S2 in 20 mL of THF was added dropwise, and the mixture was stirred for 30 minutes. The temperature was raised to room temperature and the reaction was continued for 1 hour. 40 mL of 3 M dilute hydrochloric acid was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the combined organic phases were dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain intermediate Int-1, a white solid, yield: 86%.

[0214] Step 2: Preparation of compound Int-2

[0215]

[0216] Under nitrogen protection, 20.0 mmol of Int-1 prepared in the previous step was dissolved in 60 mL of dry THF, the temperature was lowered to 0 °C, 24.0 mmol of a 1 M methylmagnesium bromide THF solution was added dropwise, and the mixture was stirred for 1 hour. The temperature was raised to room temperature, 50 mL of 2 M dilute hydrochloric acid was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the combined organic phases were dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain intermediate Int-2, a yellow oil, yield: 90%.

[0217] Step 3: Preparation of compound Int-3

[0218]

[0219] Under nitrogen protection, 20.0 mmol of Int-2 prepared in the previous step was added portionwise to 50 mL of concentrated sulfuric acid, and the mixture was stirred at 0 °C for 2 hours and then at room temperature for 2 hours. The reaction mixture was poured into 500 g of crushed ice, filtered, the cake was washed with water, and recrystallized from ethanol to obtain intermediate Int-3, a yellow solid, yield: 78%.

[0220] Step 4: Preparation of compound Int-4

[0221]

[0222] Under nitrogen protection, 20.0 mmol of Int-3 prepared in the previous step, 60.0 mmol of potassium persulfate and 20.0 mmol of copper sulfate pentahydrate were mixed, then 40 mL of water and 40 mL of acetonitrile were added. The mixture was heated to reflux and stirred for 2 hours, cooled to room temperature, concentrated under reduced pressure to remove acetonitrile, extracted with ethyl acetate, the organic phases were combined and dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain intermediate Int-4, a yellow solid, yield: 92%.

[0223] Step 5: Preparation of Compound Int-5

[0224]

[0225] Referring to the synthesis method of compound Int-2 in Step 2, only replacing Int-1 in Step 2 with Int-4, the intermediate Int-5 was prepared, a yellow solid, yield: 89%.

[0226] Step 6: Preparation of Compound Int-6

[0227]

[0228] 20.0 mmol of intermediate Int-5 was dissolved in 60 mL of dichloromethane, 20 mL of formic acid was added, and the mixture was stirred for 2 hours, concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain compound Int-6, a white solid, yield 84%.

[0229] Step 7: Preparation of Compound Int-7

[0230]

[0231] 20.0 mmol of intermediate Int-6 was dissolved in 60 mL of dichloromethane, cooled to 0 °C, 30.0 mmol of boron tribromide was added dropwise, and the mixture was stirred for 2 hours, warmed to room temperature, 50 mL of water was added, the organic phase was separated, washed three times with water, the organic phase was dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain compound Int-7, a white solid, yield 94%.

[0232] Step 8: Preparation of Compound A7

[0233]

[0234] 20.0 mmol of intermediate Int-7 and 50.0 mmol of pyridine were dissolved in 60 mL of dichloromethane. The temperature was lowered to 0 °C, and 24.0 mmol of trifluoromethanesulfonic anhydride was added dropwise. The mixture was stirred for 2 hours, then warmed to room temperature. 50 mL of 1 M dilute hydrochloric acid was added, and the organic phase was separated. It was washed three times with dilute hydrochloric acid and then once with saturated sodium bicarbonate aqueous solution. The organic phase was dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. It was separated and purified by silica gel column chromatography to obtain compound A7, a white solid, with a yield of 83%.

[0235]

[0236] 2. Preparation of intermediate A8: Referring to the synthesis method of intermediate A7 above, only replace S1 in the first step with 1-bromo-2-(3-methoxybenzyl)benzene to prepare intermediate A8, a white solid.

[0237]

[0238] 3. Preparation of intermediate A9: Referring to the synthesis method of intermediate A7 above, only replace S1 in the first step with 1-bromo-2-(4-methoxybenzyl)benzene to prepare intermediate A9, a white solid.

[0239]

[0240] 4. Preparation of intermediate A10: Referring to the synthesis method of intermediate A7 above, only replace S1 in the first step with 1-benzyl-2-bromo-3-methoxybenzene to prepare intermediate A10, a white solid.

[0241]

[0242] 5. Preparation of intermediate A11: Referring to the synthesis method of intermediate A7 above, replace S1 in the first step with o-bromodiphenylmethane and replace S2 in the first step with 2-(2-bromophenyl)-N,N-diethyl-2-methylpropanamide to prepare intermediate A11, a white solid.

[0243]

[0244] 6. Preparation of intermediate A12: Referring to the synthesis method of intermediate A7 above, replace S1 in the first step with o-bromodiphenylmethane and replace S2 in the first step with N,N-diethyl-2-(3-methoxyphenyl)-2-methylpropanamide to prepare intermediate A12, a white solid.

[0245]

[0246] 7. Preparation of Intermediate A13: Referring to the synthesis method of Intermediate A7 above, replace S1 in the first step with o-bromodiphenylmethane and replace S2 in the first step with N,N-diethyl-2-(4-methoxyphenyl)-2-methylpropanamide to prepare Intermediate A13, a white solid.

[0247]

[0248] 8. Preparation of Intermediate A14: Referring to the synthesis method from the first step to the eighth step above, replace S1 in the first step with o-bromodiphenylmethane and replace S2 in the first step with N,N-diethyl-2-(3-methoxyphenyl)-2-methylpropanamide to prepare Intermediate A14, a white solid.

[0249] Example 3

[0250] Preparation of Compound P2 includes the following steps:

[0251] First step: Preparation of Compound Int-8

[0252]

[0253] Under nitrogen protection, 10.0 mmol of A2, 12.0 mmol of o-nitroaniline, 15.0 mmol of sodium tert-butoxide, 0.1 mmol of Pd 2 (dba) 3 CHCl 3 and 80 mL of toluene are mixed, then 0.3 mmol of 10% tri-tert-butylphosphine toluene solution is added, the temperature is raised to 100 °C, and the mixture is stirred and reacted for 15 hours. After cooling to room temperature, 40 mL of water is added, the organic phase is separated, the aqueous phase is extracted with ethyl acetate, the organic phases are combined and dried, filtered, the filtrate is concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain Intermediate Int-8, a yellow solid, with a yield of 77%.

[0254] Second step: Preparation of Compound Int-9

[0255]

[0256] 20.0 mmol of Int-8 prepared in the previous step and 0.5 g of 10% palladium on carbon are mixed, then 50 mL of ethanol is added, the mixture is purged with hydrogen three times, hydrogen is introduced at room temperature, and the mixture is stirred and reacted under normal pressure for 10 hours. After filtration, the filtrate is concentrated to dryness under reduced pressure to obtain Compound Int-9, a yellow solid, which is directly used in the next step without purification, with a yield of 100%.

[0257] Third step: Preparation of Compound Int-10

[0258]

[0259] Under nitrogen protection, 10.0 mmol of PC-1 (prepared according to the synthesis method disclosed in US20200140471), 11.0 mmol of Int-9, 15.0 mmol of sodium tert-butoxide, and 0.1 mmol of Pd 2 (dba) 3 were mixed with 80 mL of toluene, then 0.2 mmol of 10% tri-tert-butylphosphine toluene solution was added. The temperature was raised to 100 °C and the mixture was stirred and reacted for 15 hours. After cooling to room temperature, 40 mL of water was added. The organic phase was separated, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure to obtain intermediate Int-10, a brown solid. Without purification, it was directly used in the next step reaction. Yield: 97%.

