A thermally induced delayed fluorescence complex and its preparation method and organic electroluminescent device

Abstract

The present invention relates to the field of organic light-emitting materials, and specifically to a heat-induced delayed fluorescence complex, a preparation method thereof, and an organic electroluminescent device. The present invention provides a heat-induced delayed fluorescence complex, a preparation method thereof, and an organic electroluminescent device. The heat-induced delayed fluorescence complex provided by the present invention has TADF characteristics, good stability, short delayed fluorescence lifetime, and high fluorescence efficiency; it utilizes the strong coordination ability of nitrogen-containing aromatic heterocyclic groups such as dipyridine and terpyridine, and after coordinating them with metal cations, increases their receptor strength and improves the rigidity of their derivatives, and utilizes the coordination effect to induce organic molecules that originally do not have TADF to form a complex with TADF characteristics after coordination and has a high luminescence efficiency. Experiments show that the complex provided by the present invention achieves an external quantum efficiency of 11.7% in the performance test of the electroluminescent device, breaking through the external quantum efficiency limit of 5% of traditional fluorescent materials.

Description

Technical Field

[0001] The present invention relates to the field of organic light-emitting materials, and particularly to a thermally activated delayed fluorescence complex, a preparation method thereof, and an organic electroluminescent device. Background Art

[0002] Compared with traditional liquid crystal displays, organic electroluminescent devices (OLEDs) have been widely used in many fields such as display panels, lighting, and biological probes due to a series of advantages such as self-luminescence, low cost, ultrathin, and bendable. Among them, as one of the key materials for fabricating OLEDs, the development process of luminescent materials has gone through three generations. The first generation is traditional fluorescent materials, which can only utilize singlet excitons during electroluminescence, and their theoretical maximum internal quantum efficiency is only 25%. The second generation is phosphorescent materials, which can make full use of singlet and triplet excitons, and their theoretical maximum internal quantum efficiency can reach 100%. However, due to the need to use precious metals, their practical applications are limited. The third generation is thermally activated delayed fluorescence (TADF) materials. Due to having a small energy difference (ΔE 1 ) between the lowest singlet excited state (S 1 ) and the lowest triplet excited state (T ST ), triplet excitons can absorb the heat of the surrounding environment, undergo reverse intersystem crossing to be upconverted into singlet excitons and undergo radiative transitions, and their theoretical maximum internal quantum efficiency can also reach 100%. Moreover, the molecular design is flexible, precious metals are not required, and it can be a pure organic material. Therefore, it has greater cost advantages and application prospects.

[0003] Most TADF molecules are pure organic compounds, and their structural characteristics are that they contain distorted electron donor and acceptor structural units. By controlling the donor / acceptor bridging mode and the torsion angle, sufficient spatial separation is generated between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) to obtain a small ΔE ST and thus have TADF characteristics. Commonly used donors mainly include carbazole, 9,10-dihydroacridine, triphenylamine, phenoxazine and other derivative groups, and the acceptors mostly select groups containing strong electron-withdrawing groups such as carbonyl, sulfone, boron, cyano and nitrogen-containing aromatic heterocycles.

[0004] Nitrogen-containing aromatic heterocycles are a common type of electron-withdrawing group. However, when used as acceptors in TADF materials, aromatic heterocycles containing multiple nitrogen atoms such as triazine (Chem. Commun. 2015, 51, 13662) or groups with multiple pyridine rings connected such as terpyridine (Chem. Eur. J., 2017, 23, 114) are required to meet the acceptor strength requirements and ensure that the obtained organic compounds have TADF characteristics. Even so, the weak acceptor strength of terpyridine and the free rotation of the connected single bond still result in low luminescence performance of its TADF derivatives. And due to the too weak acceptor strength of bipyridine, the compounds composed of bipyridine and donors usually do not have TADF characteristics. SUMMARY OF THE INVENTION

[0005] In view of this, the technical problem to be solved by the present invention is to provide a thermally activated delayed fluorescence (TADF) complex, a preparation method thereof, and an organic electroluminescent device. The complex provided by the present invention has TADF characteristics, good stability, a short delayed fluorescence lifetime, and a relatively high fluorescence efficiency.

[0006] The present invention provides a thermally activated delayed fluorescence complex having a structure of formula (I):

[0007]

[0008] Wherein, J is a nitrogen-containing aromatic group, and n is 1 or 2;

[0009] X is a halogen atom;

[0010] Q is a nitrogen-containing aromatic heterocyclic group;

[0011] There is a coordination bond between the said Q and Zn.

[0012] The inventors of the present application have creatively discovered that nitrogen-containing aromatic heterocyclic groups such as bipyridine and terpyridine have strong coordination ability. After coordinating with metal cations, it will not only increase their acceptor strength, but also improve the rigidity of their derivatives. Thus, through coordination, organic molecules originally without TADF can form complexes with TADF characteristics and have relatively high luminescence efficiency after coordination.

[0013] The Q in the thermally activated delayed fluorescence complex provided by the present application is an electron acceptor group; specifically, the said Q is a nitrogen-containing aromatic heterocyclic group; more specifically, the Q in the present invention is a bidentate or tridentate nitrogen-containing aromatic heterocyclic group with coordination ability. In some embodiments of the present invention, the said Q is a substituted or unsubstituted bipyridyl group, a substituted or unsubstituted phenanthroline group, a substituted or unsubstituted dipyridophenazine group, a substituted or unsubstituted pyridazine group, or a substituted or unsubstituted pyrazine group. In one embodiment, the said Q has a structure of formula 1, formula 2, formula 3, formula 4, formula 5 or formula 6;

[0014]

[0015] Wherein, R 3 is a substituted or unsubstituted C 1 -C 20 alkyl group or hydrogen;

[0016] Aj is a substituted or unsubstituted phenyl group;

[0017] Q 1 and Q 2 are independently C or N;

[0018] x is 0, 1 or 2.

[0019] In one embodiment, the Q-J n has a structure of formula (L2-a1), formula (L2-a2), formula (L2-b1), formula (L2-b2), formula (L2-c1), formula (L2-c2), formula (L2-d1), formula (L2-d2), formula (L2-e1), formula (L2-e2), formula (L2-f1), formula (L2-f2), formula (L2-g1), formula (L2-g2), formula (L2-h1), formula (L2-h2), formula (L3-i), formula (L3-j), formula (L3-k) or formula (L3-m);

[0020]

[0021]

[0022] wherein, R 3 is an alkyl group of C 1 ~C 20 or hydrogen.

[0023] In the thermally activated delayed fluorescence complex provided by the present application, J is a nitrogen-containing aromatic group; specifically, the J is a nitrogen-containing aromatic group having an electron-donating ability. In certain embodiments of the present invention, the J is selected from formula (D-1-a), formula (D-1-b), formula (D-1-c), formula (D-1-d), formula (D-1-e) or formula (D-1-f);

[0024]

[0025] wherein, R 1 is hydrogen, an alkyl group of C 1 ~C 30 an alkoxy group of C 1 ~C 30 a disubstituted amino group of C 2 ~C 30 or a substituted or unsubstituted aryl group of C 6 ~C 35 ; R 4 is an alkyl group of C 1 ~C 30 ; Ar 1 is an aryl group of C 6 ~C 35 a heteroaryl group of C 4 ~C 35 or hydrogen.

[0026] In one embodiment, the above Ar 1Selected from formula (Ar-a1), formula (Ar-a2), formula (Ar-b1), formula (Ar-b2), formula (Ar-c1), formula (Ar-c2), formula (Ar-d1), formula (Ar-d2), formula (Ar-e), formula (Ar-f), formula (Ar-g1), formula (Ar-g2) or hydrogen;

[0027]

[0028]

[0029] wherein, R 2 is hydrogen, C 1 -C 20 alkyl, C 6 -C 30 aryl, C 7 -C 35 substituted aryl or C 4 -C 35 substituted heteroaryl.

[0030] X in the thermally activated delayed fluorescence complex provided by the present application is a halogen atom. In certain embodiments of the present invention, the X is fluorine, chlorine, bromine or iodine.

[0031] In certain embodiments of the present invention, the thermally activated delayed fluorescence complex provided by the present application has a structure of formula (I-a), formula (I-b), formula (I-c), formula (I-d), formula (I-e), formula (I-f), formula (I-g), formula (I-h), formula (I-i), formula (I-j), formula (I-k), formula (I-l), formula (I-m), formula (I-n) or formula (I-o);

[0032]

[0033]

[0034]

[0035] The present invention also provides a preparation method of the above complex, comprising the following steps:

[0036] Coordination of the compound with the structure shown in formula α with zinc halide to obtain the above complex;

[0037]

[0038] wherein, J, Q and n in the compound with the structure shown in formula α are the same as above and will not be elaborated.

