Chiral gold(III) compound, preparation method therefor, and application thereof

Abstract

The present invention relates to the field of organic light-emitting materials, and specifically relates to a chiral gold(III) compound, a preparation method therefor, and an application thereof. Provided is a chiral gold(III) compound which exhibits thermally activated delayed fluorescence, and has a short luminescence lifetime and a high decay rate. Because the performance of organic light-emitting diodes is closely related to the luminescence lifetime of the chiral gold(III) compound, an organic light-emitting diode made on the basis of the described compound has good device properties, such as high external quantum efficiency and reduction of efficiency roll-off under actual high-brightness use. In addition, the chiral gold(III) compound is a circularly polarized light-emitting material, and experiments have detected that enantiomers of the chiral gold(III) compound can respectively emit left-handed circularly polarized light and right-handed circularly polarized light of a certain strength; circularly polarized light-emitting materials have potential application value in a wide range of fields, such as planar 3D display, optical storage, optical sensors, and optical anti-counterfeiting.

Description

Chiral gold (III) compound, preparation method and application thereof

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on July 24, 2023, with application number 202310911745.2 and invention name “Chiral gold (III) compounds, preparation methods and applications thereof”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present invention belongs to the field of organic luminescent materials, and in particular relates to a chiral gold (III) compound, a preparation method and an application thereof. Background Art

[0003] Organic light-emitting diodes (OLEDs) are a display and lighting technology that has become increasingly popular in recent years, primarily used in display screens for electronic products such as mobile phones, televisions, and laptops. Because the luminescent materials used in OLEDs significantly impact device performance, developing high-performance, low-cost, and widely manufactured luminescent materials is crucial. Luminescent materials are broadly classified into two types: phosphorescent and fluorescent. Typically, when molecules in conventional fluorescent materials are excited, electrons transition from the ground state (S0) to the singlet excited state (S1), where they undergo radiative decay and return to the ground state, emitting fluorescence. OLEDs using conventional fluorescent materials have a theoretical internal quantum efficiency (IQE) of only approximately 25% because triplet excitons are not utilized. However, in phosphorescent metal complexes, the heavy metal atom effect increases the intersystem crossing (ISC) rate, allowing molecules to transition from the singlet excited state (S1) to the triplet excited state (T1), and then radiatively return from the T1 state to the S0 ground state, emitting phosphorescent light. OLEDs using phosphorescent materials can achieve an IQE of 100% by effectively utilizing both singlet and triplet excitons. Because the radiative transition from the T1 state to the ground state S0 is spin-forbidden, phosphorescent metal complexes have a relatively low radiative decay rate, resulting in a long luminescence lifetime. A longer luminescence lifetime increases the amount of inverse system crossing (RISC) and self-quenching, leading to lower quantum efficiency. The external quantum efficiency (EQE) of corresponding OLED devices also exhibits efficiency roll-off as luminance increases. Therefore, OLED devices tend to require luminescent materials with high quantum efficiency, short luminescence lifetime, and high radiative decay rate.

[0004] Thermally activated delayed fluorescence (TADF) materials are a new generation of luminescent materials. These materials have a sufficiently small energy difference between the S1 state and the T1 state (△E STIn OLED applications, TADF materials can be thermally activated by ambient heat, effectively utilizing triplet excitons through a reverse intersystem crossing (RISC) process, converting triplet excitons into singlet excitons and emitting delayed fluorescence. Therefore, OLEDs using TADF materials can effectively utilize both singlet and triplet excitons and achieve an IQE of 100%. Chiral gold (III) compounds can be directly applied to circularly polarized electroluminescent devices, eliminating the need for polarizers and simplifying the manufacturing process and display device structure. Using chiral gold (III) compounds that exhibit TADF can further enhance the device performance of circularly polarized organic light-emitting diodes.

[0005] CN111349106A "Alkyne Gold (III) Complex and Light-Emitting Device" describes the most similar implementation scheme to the present invention, but the gold (III) complex disclosed therein is not a chiral material and cannot emit circularly polarized light or be used in circularly polarized electroluminescent devices. It can be seen that although the gold (III) complexes in the prior art can exhibit thermally activated delayed fluorescence (TADF), they have a short luminescence lifetime and a high decay rate (kr is less than 10 5 s -1 range), but they do not have chirality and cannot emit circularly polarized light and be used in circularly polarized electroluminescent devices.