[0260] Step 4: Preparation of compound Int-11

[0261]

[0262] Under nitrogen protection, 20.0 mmol of Int-10 prepared in the previous step, 1.0 mol of triethyl orthoformate, and 40.0 mmol of ammonium hexafluorophosphate were mixed. The temperature was raised to 90 °C and the mixture was stirred and reacted for 18 hours. After cooling to room temperature, it was concentrated under reduced pressure to a remaining volume of about 20 mL. 150 mL of petroleum ether was added, and the mixture was stirred and filtered. The filter cake was washed with water and dried in vacuo to obtain intermediate Int-11, a gray solid. Yield: 75%.

[0263] Step 5: Preparation of compound P2

[0264]

[0265] Under nitrogen protection, 14.0 mmol of Int-11 prepared in the previous step, 14.0 mmol of Pt(COD)Cl 2 were mixed with 500 mL of 2-methyltetrahydrofuran, then 42.0 mmol of anhydrous sodium acetate and 50 mL of toluene were added. The mixture was stirred and heated to reflux for 3 days, then cooled to room temperature and concentrated to dryness under reduced pressure. It was dispersed in dichloromethane, filtered, and the filtrate was concentrated to dryness under reduced pressure. It was separated and purified by silica gel column chromatography to obtain compound P2, a yellow solid. Yield: 52%; 1HNMR (δ, DMSO-d6): 8.71 - 8.70 (1H, d); 8.52 - 8.48 (2H, m); 8.38 - 8.37 (1H, d); 8.12 - 8.10 (1H, m); 8.01 - 7.97 (2H, m); 7.86 - 7.80 (3H, m); 7.68 - 7.66 (1H, d); 7.60 - 7.56 (4H, m); 7.51 - 7.45 (2H, m); 7.39 - 7.35 (2H, m); 7.21 - 7.16 (2H, m); 7.09 - 7.07 (1H, d); 7.03 - 6.99 (2H, m); 6.96 - 6.91 (2H, m); 6.77 - 6.75 (1H, d); 2.23 (6H, s); 1.31 (9H, s). HRMS: 982.3018 [M + H], and this product was determined to be the target product.

[0266] Example 4

[0267] The preparation route of metal compound P7 is as follows:

[0268]

[0269] Preparation of intermediate Int-12: Referring to the synthesis method of the first step in Example 3 above, only replace A2 in the first step of Example 3 with A7 to prepare intermediate Int-12, a yellow solid, with a yield of 75%.

[0270] Preparation of intermediate Int-13: Referring to the synthesis method of the second step in Example 3 above, only replace Int-8 in the second step of Example 3 with Int-12 to prepare intermediate Int-13, a yellow solid, with a yield of 100%.

[0271] Preparation of intermediate Int-14: Referring to the synthesis method of the third step in Example 3 above, only replace Int-9 in the third step of Example 3 with Int-13 to prepare intermediate Int-14, a brown solid, with a yield of 90%.

[0272] Preparation of intermediate Int-15: Referring to the synthesis method of the fourth step in Example 3 above, only replace Int-10 in the fourth step of Example 3 with Int-14 to prepare intermediate Int-15, a gray solid, with a yield of 76%.

[0273] Preparation of compound P7: Referring to the synthesis method of the fifth step in Example 3 above, only replace Int-11 in the fifth step of Example 3 with Int-15 to prepare compound P7, a yellow solid, with a yield of 44%; 1$^{1}$H NMR (δ, DMSO-d₆): 8.70 - 8.69 (1H, d); 8.51 - 8.47 (2H, m); 8.36 - 8.35 (1H, d); 8.10 - 8.08 (1H, m); 7.55 - 7.52 (1H, m); 7.48 - 7.46 (1H, m); 7.39 - 7.38 (1H, d); 7.31 - 7.20 (8H, m); 7.18 - 7.12 (5H, m); 7.09 - 7.05 (3H, m); 6.96 - 6.92 (2H, m); 6.77 - 6.75 (1H, d); 2.16 (3H, s); 1.48 (3H, s); 1.43 (6H, s); 1.35 (9H, s). HRMS: 1024.3488 [M + H], and this product was determined to be the target product.

[0274] Preparation of Intermediates A15 - A18 in Example 5

[0275] 1. Preparation of Intermediate A15

[0276]

[0277] Under nitrogen protection, 20.0 mmol of 4 - bromo - o - phenylenediamine, 100.0 mmol of sodium tert - butoxide, 42.0 mmol of o - diiodobenzene, and 2.0 mmol of copper(I) iodide were mixed, 80 mL of dry DMSO was added, the temperature was raised to 120 °C and stirred for 2 hours, cooled to room temperature, the reaction solution was poured into 200 mL of ice - water solution, stirred for 30 minutes, filtered, the filter cake was washed with water, and the solid was separated and purified by silica gel column chromatography to obtain Intermediate A15, a white solid, yield: 46%.

[0278]

[0279] 2. Preparation of Intermediate A16: Referring to the above synthetic method of Intermediate A15, only 4 - bromo - o - phenylenediamine was replaced with 3 - bromo - o - phenylenediamine to prepare Intermediate A16, a white solid, yield: 40%.

[0280]

[0281] 3. Preparation of Intermediate A17: Referring to the above synthetic method of Intermediate A15, only 4 - bromo - o - phenylenediamine was replaced with 3 - nitro - o - phenylenediamine to prepare Intermediate A17, a yellow solid, yield: 58%.

[0282]

[0283] 4. Preparation of Intermediate A18: Referring to the above synthetic method of Intermediate A15, only 4 - bromo - o - phenylenediamine was replaced with 3 - nitro - o - phenylenediamine to prepare Intermediate A18, a yellow solid, yield: 55%.

[0284] Example 6 Preparation of Metal Compound P10

[0285] The preparation route is as follows:

[0286]

[0287] Preparation of Intermediate Int-16: Referring to the synthesis method of the first step in Example 3 above, only replace A2 in the first step of Example 3 with A15 to prepare Intermediate Int-16, a yellow solid with a yield of 72%.

[0288] Preparation of Intermediate Int-17: Referring to the synthesis method of the second step in Example 3 above, only replace Int-8 in the second step of Example 3 with Int-16 to prepare Intermediate Int-17, a yellow solid with a yield of 100%.

[0289] Preparation of Intermediate Int-18: Referring to the synthesis method of the third step in Example 3 above, only replace Int-9 in the third step of Example 3 with Int-17 to prepare Intermediate Int-18, a brown solid with a yield of 85%.

[0290] Preparation of Intermediate Int-19: Referring to the synthesis method of the fourth step in Example 3 above, only replace Int-10 in the fourth step of Example 3 with Int-18 to prepare Intermediate Int-19, a gray solid with a yield of 52%.

[0291] Preparation of Compound P10: Referring to the synthesis method of the fifth step in Example 3 above, only replace Int-11 in the fifth step of Example 3 with Int-19 to prepare Compound P10, a yellow solid with a yield of 40%; 1 HNMR (δ, DMSO-d6): 8.70 - 8.69 (1H, d); 8.51 - 8.47 (2H, m); 8.36 - 8.35 (1H, d); 8.12 - 8.10 (1H, m); 7.55 - 7.52 (1H, m); 7.48 - 7.46 (1H, m); 7.39 - 7.38 (1H, d); 7.31 - 7.25 (4H, m); 7.20 - 7.16 (2H, m); 7.14 - 7.08 (5H, m); 7.04 (1H, s); 6.98 - 6.92 (6H, m); 6.77 - 6.75 (1H, d); 1.31 (9H, s). HRMS: 956.2602 [M + H], and this product is determined to be the target product.