[0039] The dosage ratio of the compound with the structure shown in Formula α to zinc halide in the present invention is 1:1 to 2.2, preferably 1.1 to 1.5. In one embodiment, the dosage ratio of the compound with the structure shown in Formula α to zinc halide is 1:1.5 to 1.6. The coordination in the present invention is carried out at a temperature of 50°C to 90°C, preferably at 80°C, and the time of the coordination is 4h to 12h, preferably 8h. The zinc halide in the present invention is selected from at least one of zinc fluoride, zinc chloride, zinc bromide or zinc iodide.

[0040] In one embodiment, the preparation method of the above-mentioned complex includes: coupling any one of the compound with the structure of Formula (III) or the compound with the structure of Formula (IV) with the brominated compound with the structure of Formula (V) to obtain the compound with the structure shown in Formula α, and then coordinating the compound with the structure shown in Formula α with zinc halide to obtain the above-mentioned complex;

[0041]

[0042] Among them, J, Q, and n are the same as above and will not be elaborated.

[0043] In some embodiments of the present invention, the dosage ratio of any one of the compound with the structure of Formula (III) or the compound with the structure of Formula (IV) to the brominated compound with the structure of Formula (V) is 1:1.1 to 1.5. In some embodiments of the present invention, the coupling is carried out at a temperature of 80°C to 170°C; in one embodiment, the coupling in the present invention is carried out at a temperature of 90°C; in another embodiment, the coupling in the present invention is carried out at a temperature of 120°C. In another embodiment, the coupling in the present invention is carried out at a temperature of 160°C; the time of the coupling is 12h to 48h. The dosage ratio, coordination temperature, coordination time of the compound with the structure shown in Formula α coordinated with zinc halide, and the selection of zinc halide are the same as above and will not be elaborated.

[0044] In another embodiment, the preparation method of the above-mentioned complex includes: coupling the compound with the structure of Formula (VI) with the compound with the structure of Formula (VII) to obtain the compound with the structure shown in Formula α, and then coordinating the compound with the structure shown in Formula α with zinc halide to obtain the above-mentioned complex.

[0045]

[0046] Among them, L is defined as a halogenated nitrogen-containing aromatic group, and Q, n, Ar 1 are the same as above and will not be elaborated. Specifically, L is selected from Formula (D-1-a1), Formula (D-1-b1), Formula (D-1-c1), Formula (D-1-d1), Formula (D-1-e1) or Formula (D-1-f1);

[0047]

[0048] R 1 、R 4 are the same as above and will not be elaborated further; Z 1 and Z 2 are independently a halogen atom or hydrogen, and Z 1 and Z 2 are the same but cannot both be hydrogen at the same time; specifically, it means that only when Z 1 and Z 2 are both halogen atoms, Z 1 and Z 2 are the same. When either Z 1 and Z 2 is hydrogen, they cannot be the same. In some embodiments of the present invention, Z 1 and Z 2 are independently fluorine, chlorine, bromine, iodine or hydrogen, and Z 1 and Z 2 are the same but cannot both be hydrogen at the same time.

[0049] The dosage ratio of any one of the compounds with the structure of formula (VI) in the present invention to the boric acid derivative compound with the structure of formula (VII) is 1:2 to 4, preferably 1:3. The coupling in the present invention is carried out at a temperature of 60°C to 100°C, preferably at 90°C; the time of the coupling is 6h to 48h, preferably 24h. The dosage ratio of the compound with the structure shown in formula α in the present invention to coordinate with zinc halide, the coordination temperature, the coordination time, and the selection of zinc halide are the same as above and will not be elaborated further.

[0050] The present invention also provides an organic electroluminescent device, including a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, and the organic layer contains the above-mentioned thermally activated delayed fluorescence complex.

[0051] The present invention provides a thermally activated delayed fluorescence complex, its preparation method, and an organic electroluminescent device. The thermally activated delayed fluorescence complex provided by the present invention has the structure of formula (I):

[0052]

[0053] Among them, J is a nitrogen-containing aromatic group, and the value of n is 1 or 2; X is a halogen atom; Q is a nitrogen-containing aromatic heterocyclic group; and Q is coordinately connected to Zn. The thermally activated delayed fluorescence complex provided by the present invention has TADF characteristics, good stability, short delayed fluorescence lifetime, and relatively high fluorescence efficiency; by utilizing the strong coordination ability of nitrogen-containing aromatic heterocyclic groups such as bipyridine and terpyridine, after coordinating them with metal cations, the acceptor strength is increased, and the rigidity of its derivatives is improved. By using the coordination effect, organic molecules originally without TADF form complexes with TADF characteristics and relatively high luminescence efficiency after coordination. Experiments show that the complex provided by the present invention achieves an external quantum efficiency of 11.7% in the performance test of electroluminescent devices, breaking through the limitation of the external quantum efficiency of 5% of traditional fluorescent materials. Description of the Drawings

[0054] Figure 1 UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 1 and 16 and room temperature fluorescence spectra of the films doped with 5 wt% in SimCP 2 ;

[0055] Figure 2 Low temperature fluorescence and low temperature phosphorescence spectra of the films doped with 5 wt% of the compounds described in Examples 1 and 16 in SimCP 2 ;

[0056] Figure 3 Transient fluorescence spectrum decay curve of the film doped with 5 wt% of the compound described in Example 1 in SimCP 2 ;

[0057] Figure 4 Transient fluorescence spectrum decay curve of the film doped with 5 wt% of the compound described in Example 16 in SimCP 2 ;

[0058] Figure 5 UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 2 and 17 and room temperature fluorescence spectra of the films doped with 5 wt% in SimCP 2 ;

[0059] Figure 6 Low temperature fluorescence and low temperature phosphorescence spectra of the films doped with 5 wt% of the compounds described in Examples 2 and 17 in SimCP 2 ;

[0060] Figure 7 Transient fluorescence spectrum decay curve of the film doped with 5 wt% of the compound described in Example 2 in SimCP 2 ;

[0061] Figure 8 The transient fluorescence spectral decay curve of the compound described in Example 17 doped at 5 wt% in SimCP 2 ;

[0062] Figure 9 The UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 3 and 18 and the room temperature fluorescence of the film doped at 5 wt% in SimCP 2 ;

[0063] Figure 10 The low temperature fluorescence and low temperature phosphorescence spectra of the film of the compounds described in Examples 3 and 18 doped at 5 wt% in SimCP 2 ;

[0064] Figure 11 The transient fluorescence spectral decay curve of the compound described in Example 3 doped at 5 wt% in SimCP 2 ;

[0065] Figure 12 The transient fluorescence spectral decay curve of the compound described in Example 18 doped at 5 wt% in SimCP 2 ;

[0066] Figure 13 The UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 5 and 20 and the room temperature fluorescence of the film doped at 5 wt% in SimCP 2 ;

[0067] Figure 14 The low temperature fluorescence and low temperature phosphorescence spectra of the film of the compounds described in Examples 5 and 20 doped at 5 wt% in SimCP 2 ;

[0068] Figure 15 The transient fluorescence spectral decay curve of the compound described in Example 5 doped at 5 wt% in SimCP 2 ;

[0069] Figure 16 The transient fluorescence spectral decay curve of the compound described in Example 20 doped at 5 wt% in SimCP 2 ;

[0070] Figure 17 The UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 8 and 23 and the room temperature fluorescence of the film doped at 5 wt% in SimCP 2 ;

[0071] Figure 18The transient fluorescence spectrum decay curve of the thin film with the compound described in Example 8 doped at 5 wt% in SimCP 2 ;

[0072] Figure 19 The transient fluorescence spectrum decay curve of the thin film with the compound described in Example 23 doped at 5 wt% in SimCP 2 ;

[0073] Figure 20 The UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 11 and 26 and the room temperature fluorescence of the thin film doped at 5 wt% in SimCP 2 ;

[0074] Figure 21 The UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 12 and 27 and the room temperature fluorescence of the thin film doped at 5 wt% in SimCP 2 ;

[0075] Figure 22 The UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 13 and 28 and the room temperature fluorescence of the thin film doped at 5 wt% in SimCP 2 ;

[0076] Figure 23 The transient fluorescence spectrum decay curve of the thin film with the compound described in Example 13 doped at 5 wt% in SimCP 2 ;

[0077] Figure 24 The transient fluorescence spectrum decay curve of the thin film with the compound described in Example 28 doped at 5 wt% in SimCP 2 ;

[0078] Figure 25 The UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 14 and 29 and the room temperature fluorescence of the thin film doped at 5 wt% in SimCP 2 ;

[0079] Figure 26 The transient fluorescence spectrum decay curve of the thin film with the compound described in Example 14 doped at 5 wt% in SimCP 2 ;

[0080] Figure 27 The transient fluorescence spectrum decay curve of the thin film with the compound described in Example 29 doped at 5 wt% in SimCP 2 ; Detailed implementation manners

[0081] The present invention discloses a thermally activated delayed fluorescence complex, a preparation method thereof, and an organic electroluminescent device. Those skilled in the art can draw on the content of this article and appropriately modify the process parameters to achieve it. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are all regarded as included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and those related can obviously make changes or appropriate alterations and combinations to the methods and applications in this article without departing from the content, spirit, and scope of the present invention to implement and apply the technology of the present invention.