[0006] Summary of the Invention

[0007] In view of this, the purpose of the present application is to provide a chiral gold (III) compound, a preparation method and application thereof. The chiral gold (III) compound provided by the present invention is a circularly polarized luminescent material that can exhibit thermally activated delayed fluorescence, has a high luminescence quantum yield and decay rate, and a short luminescence lifetime.

[0008] The present invention provides a chiral gold (III) compound, the structure of which is shown in formula (I):

[0009] In formula (I), R1 to R 11 R is independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, halogen, deuterium or hydrogen; 12 is selected from substituted or unsubstituted alkyl ether, deuterium or hydrogen;

[0010] A is a chiral group having the structure of formula (Ia);

[0011] In formula (Ia), the Aj and Ar are independently connected to the N and R in formula (I) 12 The connected benzene rings are fused into a ring through heteroatoms or are not cyclic;

[0012] The Aj, Ar and the N to which they are connected form a ring or not;

[0013] Said Aj and Ar are independently selected from substituted or unsubstituted alkyl ether substituted C6~C 12 Aryl, substituted or unsubstituted heterocyclic condensed C6~C 12 C6~C substituted aryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenylamino 12 C6~C 12 Aryl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted heterocyclic amino substituted C6~C 12 Any of aryl, substituted or unsubstituted phenyl;

[0014] Said Aj and Ar are not unsubstituted phenyl groups at the same time.

[0015] The inventors of the present application have creatively discovered that a novel gold (III) luminophore supported by a chiral ligand can exhibit thermally activated delayed fluorescence (TADF) from yellow to red. The chiral gold (III) compound having a structure represented by formula (I) of the present invention has chirality through the chiral group of A in its formula, i.e., the structure represented by formula (Ia), and can thereby emit circularly polarized luminescent materials and exhibit thermally activated delayed fluorescence, with a high luminescence quantum yield and decay rate, and a short luminescence lifetime.

[0016] In the chiral gold (III) compound of the present invention, if any of Aj and Ar in the chiral group of the structure of formula (Ia) has a structure with two fused benzene rings, partial phosphorescence will occur in a toluene solution. In order to achieve optimal performance, Aj and Ar of the present invention are independently preferably selected from any one of substituted or unsubstituted alkyl ether substituted phenyl, substituted or unsubstituted dioxo six-membered heterocyclic fused phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted diphenylamino substituted phenyl, substituted or unsubstituted dibenzoheterocyclyl substituted phenyl, substituted or unsubstituted dibenzoheterocyclyl substituted biphenyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted heterocyclic amino substituted phenyl, and unsubstituted phenyl.

[0017] In certain embodiments of the present invention, the structure of A in formula (Ia) is specifically as shown in formula (II):

[0018] In formula (II), the Ph a and Ph b are all phenyl groups, the Ph aand Ph b N and R in formula (I) are not connected to it at the same time 12 The connected benzene rings are fused into a ring through heteroatoms, and the Ph a and Ph b and the N to which they are connected form a ring directly or through C, N, O or S;

[0019] The R 13 any one selected from a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted dibenzoheterocyclyl group, a substituted or unsubstituted dibenzoheterocyclyl-substituted phenyl group, a substituted or unsubstituted heterocyclicamino-substituted phenyl group, a substituted or unsubstituted dioxo six-membered heterocyclyl group fused to the benzene ring to which it is connected, a substituted or unsubstituted benzofuranyl group fused to the benzene ring to which it is connected, a substituted or unsubstituted benzothiophenyl group fused to the benzene ring to which it is connected, and a substituted or unsubstituted benzocycloalkyl group fused to the benzene ring to which it is connected.

[0020] Specifically, the Ph a and Ph b The N to which it is connected and the benzene ring connected to the N are not fused into a ring through heteroatoms: the Ph a and Ph b Any one of the N and R in formula (I) to which it is connected can 12 The connected benzene rings are fused into a six-membered ring through heteroatoms or are not ring-forming, but the Ph a and Ph b It cannot be connected to N and R in formula (I) at the same time 12 In some embodiments, the heteroatom of the present invention is preferably selected from O or S.