[0292] Example 7 Preparation of Metal Compound P12

[0293] First Step: Preparation of Compound Int-20

[0294]

[0295] Under nitrogen protection, 120.0 mmol of A19 (prepared according to the synthesis method in the first step of Reference Example 1) was dissolved in 200 mL of glacial acetic acid, and 126.0 mmol of 60% nitric acid was added dropwise at room temperature. The mixture was stirred for 1 hour, and the reaction solution was poured into ice water, filtered, the filter cake was washed with water, and recrystallized with ethanol to obtain Intermediate Int-20, a yellow solid, yield: 80%.

[0296] Step 2: The preparation route of metal compound P12 is as follows:

[0297]

[0298] Preparation of Intermediate Int-21: Referring to the synthesis method of A7 in the eighth step of Example 2 above, only replacing Int-7 in the eighth step of Example 2 with Int-20, Intermediate Int-21 was prepared, a yellow solid, yield 92%.

[0299] Preparation of Intermediate Int-22: Referring to the synthesis method in the first step of Example 3 above, replacing A2 in the first step of Example 3 with Int-21 and replacing o-nitroaniline in the first step of Example 3 with 3,5-di-tert-butylaniline, Intermediate Int-22 was prepared, a yellow solid, yield 79%.

[0300] Preparation of Intermediate Int-23: Referring to the synthesis method in the second step of Example 3 above, only replacing Int-8 in the second step of Example 3 with Int-22, Intermediate Int-23 was prepared, a yellow solid, yield 100%.

[0301] Preparation of Intermediate Int-24: Referring to the synthesis method in the third step of Example 3 above, only replacing Int-9 in the third step of Example 3 with Int-23, Intermediate Int-24 was prepared, a brown solid, yield 78%.

[0302] Preparation of Intermediate Int-25: Referring to the synthesis method in the fourth step of Example 3 above, only replacing Int-10 in the fourth step of Example 3 with Int-24, Intermediate Int-25 was prepared, a gray solid, yield 80%.

[0303] Preparation of Compound P12: Referring to the synthesis method in the fifth step of Example 3 above, only replacing Int-11 in the fifth step of Example 3 with Int-25, Compound P12 was prepared, a yellow solid, yield 44%; 1HNMR (δ, DMSO-d6): 8.71 - 8.70 (1H, d); 8.36 - 8.34 (1H, d); 8.12 - 8.10 (1H, m); 7.56 - 7.51 (3H, m); 7.48 - 7.46 (1H, m); 7.41 - 7.38 (4H, m); 7.31 - 7.28 (2H, m); 7.22 - 7.15 (5H, m); 7.12 - 7.06 (4H, m); 6.96 - 6.93 (2H, m); 6.76 - 6.74 (1H, d); 2.24 (6H, s); 1.35 (18H, s); 1.31 (9H, s). HRMS: 1094.4272 [M + H], and this product was determined to be the target product.

[0304] Example 8 Preparation of Metal Compound P25

[0305] First Step: Preparation of Compound Int-26

[0306]

[0307] Under nitrogen protection, 20.0 mmol of 3-bromo-5-methoxyo-phenylenediamine, 100.0 mmol of sodium tert-butoxide, 44.0 mmol of o-diiodobenzene and 2.0 mmol of copper(I) iodide were mixed, 80 mL of dry DMSO was added, the temperature was raised to 120 °C and stirred for 2 hours, then cooled to room temperature. The reaction solution was poured into 200 mL of ice water solution, stirred for 30 minutes, filtered, the filter cake was washed with water, and the solid was separated and purified by silica gel column chromatography to obtain intermediate Int-26, a white solid, yield: 42%.

[0308] Second Step: Preparation of Compound Int-27

[0309]

[0310] Under nitrogen protection, 20.0 mmol of Int-26, 24.0 mmol of o-nitroaniline, 30.0 mmol of sodium tert-butoxide and 2.0 mmol of copper(I) iodide were mixed, then 0.1 mmol of Pd 2 (dba) 3 , 0.2 mmol of 10% tri-tert-butylphosphine toluene solution and 80 mL of dry toluene were added. The temperature was raised to 110 °C and stirred for 15 hours, then cooled to room temperature. 50 mL of water was added, stirred for 30 minutes, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and separated and purified by silica gel column chromatography to obtain intermediate Int-27, a yellow solid, yield: 84%.

[0311] Third Step: Preparation of Compound Int-28

[0312]

[0313] Referring to the synthesis method of the seventh step of Example 2 above, only replace Int-6 in the seventh step of Example 2 with Int-27 to prepare intermediate Int-28, a yellow solid, with a yield of 87%.

[0314] Step 4: Preparation of Compound Int-29

[0315]

[0316] Under nitrogen protection, 20.0 mmol of Int-28, 24.0 mmol of S8, 40.0 mmol of anhydrous potassium phosphate, and 2.0 mmol of copper(I) iodide were mixed, then 4.0 mmol of 2-pyridinecarboxylic acid and 50 mL of dry DMSO were added, and the temperature was raised to 110 °C and stirred for 48 hours. After cooling to room temperature, the reaction solution was poured into 250 mL of water, stirred for 30 minutes, extracted with ethyl acetate, the organic phase was washed with saturated brine, dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain intermediate Int-29, a yellow solid, with a yield of 68%.

[0317] Step 5: Preparation of Compound Int-30

[0318]

[0319] Referring to the synthesis method of the second step of Example 3 above, only replace Int-8 in the second step of Example 3 with Int-29 to prepare intermediate Int-30, a brown solid, with a yield of 100%.

[0320] Step 6: Preparation of Compound Int-31

[0321]

[0322] Under nitrogen protection, 20.0 mmol of Int-30, 20.0 mmol of 3,5-di-tert-butylbromobenzene, 30.0 mmol of sodium tert-butoxide, and 2.0 mmol of copper(I) iodide were mixed, then 0.1 mmol of Pd 2 (dba) 3 , 0.2 mmol of 10% tri-tert-butylphosphine toluene solution, and 80 mL of dry toluene were added, and the temperature was raised to 100 °C and stirred for 15 hours. After cooling to room temperature, 50 mL of water was added, stirred for 30 minutes, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain intermediate Int-31, a brown solid, with a yield of 77%.

[0323] Step 7: Preparation of Compound Int-32

[0324]

[0325] Under nitrogen protection, 10.0 mmol of Int-31, 30.0 mmol of ammonium hexafluorophosphate and 50 mL of triethyl orthoformate were heated to 70 °C and stirred for reaction for 36 hours. Then it was cooled to room temperature, concentrated to dryness under reduced pressure, added with ether and stirred for dispersion, and filtered to obtain intermediate Int-32, a brown solid, yield: 85%.