[0082] The present invention will be further described below in conjunction with embodiments:

[0083] Example 1

[0084] The synthesis of ligand ABTPy was carried out according to the following reaction equation:

[0085]

[0086] The specific steps were as follows: Under an argon atmosphere, 9,9 - dihexyl - 9,10 - dihydroacridine (3.49 g, 10 mmol), 4-(4 - bromophenyl)-(2,2'-6,2”)-terpyridine (3.88 g, 10 mmol), P(t - Bu) 3 (2.4 mL, 10% in toluene), Pd(OAc) 2 (0.2245 g, 1.0 mmol), t - BuOK (1.68 g, 15 mmol), and xylene (80 mL) were added to a 250 mL reaction flask, and the mixture was refluxed for 48 h under vigorous stirring. After natural cooling to room temperature, the reaction solution was extracted with dichloromethane (DCM), the organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 160:1) gave 2.34 g of a white solid with a yield of 36%. 1 1H NMR (500 MHz, CDCl 3)δ 8.84 (s, 2H), 8.76 (d, J = 4.8 Hz, 2H), 8.72 (d, J = 8.0 Hz, 2H), 8.14 (d, J = 8.4, 2H), 7.91 (t, J = 7.7 Hz, 2H), 7.42 (d, J = 8.4, 2H), 7.38 (dd, J = 7.5, 4.8 Hz, 2H), 7.32 (d, J = 7.8 Hz, 2H), 6.95 (t, J = 8.4 Hz, 2H), 6.88 (t, J = 7.4 Hz, 2H), 6.20 (d, J = 8.2 Hz, 2H), 2.05 - 1.87 (m, 4H), 1.24 - 1.03 (m, 16H), 0.87 - 0.76 (m, 6H).

[0087] Example 2

[0088] The synthesis of ligand ABBPy was carried out according to the following reaction equation:

[0089]

[0090] The specific steps were as follows: Under an argon atmosphere, 9,9 - dihexyl - 10 - (4 - (4 - pinacolborate)phenyl) - 9,10 - dihydroacridine (1.65 g, 3 mmol), 5 - bromo - 2,2'-bipyridine (0.71 g, 3 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Na 2 CO 3 (1.59 g, 15 mmol) and a mixed solvent of THF / EtOH / H 2 O (30 mL / 18 mL / 18 mL) were added to a 250 mL reaction flask, and the mixture was refluxed at 90 °C for 12 h. It was naturally cooled to room temperature, the reaction solution was extracted with DCM, the organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 80:1) gave 1.10 g of a white solid with a yield of 63%. 1 H NMR (500 MHz, CDCl 3)δ9.03(s,1H),8.74(d,J=4.8Hz,1H),8.56(d,J=8.2Hz,1H),8.50(dt,J=8.0Hz,1H),8.14(d,J=8.2Hz,1H),7.92 - 7.85(m,3H),7.4(d,J=8.3Hz,2H),7.36(dd,J=7.5,4.8Hz,1H),7.32(d,J=7.8Hz,2H),6.94(t,J=7.7Hz,2H),6.88(t,J=7.4Hz,2H),6.21(d,J=8.2Hz,2H),2.01 - 1.91(m,4H),1.24 - 1.05(m,16H),0.80(t,J=6.8Hz,6H).

[0091] Example 3

[0092] The synthesis of ligand AB3Phen was carried out according to the following reaction equation:

[0093]

[0094] The specific steps were as follows: Under an argon atmosphere, 9,9 - dihexyl - 10-(4-(4,4,5,5 - tetramethyl - 1,3,2 - dioxaborolan - 2 - yl)phenyl)-9,10 - dihydroacridine (2.04 g, 3.7 mmol), 3 - bromo - 1,10 - phenanthroline (0.87 g, 3.4 mmol), Pd(PPh 3 ) 4 (0.08 g, 0.07 mmol), Na 2 CO 3 (1.8 g, 17 mmol) and a mixed solvent of THF / EtOH / H 2 O (30 mL / 18 mL / 18 mL) were added to a 250 mL reaction flask, and the reaction was refluxed at 90 °C for 12 h. It was naturally cooled to room temperature, the reaction solution was extracted with DCM, the organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 80:1) gave 1.67 g of a white solid with a yield of 78%. 1 1H NMR (500 MHz, CDCl 3)δ9.55(s,1H),9.24(d,J=4.5Hz,1H),8.52(s,1H),8.30(dd,J=8.2,1.7Hz,1H),8.03(d,J=8.4Hz,2H),7.92(d,J=8.8Hz,1H),7.88(d,J=8.8Hz,1H),7.68(dd,J=8.1,4.3Hz,1H),7.46(d,J=8.3Hz,2H),7.33(d,J=7.7Hz,2H),6.95(t,J=7.6Hz,2H),6.89(t,J=7.3Hz,2H),6.24(d,J=8.1Hz,2H),2.01-1.94(m,4H),1.24-1.05(m,16H),0.81(t,J=6.8Hz,6H).

[0095] Example 4

[0096] The synthesis of ligand AB5Phen was carried out according to the following reaction equation:

[0097]

[0098] The specific steps were as follows: Under an argon atmosphere, 9,9-dihexyl-10-(4-(4-pinacolborate)phenyl)-9,10-dihydroacridine (4.06 g, 7.4 mmol), 5-bromo-1,10-phenanthroline (1.81 g, 7 mmol), Pd(PPh 3 ) 4 (0.16 g, 0.14 mmol), Na 2 CO 3 (3.7 g, 35 mmol), and a mixed solvent of THF / EtOH / H 2 O (40 mL / 24 mL / 24 mL) were added to a 250 mL reaction flask, and the mixture was refluxed and stirred at 90 °C for 12 h. It was naturally cooled to room temperature, the reaction solution was extracted with DCM, the organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) =80:1) gave 3.20 g of a white solid with a yield of 72%. 1 H NMR(500MHz,CDCl 3)δ9.31 - 9.22(m, 2H), 8.45(d, J = 8.3Hz, 1H), 8.33(d, J = 8.1Hz, 1H), 7.91(s, 1H), 7.80(d, J = 8.3Hz, 2H), 7.74 - 7.66(m, 2H), 7.46(d, J = 8.3Hz, 2H), 7.35(dd, J = 7.8Hz, 2H), 7.00(t, J = 8.3Hz, 2H), 6.91(t, J = 7.2Hz, 2H), 6.29(d, J = 8.2Hz, 2H), 2.03 - 1.92(m, 4H), 1.25 - 1.07(m, 16H), 0.81(t, J = 6.9Hz, 6H).

[0099] Example 5

[0100] The synthesis of ligand ABDPyPz was carried out according to the following reaction equation:

[0101]

[0102] The specific steps are as follows: Under an argon atmosphere, 9,9 - dihexyl - 10-(4-(4,4,5,5 - tetramethyl - 1,3,2 - dioxaborolan - 2 - yl)phenyl)-9,10 - dihydroacridine (3.09 g, 5.6 mmol), 11 - bromodipyrido[3,2 - a:2',3' - c]phenazine (2.00 g, 5.54 mmol), Pd(PPh 3 ) 4 (0.1280 g, 0.11 mmol), Na 2 CO 3 (2.93 g, 27.7 mmol) and the mixed solvent of THF / EtOH / H 2 O (40 mL / 24 mL / 24 mL) were added to a 250 mL reaction flask, and the reaction was stirred under reflux at 90 °C for 12 h. It was naturally cooled to room temperature, the reaction solution was extracted with DCM, the organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 80:1) gave 2.76 g of a yellow solid with a yield of 70%. 1 1H NMR (500 MHz, CDCl 3)δ9.76(d,J=8.1Hz,2H),9.40(d,J=4.3Hz,2H),8.69(s,1H),8.50(d,J=8.8Hz,1H),8.34(d,J=8.8Hz,1H),8.13(d,J=8.4Hz,2H),7.92(dd,J=8.1,4.5Hz,2H),7.49(d,J=8.3Hz,2H),7.34(d,J=7.8Hz,2H),6.97(t,J=8.3Hz,2H),6.90(t,J=7.2Hz,2H),6.27(d,J=8.2Hz,2H),2.05-1.91(m,4H),1.27-1.07(m,16H),0.83(t,J=6.8Hz,6H).