[0021] Specifically, the Ph a and Ph b and the N to which they are connected form a ring directly or through C, N, O or S: a and Ph b The three N atoms connected to the N atoms directly form a five-membered ring or form a six-membered ring through C, N, O or S atoms.

[0022] In some embodiments, A in Formula (Ia) is selected from one of the structures of Formula (II-1) to Formula (II-12):

[0023] In other embodiments of the present invention, the structure of A is specifically as shown in formula (III);

[0024] In formula (III), the R 14 and R15 independently selected from any one of a substituted or unsubstituted alkyl ether group, hydrogen, a substituted or unsubstituted dioxo six-membered heterocyclic group fused to a benzene ring to which it is connected, a substituted or unsubstituted benzofuranyl group fused to a benzene ring to which it is connected, and a substituted or unsubstituted benzothiophenyl group fused to a benzene ring to which it is connected; specifically, the alkyl ether group is C1-C 20 Alkyl ether group, preferably C1~C 10 Alkyl ether group, more preferably C1 to C5 alkyl ether group, even more preferably methane ether group;

[0025] Z is a heteroatom; in some embodiments, Z is preferably O or S;

[0026] The R 14 and R 15 Not hydrogen at the same time.

[0027] In some embodiments, A is selected from one of the structures of formula (III-1) to formula (III-11): In the chemical structural formula disclosed in the present invention, bold or dashed groups represent non-planarity caused by steric hindrance.

[0028] In the chiral gold (III) compound of the present invention, R1 to R 11 Preferably independently selected from substituted or unsubstituted C6 to C 20 Aryl, substituted or unsubstituted C4~C 20 Heteroaryl, substituted or unsubstituted C1~C 20 Alkyl, substituted or unsubstituted C4~C 20 Cycloalkyl, substituted or unsubstituted C4~C 20 heterocycloalkyl, fluorine, chlorine, bromine or hydrogen; R 12 Preferably selected from substituted or unsubstituted C1 to C 20 Alkyl ether or hydrogen;

[0029] Furthermore, in the chiral gold (III) compound of the present invention, R1 to R 11 Independently selected from substituted or unsubstituted C6~C 12 Aryl, substituted or unsubstituted C4~C 12 Heteroaryl, substituted or unsubstituted C1~C 10 Alkyl, substituted or unsubstituted C4~C 10 Cycloalkyl, substituted or unsubstituted C4~C 10 heterocycloalkyl, fluorine or hydrogen; R 12 Selected from substituted or unsubstituted C1-C 10 Alkyl ether or hydrogen;

[0030] Furthermore, in the chiral gold (III) compound of the present invention, R1 to R 10 R is independently selected from halogen-substituted C1-C5 alkyl, fluorine or hydrogen; 11 is selected from C1-C6 alkyl-substituted phenyl groups; R 12 is selected from substituted or unsubstituted C1-C5 alkyl ether or hydrogen;

[0031] Furthermore, in the chiral gold (III) compound of the present invention, R1 to R 10 R is independently selected from fluorine-substituted methane, fluorine or hydrogen; 11 is selected from C1-C4 alkyl-substituted phenyl groups; R 12 Selected from methane ether or hydrogen.

[0032] In some embodiments of the present invention, the chiral gold (III) compound of the present invention is:

[0033] In the chemical structural formula disclosed in the present invention, bold or dashed groups represent non-planarity caused by steric hindrance.

[0034] The chiral gold (III) compound provided by the present invention exhibits thermally activated delayed fluorescence, has a short luminescence lifetime, and a high decay rate. It is a circularly polarized luminescence material that can emit left-handed and right-handed circularly polarized light of certain intensities, and can be used in circularly polarized electroluminescent devices (CP-OLEDs).