[0326] Step 8: Preparation of metal compound P25

[0327]

[0328] Under nitrogen protection, 10.0 mmol of Int-32 prepared in the previous step, 30.0 mmol of anhydrous sodium acetate, 10.0 mmol of Pt(COD)Cl 2 and 120 mL of 2-methyltetrahydrofuran were mixed, heated to reflux and stirred for reaction for 5 days. Then it was cooled to room temperature, concentrated to dryness under reduced pressure, and separated and purified by silica gel column chromatography to obtain product P21, a dark yellow solid, yield: 43%. 1 HNMR (δ, DMSO-d6): 8.71 - 8.70 (1H, m); 8.52 - 8.48 (2H, m); 8.36 - 8.34 (1H, d); 8.13 - 8.10 (1H, m); 7.56 - 7.52 (3H, m); 7.48 - 7.44 (1H, m); 7.41 - 7.39 (2H, t); 7.31 - 7.27 (2H, m); 7.22 - 7.18 (1H, m); 7.16 - 7.10 (4H, m); 6.96 - 6.91 (5H, m); 6.77 (1H, s); 6.75 - 6.73 (1H, d); 1.35 (18H, s); 1.31 (9H, s). HRMS: 1068.3864 [M+H], and this product was determined to be the target product.

[0329] Example 9 Preparation of metal compound P31

[0330] Step 1: Preparation of compound Int-33

[0331]

[0332] Under nitrogen protection, 10.0 mmol of A20 (prepared according to the synthesis method of Example 1), 12.0 mmol of 2-nitrophenylboronic acid pinacol ester, 25.0 mmol of anhydrous potassium carbonate, 1.0 mmol of tetrabutylammonium bromide and 0.01 mmol of Pd(PPh 3 ) 4Mix, then add 20 mL of toluene, 10 mL of ethanol and 10 mL of water. Heat to reflux and stir for reaction for 15 hours. Cool to room temperature, add 50 mL of water, extract with ethyl acetate. Dry the organic phase, filter, concentrate the filtrate to dryness under reduced pressure, separate and purify by silica gel column to obtain compound Int-33, a yellow solid, with a yield of 72%.

[0333] Step 2: Preparation of compound Int-34

[0334]

[0335] Under nitrogen protection, mix 10.0 mmol of Int-33 and 35.0 mmol of triphenylphosphine, add 50 mL of o-dichlorobenzene, heat to reflux, stir for reaction for 10 hours, cool to room temperature, add 50 mL of toluene and 35.0 mmol of anhydrous magnesium chloride, heat to reflux, stir for reaction for 1 hour, cool to room temperature, filter, concentrate the filtrate to dryness under reduced pressure, separate and purify by silica gel column, and then recrystallize with ethanol to obtain compound Int-34, a white solid, with a yield of 81%.

[0336] Step 3: Preparation of compound Int-35

[0337]

[0338] Under nitrogen protection, mix 20.0 mmol of Int-34, 2.0 mmol of copper(I) iodide, 22.0 mmol of 2-bromo-4-tert-butylpyridine, 4.0 mmol of 1-methylimidazole and 40.0 mmol of lithium tert-butoxide, add 100 mL of xylene, heat to reflux, stir for reaction for 48 hours, cool to room temperature, add 50 mL of water, stir for reaction for 10 minutes, separate the organic phase, dry, filter, concentrate the filtrate to dryness under reduced pressure, separate and purify by silica gel column to obtain compound Int-35, a white solid, with a yield of 92%.

[0339] Step 4: The preparation route of compound P31 is as follows

[0340]

[0341] Preparation of Intermediate Int-36: Under nitrogen protection, 20.0 mmol of Int-35, 24.0 mmol of m-chlorophenol, 40.0 mmol of anhydrous potassium phosphate, and 2.0 mmol of cuprous iodide were mixed. Then, 4.0 mmol of 2-pyridinecarboxylic acid and 50 mL of dry DMSO were added. The temperature was raised to 110 °C and stirred for 48 hours. After cooling to room temperature, the reaction solution was poured into 250 mL of water, stirred for 30 minutes, extracted with ethyl acetate, and the organic phase was washed with saturated brine, dried, filtered. The filtrate was concentrated to dryness under reduced pressure and purified by silica gel column chromatography to obtain Intermediate Int-36, a yellow solid, with a yield of 72%.

[0342] Preparation of Intermediate Int-37: Referring to the synthesis method in the third step of Example 3 above, replace Int-9 in the third step of Example 3 with S9 and replace PC-1 in the third step of Example 3 with Int-36 to prepare Intermediate Int-37, a brown solid, with a yield of 87%.

[0343] Preparation of Intermediate Int-38: Referring to the synthesis method in the seventh step of Example 8 above, only replace Int-31 in the seventh step of Example 8 with Int-37 to prepare Intermediate Int-38, a gray solid, with a yield of 85%.

[0344] Preparation of Compound P31: Referring to the synthesis method in the eighth step of Example 8 above, only replace Int-32 in the eighth step of Example 8 with Int-38 to prepare Compound P31, a yellow solid, with a yield of 45%; 1 HNMR (δ, DMSO-d6): 8.71 - 8.70 (1H, d); 8.38 - 8.32 (3H, m); 8.01 - 7.97 (1H, m); 7.56 (2H, s); 7.41 - 7.38 (2H, m); 7.32 - 7.27 (3H, m); 7.25 - 7.16 (6H, m); 7.13 - 7.11 (1H, m); 7.08 - 7.02 (4H, m); 6.96 - 6.93 (2H, m); 2.25 (6H, s); 1.37 (18H, s); 1.32 (9H, s). HRMS: 1094.4260 [M + H], and this product was determined to be the target product.

[0345] Preparation of Metal Compound P35 in Example 10

[0346] The preparation route is as follows:

[0347]

[0348] Preparation of Intermediate Int-39: Referring to the synthesis method in the first step of Example 9 above, only replace A20 in the first step of Example 9 with A21 to prepare Intermediate Int-39, a yellow solid, with a yield of 75%.

[0349] Preparation of Intermediate Int-40: Referring to the synthesis method in the second step of Example 9 above, only replace Int-33 in the second step of Example 9 with Int-39 to prepare Intermediate Int-40, a yellow solid with a yield of 80%.

[0350] Preparation of Intermediate Int-41: Referring to the synthesis method in the third step of Example 9 above, only replace Int-34 in the third step of Example 9 with Int-40 to prepare Intermediate Int-41, a yellow solid with a yield of 94%.

[0351] Preparation of Intermediate Int-42: Referring to the synthesis method of Int-36 in the fourth step of Example 9 above, only replace Int-35 with Int-41 to prepare Intermediate Int-42, a yellow solid with a yield of 70%.

[0352] Preparation of Intermediate Int-43: Referring to the synthesis method in the third step of Example 3 above, replace Int-9 in the third step of Example 3 with S9 and replace PC-1 in the third step of Example 3 with Int-42 to prepare Intermediate Int-43, a brown solid with a yield of 82%.

[0353] Preparation of Intermediate Int-44: Referring to the synthesis method in the seventh step of Example 8 above, only replace Int-31 in the seventh step of Example 8 with Int-43 to prepare Intermediate Int-44, a black solid with a yield of 91%.

[0354] Preparation of Compound P35: Referring to the synthesis method in the eighth step of Example 8 above, only replace Int-32 in the eighth step of Example 8 with Int-44 to prepare Compound P35, a yellow solid with a yield of 34%; 1 HNMR (δ, DMSO-d6): 8.70 - 8.69 (1H, d); 8.36 - 8.31 (3H, m); 7.98 - 7.95 (1H, m); 7.54 (2H, s); 7.42 - 7.39 (2H, m); 7.32 - 7.27 (3H, m); 7.24 - 7.21 (2H, m); 7.14 - 7.07 (5H, m); 6.98 - 6.95 (2H, m); 6.92 - 6.86 (4H, m); 1.35 (18H, s); 1.31 (9H, s). HRMS: 1068.3863 [M + H], and this product is determined to be the target product.