[0103] Example 6

[0104] The synthesis of ligand ABPy was carried out according to the following reaction equation:

[0105]

[0106] Specific steps are as follows: Under an argon atmosphere, 9,9-dihexyl-9,10-dihydroacridine (2.09 g, 6 mmol), 11-bromodipyrido[3,2-a:2',3'-c]phenazine (2.17 g, 6 mmol), Pd 2 (dba) 3 (0.55 g, 0.6 mmol), Sphos (0.46 g, 0.49 mmol), t-BuONa (1.15 g, 12 mmol) and toluene (50 mL) were added to a 100 mL reaction flask, and the mixture was refluxed with vigorous stirring for 12 h. After natural cooling to room temperature, the reaction solution was extracted with DCM, the organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Silica gel column chromatography (V (DCM) :V (MeOH) = 100:1) was used for purification to obtain 1.90 g of a red solid with a yield of 50%. 1 HNMR(500MHz,CDCl 3)δ 9.73 (d, J = 8.1 Hz, 1H), 9.64 (d, J = 8.1 Hz, 1H), 9.34 (dd, J = 9.3, 4.5 Hz, 2H), 8.61 (d, J = 8.9 Hz, 1H), 8.41 (s, 1H), 7.87 (dd, J = 8.1, 4.5 Hz, 1H), 7.83 (dd, J = 8.1, 4.5 Hz, 1H), 7.79 (d, J = 8.9 Hz, 1H), 7.38 (d, J = 7.8 Hz, 2H), 6.92 (m, 4H), 6.26 (d, J = 8.2 Hz, 2H), 2.09 - 1.92 (m, 4H), 1.21 (q, J = 12.8, 9.3 Hz, 16H), 0.85 (t, J = 6.7 Hz, 6H).

[0107] Example 7

[0108] The synthesis of ligand ABPy was carried out according to the following reaction equation:

[0109]

[0110] The specific steps were as follows: Under an argon atmosphere, 9,9 - dihexyl - 9,10 - dihydroacridine (1.75 g, 5 mmol), 5 - bromo - 2,2'-bipyridine (1.17 g, 5 mmol), t - BuONa (0.48 g, 5 mmol), Pd 2 (dba) 3 (0.23 g, 0.25 mmol), dppf (0.28 g, 0.5 mmol) and toluene (40 mL) were added to a 100 mL reaction flask, and the mixture was refluxed for 12 h with vigorous stirring. After natural cooling to room temperature, the reaction solution was extracted with DCM. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 80:1) gave 1.48 g of a white solid with a yield of 59%. 1 1H NMR (500 MHz, CDCl 3 )δ 8.74 (d, J = 4.8 Hz, 1H), 8.69 (d, J = 8.3 Hz, 1H), 8.58 (s, 1H), 8.50 (d, J = 8.0 Hz, 1H), 7.88 (t, J = 7.8 Hz, 1H), 7.79 (d, J = 8.3 Hz, 1H), 7.37 (dd, J = 7.5, 4.8 Hz, 1H), 7.33 (d, J = 7.3 Hz, 2H), 6.97 - 6.86 (m, 4H), 6.17 (d, J = 7.7 Hz, 2H), 2.08 - 1.83 (m, 4H), 1.29 - 0.95 (m, 16H), 0.80 (t, J = 6.8 Hz, 6H).

[0111] Example 8

[0112] The ligand BABBPy was synthesized according to the following reaction equation:

[0113]

[0114] The specific steps were as follows: Under an argon atmosphere, 9,9-dihexyl-10-(4-(4-pinacolboronate)phenyl)-9,10-dihydroacridine (1.88 g, 3.4 mmol), 5,5'-dibromo-2,2'-bipyridine (0.52 g, 1.6 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Na 2 CO 3 (1.06 g, 10 mmol), and a mixed solvent of THF / EtOH / H 2 O (15 mL / 6 mL / 6 mL) were added to a 100 mL reaction flask, and the mixture was refluxed and stirred at 90 °C for 12 h. It was naturally cooled to room temperature, and the reaction solution was extracted with DCM. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (PE) :V (DCM) = 5:1) gave 0.73 g of a white solid with a yield of 43%. 1 H NMR (500 MHz, CDCl 3 ) δ 9.08 (s, 2H), 8.64 (d, J = 8.2 Hz, 2H), 8.19 (d, J = 8.2 Hz, 2H), 7.94 (d, J = 8.1 Hz, 2H), 7.42 (d, J = 8.3 Hz, 2H), 7.33 (dd, J = 7.8 Hz, 4H), 6.95 (t, J = 8.4 Hz, 4H), 6.89 (t, J = 7.4 Hz, 4H), 6.22 (d, J = 8.2 Hz, 4H), 2.03 - 1.89 (m, 8H), 1.26 - 1.03 (m, 32H), 0.81 (t, J = 6.8 Hz, 12H).

[0115] Example 9

[0116] The ligand BABPhen was synthesized according to the following reaction equation:

[0117]

[0118] The specific steps are as follows: Under an argon atmosphere, 9,9-dihexyl-10-(4-(4-pinacolborate)phenyl)-9,10-dihydroacridine (1.1 g, 2.0 mmol), 3,8-dibromo-o-phenanthroline (0.34 g, 1.1 mmol), Pd(PPh 3 ) 4 (0.04 g, 0.04 mmol), Na 2 CO 3 (1.06 g, 10 mmol), and a mixed solvent of THF / EtOH / H 2 O (10 mL / 6 mL / 6 mL) were added to a 100 mL reaction flask, and the mixture was refluxed and stirred at 90 °C for 12 h. It was naturally cooled to room temperature, the reaction solution was extracted with DCM, the organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (EA) = 5:1) gave 1.06 g of a white solid with a yield of 78%. 1 H NMR (500 MHz, CDCl 3 ) δ 9.63 (s, 2H), 8.60 (s, 2H), 8.06 (d, J = 8.1 Hz, 4H), 8.01 (s, 2H), 7.49 (d, J = 8.1 Hz, 4H), 7.34 (d, J = 7.7 Hz, 4H), 6.97 (t, J = 8.4 Hz, 4H), 6.90 (t, J = 7.4 Hz, 4H), 6.25 (d, J = 8.2 Hz, 4H), 2.07 - 1.94 (m, 8H), 1.29 - 1.05 (m, 32H), 0.81 (t, J = 6.8 Hz, 12H).

[0119] Example 10

[0120] The synthesis of ligand ABTrzPy was carried out according to the following reaction equation:

[0121]

[0122] The specific steps are as follows: Under an argon atmosphere, 9,9-dihexyl-9,10-dihydroacridine (2.09 g, 6 mmol), 2,4-bis(2'-pyridyl)-6-(4-bromophenyl)-1,3,5-triazine (1.95 g, 5 mmol), P(t-Bu) 3 ·HBF 4 (0.2901 g, 1.0 mmol), Pd(OAc) 2(0.1123 g, 0.5 mmol), t-BuOK (0.90 g, 8.0 mmol) and xylene (40 mL) were added to a 250 mL reaction flask, and the mixture was refluxed for 12 h with vigorous stirring. It was naturally cooled to room temperature, and the reaction solution was extracted with DCM. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (Et3N) = 100:1) gave 2.13 g of a yellow-green solid with a yield of 65%. 1 1H NMR (500 MHz, CDCl 3 ) δ 9.08 (d, J = 8.1 Hz, 2H), 9.05 (d, J = 4.8 Hz, 2H), 8.96 (d, J = 7.8 Hz, 2H), 8.08 (t, J = 7.8 Hz, 2H), 7.64 (t, J = 5.8 Hz, 2H), 7.51 (d, J = 8.2 Hz, 2H), 7.33 (dd, J = 7.5 Hz, 2H), 6.97 - 6.84 (m, 4H), 6.21 (d, J = 8.0 Hz, 2H), 2.01 - 1.94 (m, 4H), 1.26 - 1.05 (m, 19H), 0.82 (t, J = 6.7 Hz, 6H).

[0123] Example 11

[0124] The synthesis of ligand CzBTPy was carried out according to the following reaction equation:

[0125]

[0126] Specific steps: Under an argon atmosphere, 3,6-ditert-butylcarbazole (1.40 g, 5 mmol), 4-(4-bromophenyl)-(2,2'-6,2'')-terpyridine (1.94 g, 5 mmol), P(t-Bu) 3 (1.2 mL, 10% in toluene), Pd(OAc) 2 (0.1122 g, 0.5 mmol), t-BuOK (0.84 g, 7.5 mmol) and xylene (40 mL) were added to a 100 mL reaction flask, and the mixture was refluxed for 48 h with vigorous stirring. It was naturally cooled to room temperature, and the reaction solution was extracted with DCM. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 160:1) gave 2.12 g of a white solid with a yield of 72%. 1 1H NMR (400 MHz, CDCl 3)δ8.88(s,2H),8.78(d,J=4.8Hz,2H),8.74(d,J=8.0Hz,2H),8.19 - 8.12(m,4H),7.94(t,J=7.7Hz,2H),7.73(d,J=8.4Hz,2H),7.51(d,J=8.7Hz,2H),7.47 - 7.37(m,4H),1.48(s,18H).