[0035] The present invention also provides a method for preparing the chiral gold (III) compound, which is prepared from components including [Au(C^N^C)X] having a structure represented by formula (IV) and an aryl acetylene ligand having a structure represented by formula (V);

[0036] The X in the structure [Au(C^N^C)X] of the present invention is selected from F, Cl or Br, preferably selected from Cl. The R1 to R 11 and R1 to R 11 Same, no more details.

[0037] R in the aryl acetylene ligand of the structure shown in formula (V) of the present invention 12 and A and R in the above formula (I) 12The same as A, no further description is given. R in the aryl acetylene ligand of the structure shown in formula (V) of the present invention is 16 is selected from H or a protecting group; the protecting group is preferably a trialkylsilyl group having 3 to 20 carbon atoms, such as triisopropylsilyl or trimethylsilyl. The reaction temperature of the present invention is room temperature, preferably 20 to 30°C, and the reaction time is 3.5 to 24 hours. The molar ratio of [Au(C^N^C)X] to the arylacetylene ligand of the present invention is 1:1 to 1.5, preferably 1:1.

[0038] Specifically, the chiral gold (III) compound is prepared from components comprising [Au(C^N^C)X] of formula (IV), an aryl acetylene ligand of formula (V), a base, a catalyst, and an optional protecting group removing agent. More specifically, the method for preparing the chiral gold (III) compound of the present invention comprises reacting [Au(C^N^C)X] of formula (IV), an aryl acetylene ligand of formula (V), a base, a catalyst, and an optional protecting group removing agent in an organic solvent under a protective gas atmosphere to obtain the chiral gold (III) compound.

[0039] The protective gas of the present invention is selected from at least one of nitrogen, argon or helium. The base of the present invention is preferably selected from triethylamine. The catalyst of the present invention is preferably selected from CuI. The organic solvent of the present invention is selected from CH2Cl2 or CHCl3, preferably selected from CH2Cl2. The protecting group removing agent of the present invention can be selectively added or not added according to the actual situation; specifically, when R in the aryl acetylene ligand of the structure shown in formula (V) is 16 When the protecting group is a protecting group, the protecting group removing agent must be added; when R 16 When it is hydrogen, the protecting group removing agent does not need to be added. Those skilled in the art can select a specific protecting group removing agent according to the type of protecting group; in one embodiment, R in the aryl acetylene ligand of the structure shown in formula (V) 16 When it is triisopropylsilyl, the protecting group removing agent is selected from tetra-n-butylammonium fluoride (TBAF).

[0040] When the protecting group removing agent is added, the equivalent ratio of [Au(C^N^C)X], aryl acetylene ligand, base, catalyst and protecting group removing agent is 1:1-1.5:1-1.5:0.05-0.1:1.2-1.5, preferably 1:1:1.5:0.1:1.5. When the protecting group removing agent is not added, the equivalent ratio of [Au(C^N^C)X], aryl acetylene ligand, base and catalyst is 1:1-1.5:1-1.5:0.1-1.1, preferably 1:1:1.1:1.1.

[0041] In certain embodiments of the present invention, the method for preparing the chiral gold (III) compound of the present invention comprises: under a protective gas atmosphere, mixing [Au(C^N^C)X] of the structure represented by formula (IV) and a triisopropylsilane-protected aryl acetylene ligand represented by formula (V) in an organic solvent, adding triethylamine, tetra-n-butylammonium fluoride and CuI thereto, reacting at room temperature for 10 to 14 hours, preferably 12 hours, separating and purifying to obtain a chiral gold (III) compound; the equivalent ratio of the [Au(C^N^C)X], triisopropylsilane-protected aryl acetylene ligand, triethylamine, tetra-n-butylammonium fluoride and CuI is 1:1:1.5:1.5:0.1.

[0042] In some embodiments of the present invention, the preparation method of the chiral gold (III) compound of the present invention comprises: under a protective gas atmosphere, mixing an unprotected aryl acetylene ligand of the structure represented by formula (V), triethylamine and CuI in an organic solvent, and conducting a pre-reaction at room temperature for 1 to 3 hours, preferably 1.5 hours; then adding [Au(C^N^C)X] of the structure represented by formula (IV) to the reaction system, and reacting at room temperature for 2 to 3 hours, preferably 2 hours; then quenching the reaction, separating and purifying to obtain a chiral gold (III) compound; the equivalent ratio of [Au(C^N^C)X], the unprotected aryl acetylene ligand, triethylamine and CuI is 1:1:1.1:1.1.