[0355] Preparation of Metal Compound P38 in Example 11

[0356] The preparation route is as follows:

[0357]

[0358] Preparation of Intermediate Int-45: Under nitrogen protection, 10.0 mmol of A11, 12.0 mmol of 4-bromo-2-nitrophenylboronic acid, 25.0 mmol of potassium phosphate hydrate and 0.01 mmol of Pd132 were mixed. Then, 20 mL of toluene, 20 mL of ethanol and 20 mL of water were added. The temperature was raised to reflux and stirred for 5 hours. After cooling to room temperature, 50 mL of water was added. The mixture was extracted with ethyl acetate. The organic phase was dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. It was separated and purified by silica gel column chromatography to obtain compound Int-45, a yellow solid, with a yield of 66%.

[0359] Preparation of Intermediate Int-46: Referring to the synthesis method of the second step in Example 9 above, only Int-33 in the second step of Example 9 was replaced with Int-45 to prepare Intermediate Int-46, a yellow solid, with a yield of 83%.

[0360] Preparation of Intermediate Int-47: Referring to the synthesis method of the third step in Example 9 above, only Int-34 in the third step of Example 9 was replaced with Int-46 to prepare Intermediate Int-47, a yellow solid, with a yield of 90%.

[0361] Preparation of Intermediate Int-48: Referring to the synthesis method of Int-36 in the fourth step of Example 9 above, only Int-35 was replaced with Int-47 to prepare Intermediate Int-48, a yellow solid, with a yield of 81%.

[0362] Preparation of Intermediate Int-49: Under nitrogen protection, 20.0 mmol of Int-48, 20.0 mmol of S9, 30.0 mmol of sodium tert-butoxide and 2.0 mmol of copper(I) iodide were mixed. Then, 0.1 mmol of Pd 2 (dba) 3 , 0.2 mmol of Xantphos and 80 mL of dry toluene were added. The temperature was raised to 110 °C and stirred for 15 hours. After cooling to room temperature, 50 mL of water was added and stirred for 30 minutes. The organic phase was separated. The aqueous phase was extracted with ethyl acetate. The organic phase was dried, filtered, and the filtrate was filtered through a short basic alumina column and eluted with ethyl acetate. It was concentrated to dryness under reduced pressure to obtain Intermediate Int-49, a brown solid, with a yield of 65%.

[0363] Preparation of Intermediate Int-50: Referring to the synthesis method of the seventh step in Example 8 above, only Int-31 in the seventh step of Example 8 was replaced with Int-49 to prepare Intermediate Int-50, a gray solid, with a yield of 82%.

[0364] Preparation of Compound P38: Referring to the synthesis method in the eighth step of Example 8 above, only replace Int-32 in the eighth step of Example 8 with Int-50 to prepare Compound P38, a yellow solid with a yield of 38%. 1 HNMR (δ, DMSO-d6): 8.70 - 8.69 (1H, d); 8.36 - 8.32 (2H, m); 8.28 - 8.26 (1H, d); 7.55 (2H, s); 7.41 - 7.38 (2H, m); 7.36 - 7.32 (2H, m); 7.30 - 7.21 (8H, m); 7.18 - 7.12 (4H, m); 7.01 - 6.98 (2H, m); 6.94 - 6.92 (1H, d); 2.32 (3H, s); 1.56 (3H, s); 1.48 (18H, s); 1.42 (3H, s); 1.35 (9H, s); 1.14 (3H, s). HRMS: 1136.4740 [M + H], and this product was determined to be the target product.

[0365] Preparation of Metal Compound P46 in Example 12

[0366] First Step: Preparation of Compound A22

[0367]

[0368] Under nitrogen protection, 0.28 mol of 9,10-dimethylanthracene and 0.31 mol of isoamyl nitrite were dissolved in 300 mL of dichloromethane, heated to reflux, and slowly added dropwise to a solution of 0.31 mol of 3-amino-2-bromoisonicotinic acid in 200 mL of acetone. The mixture was stirred for 4 hours, concentrated to dryness under reduced pressure, 400 mL of xylene and 0.42 mol of maleic anhydride were added, heated to reflux for 24 hours, cooled to room temperature, concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain intermediate A22, a yellow solid with a yield of 42%.

[0369]

[0370] Preparation of Compound A23: Referring to the synthesis method of A22 above, only replace 3-amino-2-bromoisonicotinic acid with 5-amino-2-bromoisonicotinic acid to obtain Compound A23, a yellow solid with a yield of 36%.

[0371] Second Step: Preparation of Compound Int-51

[0372]

[0373] Under nitrogen protection, 20.0 mmol of S10, 2.0 mmol of copper(I) iodide, 22.0 mmol of A22, 4.0 mmol of 1-methylimidazole and 40.0 mmol of lithium tert-butoxide were mixed, 100 mL of xylene was added, the temperature was raised to reflux, and the mixture was stirred and reacted for 48 hours. Then it was cooled to room temperature, concentrated to dryness under reduced pressure, and purified by silica gel column chromatography to obtain compound Int-51, a white solid, with a yield of 90%.

[0374] Step 3: The preparation route of metal compound P46 is as follows:

[0375]

[0376] Preparation of intermediate Int-52: Referring to the synthesis method of Int-36 in the fourth step of Example 9 above, only replacing Int-35 with Int-51, intermediate Int-52 was prepared, a yellow solid, with a yield of 80%.

[0377] Preparation of intermediate Int-53: Referring to the synthesis method of Int-49 in Example 11 above, only replacing Int-48 with Int-52, intermediate Int-53 was prepared, a brown solid, with a yield of 67%.

[0378] Preparation of intermediate Int-54: Referring to the synthesis method of the seventh step of Example 8 above, only replacing Int-31 in the seventh step of Example 8 with Int-53, intermediate Int-54 was prepared, a gray solid, with a yield of 85%.

[0379] Preparation of compound P46: Referring to the synthesis method of the eighth step of Example 8 above, only replacing Int-32 in the eighth step of Example 8 with Int-54, compound P46 was prepared, a yellow solid, with a yield of 35%; 1 HNMR (δ, DMSO-d6): 8.71 - 8.70 (1H, d); 8.36 - 8.32 (2H, m); 8.28 - 8.26 (1H, d); 8.16 - 8.14 (1H, m); 7.55 - 7.50 (3H, m); 7.46 - 7.42 (2H, m); 7.33 - 7.32 (1H, d); 7.30 - 7.21 (8H, m); 7.19 - 7.12 (5H, m); 7.01 - 6.99 (1H, m); 6.94 - 6.92 (1H, d); 2.39 (3H, s); 2.27 (3H, s); 1.48 (18H, s). HRMS: 1136.4740 [M + H], and this product was determined to be the target product.

[0380] Preparation of metal compound P51 in Example 13

[0381] Referring to the synthesis methods of Example 8 and Example 12 above, compound P51 was prepared, and the synthesis route is as follows:

[0382]

[0383] Compound P51, yellow solid, yield 32%; 1 HNMR (δ, DMSO-d6): 8.31 - 8.30 (1H, d); 8.17 - 8.15 (1H, m); 8.13 - 8.11 (1H, d); 7.53 - 7.49 (2H, m); 7.35 - 7.31 (2H, m); 7.25 - 7.20 (3H, m); 7.17 - 7.08 (7H, m); 7.03 - 6.97 (3H, m); 6.95 - 6.87 (4H, m); 6.77 - 6.75 (1H, d); 6.68 - 6.67 (1H, d); 1.31 (18H, s). HRMS: 1012.3238 [M + H], and this product was determined to be the target product.