[0127] Example 12

[0128] The ligand TPABTPy was synthesized according to the following reaction equation:

[0129]

[0130] The specific steps were as follows: Under an argon atmosphere, 4,4'-di-tert-butyl diphenylamine (1.41 g, 5 mmol), 4-(4-bromophenyl)-(2,2'-6,2'')-terpyridine (1.94 g, 10 mmol), P(t-Bu) 3 (1.2 mL, 10% in toluene), Pd(OAc) 2 (0.1122 g, 0.5 mmol), t-BuOK (0.84 g, 7.5 mmol) and xylene (40 mL) were added to a 100 mL reaction flask. The mixture was refluxed with vigorous stirring for 48 h. After natural cooling to room temperature, the reaction solution was extracted with DCM. The organic phase was washed three times with water, dried over anhydrous sodium sulfate, filtered and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 160:1) gave 2.31 g of a white solid with a yield of 78%. 1 HNMR(400 MHz, CDCl 3 )δ8.74 - 8.69(m,4H),8.67(d,J = 7.9Hz,1H),7.87(t,J = 7.7Hz,1H),7.78(d,J = 8.2Hz,2H),7.34(dd,J = 7.5,4.9Hz,2H),7.30(d,J = 6.9Hz,4H),7.15(d,J = 6.9Hz,2H),7.08(d,J = 6.9Hz,4H),1.33(s,18H).

[0131] Example 13

[0132] The ligand TPACzBTPy was synthesized according to the following reaction equation:

[0133]

[0134] The specific steps are as follows: Under an argon atmosphere, 1,8-dibromo-9-(4-(4'-(2,2'-6,2”-terpyridine)yl)phenyl)-3,6-di-tert-butylcarbazole (0.75 g, 1.0 mmol), (4-(bis(4-(tert-butyl)phenyl)amino)phenyl)boronic acid (1.20 g, 3 mmol), tris(dibenzylideneacetone)dipalladium (0.0458 g, 0.005 mmol), 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (0.0082 g, 0.020 mmol), potassium phosphate (0.84 g, 4 mmol), THF (10 mL) and H 2 O (2 mL) were added to a 100 mL reaction flask, and the mixture was refluxed for 24 h. It was naturally cooled to room temperature, and the reaction solution was extracted with DCM. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 160:1) gave 1.04 g of a white solid with a yield of 80%. 1 H NMR (500 MHz, CDCl 3 ) δ 8.94 (s, 2H), 8.71 (d, J = 6.9 Hz, 4H), 8.19 (s, 2H), 7.94 - 7.84 (m, 2H), 7.56 (d, J = 8.0 Hz, 2H), 7.43 - 7.34 (m, 2H), 7.30 (s, 2H), 6.95 - 6.83 (m, 10H), 6.74 (d, J = 8.4 Hz, 4H), 6.68 (d, J = 8.7 Hz, 8H), 6.54 (d, J = 8.4 Hz, 4H), 1.50 (s, 18H), 1.08 (s, 36H).

[0135] Example 14

[0136] The ligand TPACzBBPy was synthesized according to the following reaction equation:

[0137]

[0138] The specific steps are as follows: Under an argon atmosphere, 1,8-dibromo-9-(4-(5-(2,2'-bipyridine)yl)phenyl)-3,6-di-tert-butylcarbazole (0.34 g, 0.5 mmol), 4-(bis(4-(tert-butyl)phenyl)amino)phenylboronic acid (0.60 g, 1.5 mmol), tris(dibenzylideneacetone)dipalladium (0.0229 g, 0.0025 mmol), 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (0.0041 g, 0.010 mmol), potassium phosphate (0.42 g, 2 mmol), THF (5 mL) and H 2O (1 mL) was added to a 50 mL reaction flask, and the mixture was refluxed for 24 h. It was naturally cooled to room temperature. The reaction solution was extracted with DCM. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 160:1) gave 0.51 g of a white solid with a yield of 84%. 1 1H NMR (400 MHz, CDCl 3 ) δ 8.97 (s, 1H), 8.36 (d, J = 4.0 Hz, 1H), 8.60 - 8.46 (m, 2H), 8.18 (s, 2H), 8.03 (d, J = 8.2 Hz, 1H), 7.83 (t, J = 7.8 Hz, 1H), 7.36 - 7.30 (m, 1H), 7.28 (s, 2H), 7.17 (d, J = 8.2 Hz, 2H), 7.04 (d, J = 8.6 Hz, 4H), 6.84 - 6.75 (m, 12H), 6.63 (d, J = 8.4 Hz, 4H), 1.50 (s, 18H), 1.20 (s, 36H).

[0139] Example 15

[0140] The synthesis of ligand TPACzBTrzPy was carried out according to the following reaction equation:

[0141]

[0142] Specific steps were as follows: Under an argon atmosphere, 1,8 - dibromo - 9 - (4 - (2 - (4,6 - bis(2 - pyridyl)-1,3,5 - triazine)yl)phenyl)-3,6 - di - tert - butylcarbazole (0.75 g, 1 mmol), (4 - (bis(4 - (tert - butyl)phenyl)amino)phenyl)boronic acid (1.20 g, 3 mmol), tris(dibenzylideneacetone)dipalladium (0.0458 g, 0.005 mmol), 2 - bicyclohexylphosphine - 2',6' - dimethoxybiphenyl (0.0082 g, 0.020 mmol), potassium phosphate (0.84 g, 4 mmol), THF (10 mL) and H 2 O (2 mL) were added to a 100 mL reaction flask, and the mixture was refluxed for 24 h. It was naturally cooled to room temperature. The reaction solution was extracted with DCM. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography (V (DCM) :V (MeOH) = 160:1) gave 0.87 g of a green solid with a yield of 67%. 1 1H NMR (500 MHz, CDCl 3)δ 8.98 (d, J = 4.6 Hz, 2H), 8.89 (d, J = 7.9 Hz, 2H), 8.37 (d, J = 8.6 Hz, 2H), 8.19 (s Hz, 2H), 7.85 (t, J = 7.7 Hz, 2H), 7.51 (dd, J = 7.5, 4.7 Hz, 2H), 7.32 (s, 2H), 6.95 (d, J = 8.6 Hz, 8H), 6.88 (d, J = 8.5 Hz, 2H),

[0143] 6.77 - 6.66 (m, 12H), 6.52 (d, J = 8.6 Hz, 4H), 1.50 (s, 18H), 1.09 (s, 36H). Complex synthesis

[0144] Example 16

[0145] The complex Zn(ABTPy)Cl was synthesized according to the following reaction equation 2 :

[0146]

[0147] The specific steps are as follows: Under an argon atmosphere, ZnCl 2 (0.20 g, 1.5 mmol), ABTPy (0.66 g, 1.0 mmol), THF (10 mL) and MeOH (5 mL) were added to the reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH and dried to obtain 0.78 g of a yellow solid with a yield of 98%. 1 1H NMR (500 MHz, CDCl 3 )δ 9.16 (d, J = 5.9 Hz, 2H), 8.44 (s, 2H), 8.30 (d, J = 8.0 Hz, 2H), 8.04 (d, J = 8.3 Hz, 2H), 7.98 (t, J = 7.8 Hz, 2H), 7.64 (dd, J = 7.5, 5.0 Hz, 2H), 7.44 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 7.5 Hz, 2H), 7.03 - 6.88 (m, 4H), 6.15 (d, J = 8.0 Hz, 2H), 2.05 - 1.93 (m, 4H), 1.28 - 1.05 (m, 16H), 0.83 (t, J = 6.7 Hz, 6H). 13 13C NMR (500 MHz, CDCl 3)δ154.31,150.02,149.82,146.80,144.46,141.60,139.77,135.33,132.80,130.15,127.17,126.63,126.32,126.22,121.19,120.74,119.34,113.76,46.08,44.13,31.71,29.80,24.97,22.70,14.11.