[0043] In other embodiments of the present invention, the preparation method of the chiral gold (III) compound of the present invention comprises: mixing [Au(C^N^C)X] of the structure represented by formula (IV) and the triisopropylsilane-protected aryl acetylene ligand represented by formula (V) in an organic solvent, adding triethylamine, tetra-n-butylammonium fluoride and CuI thereto, reacting at room temperature for 20 to 24 hours, preferably 24 hours, separating and purifying to obtain a chiral gold (III) compound; the equivalent ratio of the [Au(C^N^C)X], triisopropylsilane-protected aryl acetylene ligand, triethylamine, tetra-n-butylammonium fluoride and CuI is 1:1:1.5:1.5:0.1.

[0044] The present invention provides use of the chiral gold (III) compound described above in an organic electronic device, wherein the organic electronic device is an organic electroluminescent device, a luminescent electrochemical cell or a chemical sensor.

[0045] The present invention also provides an organic electroluminescent device comprising an anode, a cathode, and a light-emitting layer disposed between the anode and cathode, wherein the light-emitting layer comprises the chiral gold (III) compound described above or the chiral gold (III) compound prepared by the above-described preparation method. Specifically, the organic electroluminescent device of the present invention comprises a stacked anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode. The preparation method of the organic electroluminescent device of the present invention is well known to those skilled in the art.

[0046] The present invention provides a chiral gold (III) compound, a preparation method and application thereof. The chiral gold (III) compound provided by the present invention exhibits thermally activated delayed fluorescence, has a short luminescence lifetime, and a high decay rate. Since the performance of an organic light-emitting diode is closely related to the luminescence lifetime of the chiral gold (III) compound, the organic light-emitting diode prepared based on the chiral gold (III) compound of the present invention can exhibit better device performance, such as higher external quantum efficiency and reduced efficiency roll-off under actual high-brightness use. In addition, the chiral gold (III) compound provided by the present invention is a circularly polarized luminescent material. Experimental detection shows that their enantiomers can emit left-handed and right-handed circularly polarized light of a certain intensity, respectively. Circularly polarized luminescent materials also have potential application value in a wide range of fields such as flat 3D display, optical storage, optical sensors, and optical anti-counterfeiting. Experiments show that the luminescence quantum yield of the chiral gold (III) compound provided by the present invention in PMMA film generally reaches 0.5 to 0.9, the luminescence lifetime is less than 3 microseconds, and the radiation decay rate constant is estimated to be 1.1×10 5 ~7.0×10 5 s -1 , which is much higher than the values ​​observed in phosphorescent gold (III) luminescent materials (10 3 s -1 The OLED made of the chiral gold (III) compound provided by the present invention has a practical high brightness (1000 cd m -2 ) under different conditions, the external quantum efficiencies reached 11.2-18.1% respectively. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 is a TADF spectrum of luminophores Au1 to Au3 measured in a PMMA film;

[0048] FIG2 is a TADF spectrum of luminophores Au1 to Au3 measured in toluene;

[0049] FIG3 is a TADF spectrum of luminophores Au4 to Au6 measured in PMMA film or mCP;

[0050] FIG4 is a TADF spectrum of luminophores Au4 to Au6 measured in toluene;

[0051] FIG5 is a spectrum of luminophore Au7 measured in PMMA film and toluene, respectively;

[0052] FIG6 is an absorption spectrum of Au4 and Au4-enantiomers measured in toluene;

[0053] FIG7 is a TADF spectrum of Au4 and Au4-enantiomer measured in toluene;

[0054] FIG8 is a TADF spectrum of Au6-enantiomer measured in toluene;

[0055] FIG9 is an electroluminescence spectrum of a light-emitting device based on the luminescent body Au4;

[0056] FIG10 is a graph showing the external quantum efficiency of a light-emitting device based on the luminescent material Au4;

[0057] FIG11 is a brightness test diagram of a light-emitting device based on the luminous body Au4;