[0384] Preparation of Metal Compound P115 in Example 14

[0385] First Step: Preparation of Compound Int-59

[0386]

[0387] Under nitrogen protection, 20.0 mmol of A2 and 20.0 mmol of potassium tert-butoxide were dissolved in 80 mL of dry THF, cooled to -78 °C, and 24.0 mmol of 2.5 M n-butyllithium hexane solution was slowly added dropwise. After stirring for 10 minutes, 30.0 mmol of trimethyl borate was added dropwise, and the mixture was stirred for 10 minutes. Then it was warmed to 0 °C, 50 mL of 3 M dilute hydrochloric acid was added, and the mixture was stirred for 30 minutes. The organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phases were combined and dried, filtered, the filtrate was concentrated to dryness under reduced pressure, stirred and dispersed with petroleum ether, and filtered to obtain intermediate Int-59, a white solid, yield: 72%.

[0388] Second Step: Preparation of Compound Int-60

[0389]

[0390] Under nitrogen protection, 24.0 mmol of Int-59, 20.0 mmol of 3-bromo-5-chloroanisole, and 40.0 mmol of potassium phosphate hydrate were dissolved in 60 mL of THF, and then 0.1 mmol of Pd(PPh 3 ) 4And 20 mL of water were added, and the temperature was raised to reflux. The mixture was stirred for 10 hours, cooled to room temperature, 50 mL of ethyl acetate was added, and the organic phase was separated. The aqueous phase was extracted with ethyl acetate. The combined organic phases were dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. It was separated and purified by silica gel column chromatography to obtain intermediate Int-60, a white solid, yield: 76%.

[0391] Step 3: Preparation of Compound Int-61

[0392]

[0393] Under nitrogen protection, 20.0 mmol of Int-60 was dissolved in 60 mL of dichloromethane, the temperature was cooled to 0 °C, and 30.0 mmol of boron tribromide was slowly added dropwise. The mixture was stirred for 2 hours, 50 mL of 1 M dilute hydrochloric acid was added, and the mixture was stirred for 30 minutes. The organic phase was separated. The aqueous phase was extracted with ethyl acetate. The combined organic phases were dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. It was separated and purified by silica gel column chromatography to obtain intermediate Int-61, a white solid, yield: 95%.

[0394] Step 4: The preparation route of metal compound P115 is as follows

[0395]

[0396] Preparation of intermediate Int-62: Referring to the synthesis method of Int-36 in Step 4 of Example 9 above, replacing Int-35 with S8 and m-chlorophenol with Int-61, intermediate Int-62 was prepared, a yellow solid, yield 84%.

[0397] Preparation of intermediate Int-63: Referring to the synthesis method of Int-49 in Example 11 above, only replacing Int-48 with Int-62, intermediate Int-63 was prepared, a brown solid, yield 78%.

[0398] Preparation of intermediate Int-64: Referring to the synthesis method of Step 7 of Example 8 above, only replacing Int-31 in Step 7 of Example 8 with Int-63, intermediate Int-64 was prepared, a gray solid, yield 82%.

[0399] Preparation of compound P115: Referring to the synthesis method of Step 8 of Example 8 above, only replacing Int-32 in Step 8 of Example 8 with Int-64, compound P115 was prepared, a yellow solid, yield 48%; 11H NMR (δ, DMSO-d6): 8.56 - 8.54 (1H, d); 8.22 - 8.20 (1H, d); 8.16 - 8.14 (2H, m); 7.86 - 7.80 (6H, m); 7.76 - 7.74 (1H, d); 7.62 - 7.57 (4H, m); 7.48 - 7.44 (1H, m); 7.35 - 7.31 (2H, m); 7.21 - 7.20 (1H, d); 7.12 (1H, s); 7.02 - 6.91 (8H, m); 6.75 - 6.73 (1H, d); 2.19 (6H, s); 1.37 (9H, s); 1.31 (18H, s). HRMS: 1170.4584 [M + H], and this product was determined to be the target product.

[0400] Preparation of Other Compounds

[0401] Referring to the synthesis methods of Examples 1 - 14 above, compounds P1, P3 - P6, P8, P9, P11, P13 - P24, P26 - P30, P32 - P34, P36, P37, P39 - P45, P47 - P50, P52 - P114, P116 - P132 were prepared, and the specific structures are shown in Table 1 of the present invention.

[0402] Preparation of Organic Electroluminescent Devices 1 - 132

[0403] The glass substrate with a patterned ITO electrode was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonically treated in an acetone / ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with an ultraviolet light cleaning machine for 10 minutes, and bombarded with a low-energy cation beam on the surface.

[0404] Place the above-treated ITO glass substrate in a vacuum chamber and evacuate to less than 1×10 -5 Pa, and deposit metallic silver as the anode on the above ITO film, with a deposition film thickness of Continue to deposit compound HATCN as the hole injection layer, with a deposition film thickness of Continue to deposit HTM as the hole transport layer on the above hole injection layer film, with a deposition film thickness of

[0405] Deposit BPrime as the electron blocking layer on the above hole transport layer, with a deposition film thickness of

[0406] On the above-mentioned electron blocking layer, the corresponding metal complexes (P1 to P132) and H1 + H2 in Table 2 below are evaporated to form the organic light-emitting layer of the device. Among them, H1 + H2 is the host material, and the mass ratio of H1 to H2 is 1:1. The corresponding metal complexes in Table 2 are the doping materials, and the doping concentration is 12% (the doping mass is 12% of the mass of the host material). The evaporation film thickness is

[0407] On the above-mentioned organic light-emitting layer, a layer of compound DPO is further evaporated to form the hole blocking layer of the device. The evaporation film thickness is

[0408] On the above-mentioned hole blocking layer, a layer of LiQ and ET018 is further evaporated to form the electron transport layer of the device. Among them, LiQ is 50% of the mass of ET018. The evaporation film thickness is

[0409] On the above-mentioned electron transport layer, a layer of LiF is further evaporated to form the electron injection layer of the device. The evaporation film thickness is

[0410] On the above-mentioned electron injection layer, metal magnesium and silver are evaporated to form the cathode layer of the device. Among them, the mass ratio of magnesium to silver is 1:10. The evaporation film thickness is

[0411] Finally, on the cathode layer, a compound HTM is evaporated to form the capping layer. The evaporation film thickness is Fabricate the organic electroluminescent element of the present invention, as shown in the attached Figure 1 Device 100.

[0412] Preparation of Comparative Element 1

[0413] Use the compound shown in BD012 to replace the metal complexes (P1 to P132) in the above-mentioned organic electroluminescent device, and the other steps are the same as above to fabricate Comparative Element 1.