[0148] Example 17

[0149] The complex Zn(ABBPy)Cl was synthesized according to the following reaction equation 2 :

[0150]

[0151] The specific steps were as follows: Under an argon atmosphere, ABBPy (0.52 g, 0.9 mmol), ZnCl 2 (0.14 g, 1.0 mmol), THF (10 mL) and MeOH (5 mL) were added to the reaction flask, and the mixture was refluxed for 8 h. After natural cooling to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH, and 0.56 g of yellow solid was obtained after drying, with a yield of 87%. 1 1H NMR (500 MHz, CDCl 3 )δ9.18 (s, 1H), 8.92 (d, J = 4.8 Hz, 1H), 8.46 (d, J = 8.4 Hz, 1H), 8.36 (d, J = 8.3 Hz, 1H), 8.32 (d, J = 8.1 Hz, 1H), 8.24 (t, J = 7.8 Hz, 1H), 7.93 (d, J = 8.2 Hz, 2H), 7.79 (dd, J = 7.4, 5.0 Hz, 1H), 7.48 (d, J = 8.2 Hz, 2H), 7.33 (d, J = 7.6 Hz, 2H), 6.95 (t, J = 8.2 Hz, 2H), 6.90 (td, J = 7.5 Hz, 2H), 6.15 (dd, J = 8.1 Hz, 2H), 2.01 - 1.93 (m, 4H), 1.24 - 1.03 (m, 16H), 0.81 (t, J = 6.8 Hz, 6H).

[0152] Example 18

[0153] The complex Zn(AB3Phen)Cl was synthesized according to the following reaction equation 2 :

[0154]

[0155] The specific steps are as follows: Under an argon atmosphere, AB3Phen (0.60 g, 1.0 mmol), ZnCl 2 (0.14 g, 1.0 mmol), THF (10 mL), and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH and dried to obtain 0.52 g of a yellow solid with a yield of 70%. 1 1H NMR (500 MHz, CDCl 3 ) δ 9.53 (s, 1H), 9.23 (d, J = 4.8 Hz, 1H), 8.87 (s, 1H), 8.69 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 8.9 Hz, 1H), 8.13 (d, J = 9.0 Hz, 1H), 8.09 - 8.00 (m, 3H), 7.34 (d, J = 7.6 Hz, 2H), 6.96 (t, J = 7.6 Hz, 2H), 6.91 (t, J = 7.3 Hz, 2H), 6.18 (d, J = 8.1 Hz, 2H), 2.05 - 1.92 (m, 4H), 1.26 - 1.03 (m, 16H), 0.82 (t, J = 6.6 Hz, 6H). 13 13C NMR (400 MHz, CDCl 3 ) δ 149.90, 148.99, 143.66, 141.80, 140.85, 140.04, 139.56, 138.84, 136.92, 134.78, 133.11, 130.35, 129.25, 129.17, 127.78, 127.43, 126.53, 126.28, 126.23, 125.83, 120.57, 113.73, 46.11, 44.12, 31.68, 29.82, 24.95, 22.69, 14.08.

[0156] Example 19

[0157] The synthesis of the complex Zn(AB5Phen)Cl was carried out according to the following reaction equation: 2 as follows:

[0158]

[0159] The specific steps are as follows: Under an argon atmosphere, AB5Phen (0.60 g, 1.0 mmol), ZnCl 2(0.14 g, 1.0 mmol), THF (10 mL) and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH and dried to obtain 0.55 g of a yellow solid with a yield of 74%. 1 HNMR (500 MHz, CDCl 3 ) δ 9.31 - 9.22 (m, 2H), 8.80 (d, J = 8.5 Hz, 1H), 8.70 (d, J = 8.2 Hz, 1H), 8.16 (s, 1H), 8.13 - 8.04 (m, 2H), 7.79 (d, J = 8.1 Hz, 2H), 7.54 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 7.8 Hz, 2H), 6.99 (d, J = 8.1 Hz, 2H), 6.93 (t, J = 7.4 Hz, 2H), 6.25 (d, J = 8.1 Hz, 2H), 2.05 - 1.93 (m, 4H), 1.26 - 1.05 (m, 16H), 0.81 (t, J = 6.6 Hz, 6H). 13 C NMR (400 MHz, CDCl 3 ) δ 149.72, 143.00, 141.91, 141.18, 140.31, 139.96, 139.58, 138.77, 136.22, 132.53, 132.40, 128.82, 128.68, 127.11, 126.60, 126.35, 126.31, 126.22, 125.87, 120.62, 113.74, 46.07, 44.14, 31.69, 29.80, 24.96, 22.67, 14.07.

[0160] Example 20

[0161] The synthesis of the complex Zn(ABDPyPz)Cl was carried out according to the following reaction equation: 2 The synthesis is as follows:

[0162]

[0163] Specifically, under an argon atmosphere, ABDPyPz (0.58 g, 0.8 mmol), ZnCl 2 (0.2 g, 1.5 mmol), THF (10 mL) and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH and dried to obtain 0.64 g of a yellow solid with a yield of 93%. 1HNMR(500MHz,CDCl 3 ) δ 9.99 (d, J = 8.2 Hz, 2H), 9.29 (m, 2H), 8.75 (s, 1H), 8.58 (d, J = 8.8 Hz, 1H), 8.45 (d, J = 8.9 Hz, 1H), 8.23 (dd, J = 8.2, 4.9 Hz, 2H), 8.14 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H), 6.97 (t, J = 8.4 Hz, 2H), 6.91 (t, J = 7.5 Hz, 2H), 6.26 (d, J = 8.2 Hz, 2H), 2.05 - 1.92 (m, 4H), 1.24 - 1.05 (m, 16H), 0.83 (t, J = 6.7 Hz, 6H). 13 C NMR(500MHz,CDCl 3 ) δ 151.10, 144.21, 143.38, 142.80, 142.62, 141.99, 139.53, 138.90, 138.57, 137.87, 132.54, 132.29, 130.38, 130.27, 129.29, 129.23, 129.04, 128.22, 127.21, 127.00, 126.54, 126.26, 126.21, 125.30, 120.47, 113.78, 46.12, 44.14, 31.71, 29.84, 24.97, 22.70, 14.09.

[0164] Example 21

[0165] The complex Zn(ADPyPz)Cl was synthesized according to the following reaction equation: 2 Synthesis:

[0166]

[0167] Specific steps: Under an argon atmosphere, ADPyPz (0.50 g, 0.8 mmol), ZnCl 2 (0.14 g, 1.0 mmol), THF (10 mL) and MeOH (5 mL) were added to the reaction flask, and the mixture was refluxed for 8 h. After natural cooling to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH and dried to obtain 0.51 g of a yellow solid with a yield of 83%. 1 HNMR(500MHz,CDCl 3)δ9.96(d, J = 8.2Hz, 1H), 9.87(d, J = 8.2Hz, 1H), 9.35 - 9.28(m, 2H), 8.66(d, J = 8.9Hz, 1H), 8.47(s, 1H), 8.26 - 8.15(m, 2H), 7.92(d, J = 9.0Hz, 1H), 7.40(d, J = 7.5Hz, 2H), 7.01 - 6.89(m, 2H), 6.30(d, J = 8.0Hz, 2H), 2.07 - 2.00(m, 4H), 1.29 - 1.07(m, 16H), 0.84(t, J = 6.9Hz, 6H). 13 C NMR(400MHz, CDCl 3 )δ151.29, 151.25, 145.48, 144.11, 142.85, 142.75, 142.42, 141.38, 139.31, 139.14, 137.70, 137.62, 136.07, 132.90, 132.15, 128.92, 128.84, 127.30, 126.89, 126.78, 126.37, 121.29, 114.20, 77.25, 45.93, 44.23, 31.68, 29.79, 24.98, 22.68, 14.10.

[0168] Example 22

[0169] The complex Zn(ABPy)Cl was synthesized according to the following reaction equation: 2 Synthesis:

[0170]

[0171] Specific steps: Under an argon atmosphere, ABPy (0.45 g, 0.9 mmol), ZnCl 2 (0.14 g, 1.0 mmol), THF (10 mL) and MeOH (5 mL) were added to the reaction flask, and the mixture was refluxed for 8 h. After natural cooling to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH and dried to obtain 0.42 g of an orange-red solid with a yield of 73%. 1 HNMR(500MHz, CDCl 3)δ8.91(d, J = 5.0Hz, 1H), 8.80(s, 1H), 8.52(d, J = 8.4Hz, 1H), 8.37(d, J = 8.1Hz, 1H), 8.22(t, J = 7.8Hz, 1H), 8.12(7.6Hz), 7.75(t, J = 6.2Hz, 1H), 7.36(d, 7.8Hz, 2H), 7.02 - 6.93(m, 4H), 6.14(d, 7.8Hz, 2H), 2.01 - 1.94(m, 4H), 1.24 - 1.00(m, 16H), 0.80(t, J = 6.7Hz, 6H).