[0058] FIG12 is a graph showing the current density of a light-emitting device based on the luminescent body Au4;

[0059] FIG13 is an electroluminescence spectrum of a light-emitting device based on the luminescent body Au5;

[0060] FIG14 is a graph showing the external quantum efficiency of a light-emitting device based on the luminescent material Au5;

[0061] FIG15 is a brightness test diagram of a light-emitting device based on the luminous body Au5;

[0062] FIG16 is a graph showing the current density of a light-emitting device based on the luminescent material Au5;

[0063] FIG17 is an electroluminescence spectrum of a light-emitting device based on the luminescent body Au6;

[0064] FIG18 is a graph showing the external quantum efficiency of a light-emitting device based on the luminescent material Au6;

[0065] FIG19 is a brightness test diagram of a light-emitting device based on the luminous body Au6;

[0066] FIG20 is a graph showing the current density of a light-emitting device based on the luminescent material Au6. DETAILED DESCRIPTION

[0067] The present invention discloses chiral gold (III) compounds, preparation methods, and applications thereof. Those skilled in the art can refer to the contents of this invention and appropriately improve the process parameters to achieve the desired results. It should be noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications herein without departing from the content, spirit, and scope of the present invention to implement and apply the technology of the present invention.

[0068] All luminescence lifetime tests in the present invention were performed using a "Quanta Ray GCR 150-10 pulsed Nd:YAG laser system" (laser wavelength: 355 nm). At a fixed luminescence wavelength, the decay of the luminescence intensity over time was observed, and the luminescence lifetime was measured according to Formula 1. Finally, the luminescence lifetime was determined by fitting the exponential decay using Origin software.

[0069] I(t)=I0 e -t / τ Formula 1; In formula 1, the initial luminous intensity is I0, the luminous intensity at time t is I(t), and the luminous lifetime is τ.

[0070] Radiative decay rate constant (k r ) is calculated as shown in Formula 2:

[0071] k r =Φ / τ Formula 2; In Formula 2, the luminescence quantum yield is Φ and the luminescence lifetime is τ.

[0072] The luminescence quantum yield was measured using a “Hamamatsu C11347 Quantaurus-QY Absolute PL quantum yields measurement system”.

[0073] The present invention will be further described below with reference to the embodiments:

[0074] Example 1

[0075] (1) Under argon protection, [Au(C^N^C)Cl] (60 mg, 1 equiv.) and triisopropylsilane-protected arylacetylene ligand (1 equiv.) were mixed in a CH2Cl2 solution, and triethylamine (1.5 equiv.), tetra-n-butylammonium fluoride (TBAF) (1.5 equiv.) and CuI (0.1 equiv.) were added to the reaction mixture and reacted at room temperature for 12 hours.

[0076] (2) After the reaction, most of the solvent was evaporated under reduced pressure, the mixture solution was concentrated to 2 mL, and EtOH was added to precipitate the crude material. The crude material was filtered and washed with EtOH and Et2O, respectively.

[0077] (3) Finally, Et2O is added to an appropriate amount of CH2Cl2 solution containing the complex to recrystallize to obtain the luminescent body Au1;

[0078] The structural formula of the luminescent body Au1 is The yield, appearance, H NMR spectrum and high-resolution mass spectrometry data of the luminophore Au1 are as follows:

[0079] Au1: Yield: 61 mg (62%, yellow solid).

[0080] 1 H NMR (500MHz, DMSO-d6) δ / ppm=8.21(t,J=8.2Hz,1H),7.93(d,J=8.3Hz,2H),7.45(d,J=6.2Hz,2H),7.29(t,J =10.7Hz,2H),6.97(t,J=8.2Hz,2H),6.86(s,2H),6.79(d,J=8.4Hz,2H),6.64(d,J=8.1Hz,2H),3.62(s,6H);

[0081] HR-MS(EI):m / z calcd.for[C 39 H 21 AuF4N2O4] + [M] + :854.1097,found:854.1093.