[0414] The structural formulas of the aforementioned HATCN, HTM, BPrime, H1, H2, BD012, DPO, and ET018 are as follows:

[0415]

[0416] Element Effect Evaluation:

[0417] Use a digital source meter and a luminance meter to measure the driving voltage, current efficiency, and lifespan of the above-mentioned light-emitting elements. Specifically, increase the voltage at a rate of 0.1 V per second, and measure when the current density of the organic electroluminescent element reaches 10 mA / cm 2The voltage at this time is the driving voltage, and the brightness at this time is measured simultaneously; the ratio of brightness to current density is the current efficiency; the LT95% life test is as follows: Use a luminance meter to measure the brightness decay of the organic electroluminescent element to 950 cd / m 2 at a brightness of 1000 cd / m, maintain a constant current, and measure the time in hours when the brightness decay of the organic electroluminescent element is 950 cd / m 2 . Some of the test results are summarized in Table 2, and the * data is normalized compared to Comparative Element 1.

[0418] Table 2

[0419]

[0420]

[0421]

[0422] As can be seen from Table 2, compared with Comparative Element 1, the organic electroluminescent elements 1 to 132 prepared with the metal compound of the present invention have a lower driving voltage, a higher luminous efficiency and an excellent life, and are excellent organic electroluminescent materials.

[0423] Compared with the metal complex BD012 of Comparative Element 1 and the metal compounds P1 to P132 of the present invention, the difference is that in the metal-to-ligand charge transfer process of C^Pt^N of the metal complex of the present invention, sterically bulky groups such as triptycene and homotriptycene are used to enhance the steric hindrance and polarity in the metal polarization direction, improving the stability and quantum efficiency of the ligand. BD012 of Comparative Example 1 only introduces substituents with large planar steric hindrance on the benzimidazole nitrogen, which only plays a role in stabilizing the C-N bond and has small steric hindrance. Therefore, the metal complex of the present disclosure has a low driving voltage, high efficiency and excellent element life performance in terms of element performance.

[0424] The above are only representative examples of the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, and all should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claimed rights.

Claims

1. A metal complex, characterized in that The metal complex has a structure shown in formula (I): wherein ring A, ring B, ring C and ring D are each independently selected from a monocyclic or polycyclic condensed ring system, wherein each ring of the monocyclic and polycyclic condensed ring system is independently a 5-6 membered carbocyclic ring or a 5-6 membered heterocyclic ring, and in the rings A, B, C, D, R a , R b , R c and R d At least one of the structures comprises or is selected from the structure shown in formula (2), formula (3) or formula (4): Metal M represents a metal element with a relative atomic mass greater than 40; X 1 ~X 6 Each is independently selected from C, B or N; Z 1 ~Z 4 Each is independently selected from C or N; X 7 ~X 18 Each independently selected from CR 5 , or N; L 1 , L 2 , L 3 Each independently selected from a single bond, O, S, S=O, SO2, Se, NR 6 , PR 6 , R 6 P=O、CR 6 R 7 、C=O、SiR 6 R 7 ,GeR 6 R 7 or BR 6 ; R a , R b , R c and R d Each independently represents mono- or poly-substituted to saturated substitution, or unsubstituted; R a , R b , R c , R d Each is independently selected from the group consisting of formula (2), formula (3), formula (4), hydrogen, or a group consisting of the following groups: deuterium, halogen atom, cyano group, acyl group, carboxyl group, ether group, ester group, isocyano group, sulfide group, selenoalkyl group, sulfinyl group, sulfonyl group, phosphine group, substituted or unsubstituted C1-C 40 Straight chain alkyl, substituted or unsubstituted C1~C 40 Straight chain heteroalkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C1~C 40 Alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Aromatic amino, substituted or unsubstituted C3~C 40 Silane, substituted or unsubstituted C2~C 40 Alkenyl, substituted or unsubstituted C4~C 40 Cycloalkenyl, substituted or unsubstituted C2~C 40 Heteroalkenyl, substituted or unsubstituted C2~C 40 Alkynyl, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 Heteroaryl and combinations thereof, any adjacent two or more R a , R b , R c , R d They may be arbitrarily joined or fused to form a substituted or unsubstituted ring; R 1 ~R 7 Each is independently selected from hydrogen, or selected from the group consisting of the following groups: deuterium, halogen atoms, cyano groups, acyl groups, carboxyl groups, ether groups, ester groups, isocyano groups, sulfenyl groups, seleno groups, sulfinyl groups, sulfonyl groups, phosphino groups, substituted or unsubstituted C1-C 40 Straight chain alkyl, substituted or unsubstituted C1~C 40 Straight chain heteroalkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C1~C 40 Alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Aromatic amino, substituted or unsubstituted C3~C 40 Silane, substituted or unsubstituted C2~C 40 Alkenyl, substituted or unsubstituted C4~C 40 Cycloalkenyl, substituted or unsubstituted C2~C 40 Heteroalkenyl, substituted or unsubstituted C2~C 40 Alkynyl, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 Heteroaryl and combinations thereof, any adjacent two or more R 1 ~R 7 They may be arbitrarily joined or fused to form a substituted or unsubstituted ring.

2. The metal complex according to claim 1, characterized in that The metal complex is selected from the group consisting of compounds of formula M(LA)(LB): Wherein LA-LB is selected from the group consisting of: and / or LA-LB selected from the group consisting of: wherein ring A1, ring B1, ring C1, ring C2 and ring D are each independently selected from any one of the structures of formula (2), formula (3) or formula (4); W is selected from O, S, CR 8 R 9 、SiR 8 R 9 , CR 8 R 9 CR 10 R 11 or NR x ; Y is selected from O, S or NR x , preferably selected from S or NR x , more preferably selected from NR x ; R in LA1~LA24 x are each independently selected from formula (2), formula (3) or formula (4), and X in formula (2), formula (3) and formula (4) 7 ~X 18 At least one of them is C and R x connect; R in LA25~LA60、LB1~LB140 x Each occurrence is independently selected from Formula (2), Formula (3), Formula (4), or a group consisting of: substituted or unsubstituted C1-C 40 Straight chain alkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C2~C 40 Alkenyl, substituted or unsubstituted C4~C 40 Cycloalkenyl, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 Heteroaryl and combinations thereof, R x Can be connected with adjacent R a , R 5 , R c or R d Any combination or fusion to form a substituted or unsubstituted ring; R Y Each occurrence is independently selected from Formula (2), Formula (3), Formula (4), or a group consisting of: substituted or unsubstituted C1-C 40 Straight chain alkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C2~C 40 Alkenyl, substituted or unsubstituted C4~C 40 Cycloalkenyl, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 Heteroaryl and combinations thereof; R 8 ~R 11 Each is independently selected from hydrogen, or selected from the group consisting of the following groups: deuterium, halogen atoms, cyano groups, acyl groups, carboxyl groups, ether groups, ester groups, isocyano groups, sulfenyl groups, seleno groups, sulfinyl groups, sulfonyl groups, phosphino groups, substituted or unsubstituted C1-C 40 Straight chain alkyl, substituted or unsubstituted C1~C 40 Straight chain heteroalkyl, substituted or unsubstituted C3~C 40 Branched or cyclic alkyl, substituted or unsubstituted C1~C 40 Alkoxy, substituted or unsubstituted C6~C 60 Arylalkyl, substituted or unsubstituted C6~C 60 Aryloxy, substituted or unsubstituted C6~C 60 Aromatic amino, substituted or unsubstituted C3~C 40 Silane, substituted or unsubstituted C2~C 40 Alkenyl, substituted or unsubstituted C4~C 40 Cycloalkenyl, substituted or unsubstituted C2~C 40 Heteroalkenyl, substituted or unsubstituted C2~C 40 Alkynyl, substituted or unsubstituted C6~C 60 Aryl, substituted or unsubstituted C2~C 60 Heteroaryl and combinations thereof, any adjacent two or more R 8 ~R 11 They may be arbitrarily joined or fused to form a substituted or unsubstituted ring; Preferably, R 8 ~R 11 are independently selected from hydrogen, or from the group consisting of deuterium, halogen atoms, substituted or unsubstituted C1-C 20 Straight chain alkyl, substituted or unsubstituted C1~C 20 Straight chain heteroalkyl, substituted or unsubstituted C3~C 20 Branched or cyclic alkyl, substituted or unsubstituted C1~C 20 Alkoxy, substituted or unsubstituted C6~C 30 Arylalkyl, substituted or unsubstituted C6~C 30 Aryloxy, substituted or unsubstituted C6~C 30 Aromatic amino, substituted or unsubstituted C3~C 20 Silane, substituted or unsubstituted C2~C 20 Alkenyl, substituted or unsubstituted C4~C 20 Cycloalkenyl, substituted or unsubstituted C2~C 20 Heteroalkenyl, substituted or unsubstituted C2~C 20 Alkynyl, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 Heteroaryl and combinations thereof, any adjacent two or more R 8 ~R 11 They may be arbitrarily joined or fused to form a substituted or unsubstituted ring; Preferably, R 8 ~R 11 are independently selected from hydrogen, or from the group consisting of deuterium, halogen atoms, substituted or unsubstituted C1-C 10 Straight chain alkyl, substituted or unsubstituted C3~C 10 Branched or cyclic alkyl, substituted or unsubstituted C6~C 20 Aryl; Preferably, R 8 ~R 11 Each is independently selected from hydrogen, or selected from the group consisting of deuterium, fluorine, chlorine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl; Preferably, W is selected from O, S, C(CH3)2, C(C6H5)2, Si(CH3)2, Si(C6H5)2 or NR x ; More preferably, W is selected from O, S, C(CH3)2, C(C6H5)2, Si(CH3)2, Si(C6H5)2.