[0172] Example 23

[0173] The complex Zn(BABBPy)Cl was synthesized according to the following reaction equation: 2 Synthesis:

[0174]

[0175] Specific steps: Under an argon atmosphere, BABBPy (0.5017 g, 0.5 mmol), ZnCl 2 (0.11 g, 0.8 mmol), THF (10 mL) and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. After natural cooling to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH, and after drying, 0.46 g of a yellow solid was obtained with a yield of 81%. 1 HNMR (400 MHz, CDCl 3 )δ9.22(d, J = 2.1Hz, 2H), 8.49(d, J = 8.3Hz, 2H), 8.42(d, J = 8.4Hz, 2H), 7.95(d, J = 8.1Hz, 4H), 7.51(d, J = 8.1Hz, 4H), 7.34(d, J = 7.7Hz, 4H), 7.01 - 6.86(m, 8H), 6.16(d, J = 8.1Hz, 4H), 2.02 - 1.93(m, 8H), 1.26 - 1.02(m, 32H), 0.81(t, J = 6.7Hz, 12H). 13 C NMR (500 MHz, CDCl 3 )δ147.07, 146.34, 142.77, 140.76, 138.94, 138.11, 133.22, 132.00, 128.90, 125.49, 125.25, 125.19, 120.83, 119.55, 112.71, 45.08, 43.09, 30.65, 28.78, 23.92, 21.67, 13.06.

[0176] Example 24

[0177] The complex Zn(BABphen)Cl2 was synthesized according to the following reaction equation:

[0178]

[0179] Specific steps are as follows: Under an argon atmosphere, BABphen (0.56 g, 0.5 mmol), ZnCl 2 (0.11 g, 0.8 mmol), THF (10 mL) and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH, and 0.49 g of orange-yellow solid was obtained after drying, with a yield of 84%. 1 1H NMR (400 MHz, CDCl 3 ) δ 9.57 (s, 2H), 8.89 (s, 2H), 8.21 (s, 2H), 8.06 (d, J = 8.3 Hz, 4H), 7.55 (m, J = 8.4 Hz, 4H), 7.35 (d, J = 7.7 Hz, 4H), 6.95 (m, 8H), 6.19 (d, J = 8.1 Hz, 4H), 2.04 - 1.94 (m, 8H), 1.26 - 1.04 (m, 32H), 0.82 (t, J = 6.7 Hz, 12H). 13 13C NMR (400 MHz, CDCl 3 ) δ 148.13, 142.66, 140.78, 138.62, 137.76, 135.93, 133.79, 132.11, 129.34, 128.16, 126.89, 125.52, 125.27, 125.21, 119.56, 112.72, 45.10, 43.10, 30.66, 28.80, 23.94, 21.67, 13.06.

[0180] Example 25

[0181] The complex Zn(ABTrzPy)Cl 2 was synthesized according to the following reaction equation:

[0182]

[0183] Specific steps are as follows: Under an argon atmosphere, ABTrzPy (0.46 g, 0.7 mmol), ZnCl 2(0.14 g, 1.0 mmol), THF (10 mL), and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH, and after drying, 0.42 g of orange-yellow solid was obtained with a yield of 75%. 1 HNMR (400 MHz, CDCl 3 ) δ 9.18 (d, J = 4.8 Hz, 2H), 9.05 (d, J = 8.4 Hz, 2H), 8.92 (d, J = 7.8 Hz, 2H), 8.22 (t, J = 7.7 Hz, 2H), 7.91 (dd, J = 7.6, 4.9 Hz, 2H), 7.59 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 7.3 Hz, 2H), 7.01 - 6.90 (m, 4H), 6.24 (d, J = 7.7 Hz, 2H), 2.04 - 1.94 (m, 4H), 1.27 - 1.05 (m, 16H), 0.82 (t, J = 6.7 Hz, 6H). 13 C NMR (400 MHz, CDCl 3 ) δ 174.38, 165.16, 149.39, 147.81, 144.73, 140.45, 138.85, 132.01, 131.91, 131.42, 129.36, 125.62, 125.56, 125.30, 123.18, 119.91, 112.92, 44.89, 43.15, 30.66, 28.78, 23.93, 21.66, 13.06.

[0184] Example 26

[0185] The synthesis of the complex Zn(CzBTPy)Cl2 was carried out according to the following reaction equation:

[0186]

[0187] Specific steps were as follows: Under an argon atmosphere, ZnCl 2 (0.14 g, 1.0 mmol), CzBTPy (0.42 g, 0.72 mmol), THF (10 mL), and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH, and after drying, 0.45 g of green solid was obtained with a yield of 89%. 1 HNMR (400 MHz, CDCl 3)δ9.21(d, J = 4.9Hz, 2H), 8.49(s, 2H), 8.32(d, J = 7.9Hz, 2H), 8.18(s 2H), 8.11(t, J = 7.7Hz, 2H), 8.03(d, J = 8.2Hz, 2H), 7.87(d, J = 8.2Hz, 2H), 7.76 - 7.70(m, 2H), 7.52(d, J = 8.7Hz, 2H), 7.48(d, J = 8.7Hz, 2H), 1.49(s, 18H).

[0188] Example 27

[0189] The synthesis of the complex Zn(TPABTPy)Cl was carried out according to the following reaction equation 2 :

[0190]

[0191] Specific steps are as follows: Under an argon atmosphere, ZnCl 2 (0.14g, 1.0mmol), TPABTPy(0.40g, 0.68mmol), THF(10mL) and MeOH(5mL) were added to the reaction flask, and the mixture was refluxed for 8h. After naturally cooling to room temperature, 30mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3h. After filtration, it was washed with a large amount of MeOH, and 0.39g of yellow solid was obtained after drying, with a yield of 79%. 1 HNMR(400MHz, CDCl 3 )δ9.14(d, J = 4.8Hz, 2H), 8.28(s, 2H), 8.20(d, J = 7.9Hz, 2H), 8.02(t, J = 7.6Hz, 2H), 7.68 - 7.60(m, 4H), 7.37(d, J = 8.3Hz, 5H), 7.13(d, J = 8.3Hz, 7H), 1.36(s, 18H).

[0192] Example 28

[0193] The synthesis of the complex Zn(TPACzBTPy)Cl was carried out according to the following reaction equation 2 :

[0194]

[0195] Specific steps are as follows: Under an argon atmosphere, ZnCl 2(0.07 g, 0.5 mmol), TPACzBTPy (0.40 g, 0.31 mmol), THF (10 mL) and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH, and 0.41 g of yellow solid was obtained after drying, with a yield of 93%. 1 H NMR (500 MHz, CDCl 3 ) δ 9.17 - 9.12 (m, 2H), 8.29 (s, 2H), 8.21 (d, J = 2.1 Hz, 2H), 7.81 (d, J = 6.0 Hz, 2H), 7.63 - 7.56 (m, 4H), 7.32 (d, J = 2.0 Hz, 2H), 7.28 (d, J = 8.1 Hz, 2H), 7.16 (d, J = 8.2 Hz, 8H), 7.00 (d, J = 8.1 Hz, 2H), 6.92 (d, J = 8.2 Hz, 8H), 6.82 (d, J = 8.1 Hz, 4H), 6.76 (d, J = 8.1 Hz, 4H), 1.51 (s, 18H), 1.20 (s, 36H).

[0196] Example 29

[0197] The synthesis of the complex Zn(TPACzBBPy)Cl was carried out according to the following reaction equation: 2 :

[0198]

[0199] Specific steps: Under an argon atmosphere, ZnCl 2 (0.06 g, 0.4 mmol), TPACzBBPy (0.33 g, 0.27 mmol), THF (10 mL) and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH, and 0.30 g of orange - red solid was obtained after drying, with a yield of 82%.

[0200] Example 30

[0201] The synthesis of the complex Zn(TPACzBTrzPy)Cl was carried out according to the following reaction equation: 2 :

[0202]

[0203] Specific steps: Under an argon atmosphere, ZnCl 2(0.07 g, 0.5 mmol), TPACzBTrzPy (0.40 g, 0.31 mmol), THF (10 mL), and MeOH (5 mL) were added to a reaction flask, and the mixture was refluxed for 8 h. It was naturally cooled to room temperature, 30 mL of MeOH was added to the reaction solution, and the mixture was stirred at room temperature for 3 h. After filtration, it was washed with a large amount of MeOH and dried to obtain 0.43 g of a dark red solid with a yield of 96%. 1 H NMR (400 MHz, CDCl 3 ) δ 9.14 (d, J = 5.6 Hz, 2H), 8.86 (d, J = 7.7 Hz, 2H), 8.32 (d, J = 8.5 Hz, 2H), 8.20 (s, 2H), 8.02 (t, J = 7.7 Hz, 2H), 7.83 (dd, J = 7.2, 5.0 Hz, 2H), 7.34 (s, 2H), 7.08 (d, J = 8.1 Hz, 8H), 6.95 (d, J = 8.4 Hz, 2H), 6.85 - 6.66 (m, 12H), 6.58 (d, J = 8.1 Hz, 4H), 1.51 (s, 18H), 1.12 (s, 36H).