[0082] Example 2

[0083] (1) Under argon protection, [Au(C^N^C)Cl] (65 mg, 1 equiv.) and triisopropylsilane-protected arylacetylene ligand (1 equiv.) were mixed in a CH2Cl2 solution, and triethylamine (1.5 equiv.), TBAF (tetra-n-butylammonium fluoride) (1.5 equiv.) and CuI (0.1 equiv.) were added to the reaction mixture and reacted at room temperature for 12 hours.

[0084] (2) After the reaction, most of the solvent was evaporated under reduced pressure, the mixture solution was concentrated to 2 mL, and EtOH was added to precipitate the crude material. The crude material was filtered and washed with EtOH and Et2O, respectively.

[0085] (3) Finally, Et2O is added to an appropriate amount of CH2Cl2 solution containing the complex to recrystallize to obtain the luminescent body Au2;

[0086] The structural formula of the luminous body Au2 is The yield, appearance, H NMR spectrum and high-resolution mass spectrometry data of the luminescent material Au2 are as follows:

[0087] Au2: Yield: 69 mg (63%, yellow solid).

[0088] 1 H NMR (500MHz, DMSO-d6) δ / ppm=8.19(t,J=8.2Hz,1H),7.86(d,J=8.2Hz,2H),7.37(d,J= 6.4Hz,2H),7.18(t,J=10.6Hz,2H),6.80(s,2H),6.64–6.25(m,4H),4.39–4.05(m,8H);

[0089] HR-MS(EI):m / z calcd.for[C 41 H 21 AuF4N2O6] + [M] + :910.0996,found:910.0987.

[0090] Example 3

[0091] (1) Under argon protection, the aryl acetylene ligand (1 equiv.), CuI (1.1 equiv.) and dry Et3N (1.1 equiv.) were mixed in a deoxygenated and dried CH2Cl2 solution and reacted at room temperature for 1.5 hours.

[0092] (2) [Au(C^N^C)Cl] (48 mg, 1 equiv.) and CHCl3 (10 mL) were added to the reaction mixture and reacted at room temperature for 2 hours.

[0093] (3) After the reaction, water is added to quench the reaction and a crude substance is precipitated. The crude substance is filtered and washed with water, EtOH, and CH2Cl2, respectively. The resulting product is insoluble in most solvents, and the luminescent material Au3 is obtained;

[0094] The structural formula of the luminous body Au3 is The yield, appearance and high-resolution mass spectrometry data of the luminophore Au3 are as follows:

[0095] Au3: Yield: 43 mg (55%, yellow solid).

[0096] HR-MS(ESI):m / z calcd.for[C 45 H 26 AuF4N2] + ,[M+H] + :867.1692,found:867.1671.

[0097] Example 4

[0098] (1) Under argon protection, [Au(C^N^C)Cl] (65 mg, 1 equiv.) and triisopropylsilane-protected arylacetylene ligand (1 equiv.) were mixed in a CH2Cl2 solution, and triethylamine (1.5 equiv.), TBAF (tetra-n-butylammonium fluoride) (1.5 equiv.) and CuI (0.1 equiv.) were added to the reaction mixture and reacted at room temperature for 24 hours.

[0099] (2) After the reaction, the solvent was evaporated under reduced pressure, and the obtained crude material was purified by silica gel column chromatography to obtain the luminescent material Au4; the structural formula of the luminescent material Au4 is The yield, appearance, H NMR spectrum and high-resolution mass spectrometry data of the luminescent material Au4 are as follows:

[0100] Au4: Yield: 67 mg (68%, yellow solid).

[0101] 1H NMR(500MHz,CD2Cl2)δ / ppm 8.18(d,J=1.8Hz,2H),7.79(s,2H),7.75(d,J=8.1Hz,2H),7.65(d,J=1.7Hz,1H),7.57(d,J=1.7Hz,2H),7 .51(dd,J=8.2,1.9Hz,2H),6.63(s,2H),6.49(s,4H),4.28–4.23(m,2H),4.20–4.14(m,6H),1.42(s,18H).

[0102] HRMS(EI):m / z Calcd.for C 57 H 43 AuF6N2O6[M+H] + :1163.2769,found:1163.2712.