3. The metal complex according to claim 1 or 2, characterized in that The metal M is selected from Ir, Pt, Pd, Ru, Rh, Os, Au, Cu, Ni, Co, Ga or Ge, preferably Pt or Pd, more preferably Pt; L 1 , L 2 Each independently selected from a single bond, O, S, Se, NR 6 , PR 6 , BR 6 , CR 6 R 7 or SiR 6 R 7 Preferably, L 1 Selected from O, S or Se, L 2 Selected from single bond, NR 6 , PR 6 or BR 6 ; R a , R b , R c , R d Each independently selected from the group consisting of formula (2), formula (3), formula (4), a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, an isocyano group, R A1 ~R A30 , R B1 ~R B195 , R C1 ~R C80 , R substituted by one or more deuterium atoms A1 ~R A30 , R substituted by one or more deuterium atoms B1 ~R B195 , R substituted by one or more deuterium atoms C1 ~R C80 The group composed of; R 1 ~R 11 are independently selected from a hydrogen atom, a deuterium atom, a cyano group, R A1 ~R A30 , R B1 ~R B195 , R C1 ~R C80 , R substituted by one or more deuterium atoms A1 ~R A30 , R substituted by one or more deuterium atoms B1 ~R B195 , R substituted by one or more deuterium atoms C1 ~R C80 The group composed of; R X , R Y Each occurrence is independently selected from formula (2), formula (3), formula (4), or selected from R A1 ~R A25 , R B1 ~R B185 , R C1 ~R C79 , R substituted by one or more deuterium atoms A1 ~R A25 , R substituted by one or more deuterium atoms B1 ~R B185 , R substituted by one or more deuterium atoms C1 ~R C79 The group composed of; Among them, R A1 ~R A30 The structural formula shown is as follows: R B1 ~R B195 The structure shown is as follows: R C1 ~R C80 The structure shown is as follows:

4. The metal complex according to any one of claims 1 to 3, characterized in that Formula (2) has a structure shown in the following formula (2-1), (2-2) or (2-3), formula (3) has a structure shown in any one of the following formulas (3-1) to (3-8), and formula (4) has a structure shown in the following formula (4-1), (4-2) or (4-3): R 1 To R 4 has the same meaning as in claim 1 or 3; Preferably, R 1 To R 4 independently selected from hydrogen, deuterium, halogen atoms, C1-C 10 Straight or branched alkyl, C3~C 12 Cyclic alkyl; More preferably, R 1 To R 4 Independently selected from hydrogen, deuterium, fluorine, methyl, ethyl, propyl, isopropyl, tert-butyl.

5. The metal complex according to any one of claims 1 to 4, characterized in that The metal complex is selected from the compounds represented by any one of the following structures: Among them, R a To R d The definition of is the same as that in claim 1 or 3, and in formula (I-1), R a To R d At least one, preferably one to two, of the compounds are structures represented by formula (2), formula (3) or formula (4); In formula (I-2), (I-3), (I-4) and (I-5), ring B, ring C1, ring C2 and ring D are each independently selected from any one of the structures of formula (2), formula (3) or formula (4); In formula (I-6), It is fused to any one of the structures in formula (2), (3) or (4), preferably fused to an adjacent ring atom on the aromatic ring in any one of the structures in formula (2), (3) or (4); Preferably, R a To R d Independently selected from the structure represented by formula (2), formula (3) or formula (4), or hydrogen, or the group consisting of the following groups: Deuterium, halogen atoms, substituted or unsubstituted C1~C 10 Straight chain alkyl, substituted or unsubstituted C3~C 12 Branched or cyclic alkyl, substituted or unsubstituted C6~C 20 Arylalkyl, substituted or unsubstituted C6~C 20 Aryl and combinations thereof; More preferably, R a To R d Independently selected from the structure represented by formula (2), formula (3) or formula (4), or hydrogen, or the group consisting of the following groups: deuterium, halogen atoms, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, phenyl substituted by C1-C6 straight chain or branched alkyl.

6. The metal complex according to claim 1, characterized in that The metal complex is selected from the group consisting of the following compounds and deuterated derivatives of the following compounds:

7. Use of the metal complex according to any one of claims 1 to 6 in the preparation of an organic electroluminescent device; Preferably, the metal complex is used as a doping material for an organic light-emitting layer of the organic electroluminescent device; Preferably, the organic light-emitting layer comprises a host material and a doping material, and the metal complex accounts for 1 to 50% by mass of the host material, preferably 1 to 20%, and more preferably 5 to 15%.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an organic layer, and the organic layer comprises the metal complex according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic electroluminescent device further comprises an anode and a cathode, and the organic layer is arranged between the anode and the cathode; Preferably, the organic layer comprises a light-emitting layer, the light-emitting layer comprises a host material and a doping material, and the doping material comprises the metal complex according to any one of claims 1 to 6; Preferably, the host material is selected from the group consisting of triphenylene, carbazole, indolecarbazole, dibenzothiophenyl, dibenzofuranyl, fluorene, dibenzoselenophene, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthryl, aza-triphenylene, aza-carbazole, aza-indolecarbazole, aza-dibenzothiophenyl, aza-dibenzofuranyl, aza-dibenzoselenophene and aza-(5,9-diaza-13b-boronaphtho[3,2,1-de]anthryl) or a combination derived from these systems; Preferably, the doping material accounts for 1 to 20% of the mass of the host material, preferably 5 to 15%; Preferably, the metal complex accounts for 1-20% by mass of the host material, preferably 5-15%.

10. A consumer product comprising the organic electroluminescent device according to claim 8 or 9.

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