[0204] Example 31: Testing of the photophysical, electrochemical, and thermal properties of the compound

[0205] The photophysical properties of the compound obtained in the example of the present invention were tested. The results are shown in Figures 1 to 27 , Figure 1 is the UV / visible absorption of the dichloromethane solution of the compounds described in Examples 1 and 16 and the room-temperature fluorescence diagram of the thin film doped with 5 wt% in SimCP 2 ; Figure 2 is the low-temperature fluorescence and low-temperature phosphorescence spectra of the thin film doped with 5 wt% of the compounds described in Examples 1 and 16 in SimCP 2 ; Figure 3 is the transient fluorescence spectrum decay curve of the thin film doped with 5 wt% of the compound described in Example 1 in SimCP 2 ; Figure 4 is the transient fluorescence spectrum decay curve of the thin film doped with 5 wt% of the compound described in Example 16 in SimCP 2 ; Figure 5 is the UV / visible absorption of the dichloromethane solution of the compounds described in Examples 2 and 17 and the room-temperature fluorescence diagram of the thin film doped with 5 wt% in SimCP 2 ; Figure 6 is the low-temperature fluorescence and low-temperature phosphorescence spectra of the thin film doped with 5 wt% of the compounds described in Examples 2 and 17 in SimCP 2 ; Figure 7 is the transient fluorescence spectrum decay curve of the thin film doped with 5 wt% of the compound described in Example 2 in SimCP2 The transient fluorescence spectrum decay curve of the thin film in Figure 8 The compound described in Example 17 was doped at 5 wt% in SimCP 2 The transient fluorescence spectrum decay curve of the thin film in Figure 9 The UV / visible absorption of the dichloromethane solution of the compounds described in Examples 3 and 18 and the room temperature fluorescence of the thin film doped at 5 wt% in SimCP 2 The room temperature fluorescence diagram of the thin film in Figure 10 The compound described in Examples 3 and 18 was doped at 5 wt% in SimCP 2 The low temperature fluorescence and low temperature phosphorescence spectrum diagrams of the thin film in Figure 11 The compound described in Example 3 was doped at 5 wt% in SimCP 2 The transient fluorescence spectrum decay curve of the thin film in Figure 12 The compound described in Example 18 was doped at 5 wt% in SimCP 2 The transient fluorescence spectrum decay curve of the thin film in Figure 13 The UV / visible absorption of the dichloromethane solution of the compounds described in Examples 5 and 20 and the room temperature fluorescence of the thin film doped at 5 wt% in SimCP 2 The room temperature fluorescence diagram of the thin film in Figure 14 The compound described in Examples 5 and 20 was doped at 5 wt% in SimCP 2 The low temperature fluorescence and low temperature phosphorescence spectrum diagrams of the thin film in Figure 15 The compound described in Example 5 was doped at 5 wt% in SimCP 2 The transient fluorescence spectrum decay curve of the thin film in Figure 16 The compound described in Example 20 was doped at 5 wt% in SimCP 2 The transient fluorescence spectrum decay curve of the thin film in Figure 17 The UV / visible absorption of the dichloromethane solution of the compounds described in Examples 8 and 23 and the room temperature fluorescence of the thin film doped at 5 wt% in SimCP 2 The room temperature fluorescence diagram of the thin film in Figure 18 The compound described in Example 8 was doped at 5 wt% in SimCP 2 The transient fluorescence spectrum decay curve of the thin film in Figure 19 The compound described in Example 23 was doped at 5 wt% in SimCP 2 The transient fluorescence spectrum decay curve of the thin film in Figure 20 The UV / visible absorption of the dichloromethane solution of the compounds described in Examples 11 and 26 and the room temperature fluorescence of the thin film doped at 5 wt% in SimCP 2 The room temperature fluorescence diagram of the thin film in Figure 21UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 12 and 27 and room temperature fluorescence spectra of the films doped with 5 wt% in SimCP 2 ; Figure 22 UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 13 and 28 and room temperature fluorescence spectra of the films doped with 5 wt% in SimCP 2 ; Figure 23 Transient fluorescence spectral decay curves of the films doped with 5 wt% of the compound described in Example 13 in SimCP 2 ; Figure 24 Transient fluorescence spectral decay curves of the films doped with 5 wt% of the compound described in Example 28 in SimCP 2 ; Figure 25 UV / Vis absorption of the dichloromethane solution of the compounds described in Examples 14 and 29 and room temperature fluorescence spectra of the films doped with 5 wt% in SimCP 2 ; Figure 26 Transient fluorescence spectral decay curves of the films doped with 5 wt% of the compound described in Example 14 in SimCP 2 ; Figure 27 Transient fluorescence spectral decay curves of the films doped with 5 wt% of the compound described in Example 29 in SimCP 2 ;

[0206] The detection results are shown in Tables 1 - 3. Table 1 is the table of the test results of the photophysical properties of the luminescence performance of the compounds described in Examples 1, 2, 3, 5, 8, 11, 12, 13, 14, 16, 17, 18, 20, 23, 26, 27, 28 and 29 of the present invention; Table 2 is the table of the transient fluorescence spectral decay test and fluorescence quantum efficiency of the compounds described in Examples 1, 2, 3, 5, 8, 13, 14, 16, 17, 18, 20, 23, 28 and 29 of the present invention; Table 3 is the table of the temperature at 5% thermal weight loss of the compounds described in Examples 16, 17, 18, 20 and 23 of the present invention.

[0207] Table 1

[0208]

[0209]

[0210] Table 2

[0211]

[0212] Table 3

[0213]

[0214] As can be seen from Table 1 and Table 2, compared with the compound itself, the coordination unit formed by the connection of acridine and the nitrogen-containing heteroaromatic receptor unit coordinates with zinc to inhibit the vibration of the nitrogen-containing heteroaromatic receptor by using a coordination bond and increase its receptor strength, causing the luminescence of the compound to redshift, and its ΔE ST significantly decreases;

[0215] As can be seen from Table 2, the coordination unit itself does not have the property of thermally activated delayed fluorescence emission. After the formation of the complex, the complex has significant thermally activated delayed fluorescence emission properties, and the luminescence efficiency of the complex is significantly improved; the coordination unit itself has weak thermally activated delayed fluorescence emission properties, and after the formation of the complex, the complex has significant thermally activated delayed fluorescence emission properties, and the luminescence efficiency of the complex is significantly improved, up to 100% at most;

[0216] As can be seen from Table 3, the complexes all have good thermal stability, and the temperature at which the thermal weight loss is 5% is higher than 370 °C. Therefore, the compounds generated after the coordination of the nitrogen-containing ligands have more significant thermally activated delayed fluorescence emission properties, higher luminescence efficiency, and good thermal stability.

[0217] Example 32: Test on the electroluminescence performance of the complex obtained in Example 16

[0218] Using the complex obtained in Example 16 as the light-emitting layer, a device structure ITO / PEDOT / complex / TmPyPB(50nm) / LiF(1nm) / Al(100nm) was adopted to characterize the electroluminescence performance of the complex. The light-emitting layer was obtained by spin-coating a chlorobenzene solution (10 mg / mL) of the complex in Example 16 and annealing at 100 °C for 30 minutes. The performance of the obtained light-emitting device was tested, and the results are shown in Table 4. Table 4 is the electroluminescence device performance table of the complex described in Example 16 of the present invention.

[0219] Table 4

[0220]

[0221] As can be seen from Table 4, the compound can achieve an external quantum efficiency of 11.7%, breaking through the limitation of the external quantum efficiency of 5% of traditional fluorescent materials, and once again confirming that the complex has thermally activated delayed fluorescence properties.

[0222] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution of the present invention and its inventive concept, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

Claims

1. A thermally induced delayed fluorescence complex, characterized in that: The complex has a structure of Formula (Ia), Formula (Ib), Formula (Ic), Formula (Id), Formula (Ie), Formula (If), Formula (Ig), Formula (Ih), Formula (Ii), Formula (Ij), Formula (Ik), Formula (Il), Formula (Im), Formula (In) or Formula (Io); Formula (Ia); Formula (Ib); Formula (Ic); Formula(Id); Formula (Ie); Formula (If); Formula (Ig); Formula (Ih); Formula (Ii); Formula (Ij); Formula (Ik); Formula (I1); Formula (Im); Formula (In); Formula (Io).

2. An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer between the first electrode and the second electrode, characterized in that: The organic layer contains the thermally induced delayed fluorescence complex according to claim 1.

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