[0103] Example 5

[0104] (1) Under argon protection, [Au(C^N^C)Cl] (63 mg, 1 equiv.) and triisopropylsilane-protected arylacetylene ligand (1 equiv.) were mixed in a CH2Cl2 solution, and triethylamine (1.5 equiv.), TBAF (tetra-n-butylammonium fluoride) (1.5 equiv.) and CuI (0.1 equiv.) were added to the reaction mixture and reacted at room temperature for 24 hours.

[0105] (2) After the reaction, the solvent was evaporated under reduced pressure, and the obtained crude material was purified by silica gel column chromatography to obtain the luminescent material Au5; the structural formula of the luminescent material Au5 is The yield, appearance, H NMR spectrum and high-resolution mass spectrometry data of the luminescent material Au5 are as follows:

[0106] Au5: Yield: 61 mg (62%, yellow solid).

[0107] 1H NMR(500MHz,CD2Cl2)δ / ppm 8.27–8.03(m,2H),7.74(s,2H),7.68(d,J=8.1Hz,2H),7.62(d,J=1.7Hz,1H),7.57(d,J=1.7Hz,2H),7.53–7.42(m,2H),7.37–7.23 (m,4H),7.18(d,J=8.2Hz,2H),7.10(ddd,J=8.3,7.2,1.3Hz,2H),6.74(s,2H),6.72–6.60(m,2H),6.14–5.93(m,2H),1.40(s,18H).

[0108] HRMS(EI):m / z Calcd.for C 65 H 43 AuF6N2O4[M+H] + :1227.2871,found:1227.2824.

[0109] Example 6

[0110] (1) Under argon protection, [Au(C^N^C)Cl] (80 mg, 1 equiv.) and triisopropylsilane-protected arylacetylene ligand (1 equiv.) were mixed in a CH2Cl2 solution, and triethylamine (1.5 equiv.), TBAF (tetra-n-butylammonium fluoride) (1.5 equiv.) and CuI (0.1 equiv.) were added to the reaction mixture and reacted at room temperature for 24 hours.

[0111] (2) After the reaction, the solvent was evaporated under reduced pressure, and the obtained crude material was purified by silica gel column chromatography to obtain the luminescent material Au6; the structural formula of the luminescent material Au6 is The yield, appearance, H NMR spectrum and high-resolution mass spectrometry data of the luminescent material Au6 are as follows:

[0112] Au6: Yield: 69 mg (63%, yellow solid).

[0113] 1H NMR(500MHz,CDCl3)δ / ppm 7.93(d,J=1.8Hz,2H),7.66(d,J=5.1Hz,3H),7.57(d,J=8.1Hz,2H),7.52( d,J=1.7Hz,2H),7.37(dd,J=8.1,1.8Hz,2H),6.81(s,2H),6.69(s,2H),6.5 6(dd,J=19.2,8.2Hz,3H),5.79(s,1H),4.25(ddd,J=10.7,7.4,2.6Hz,1H), 3.99(dt,J=11.4,3.0Hz,1H),3.88(dt,J=17.8,11.6Hz,2H),1.41(s,18H).

[0114] HRMS(EI):m / z Calcd.for C 55 H 41 AuF6N2O4[M+H] + :1105.2714,found:1105.2675.

[0115] Example 7

[0116] (1) Under argon protection, [Au(C^N^C)Cl] (60 mg, 1 equiv.) and triisopropylsilane-protected arylacetylene ligand (1 equiv.) were mixed in a CH2Cl2 solution, and triethylamine (1.5 equiv.), TBAF (tetra-n-butylammonium fluoride) (1.5 equiv.) and CuI (0.1 equiv.) were added to the reaction mixture and reacted at room temperature for 24 hours.

[0117] (2) After the reaction, most of the solvent was evaporated under reduced pressure, the mixture solution was concentrated to 2 mL, and EtOH was added to precipitate the crude material. The crude material was filtered and washed with EtOH and Et2O, respectively.

[0118] (3) Finally, Et2O is added to a proper amount of CH2Cl2 solution containing the complex to recrystallize to obtain luminescent body Au7; the structural formula of the luminescent body Au7 is The yield, appearance, H NMR spectrum and high-resolution mass spectrometry data of the luminophore Au7 are as follows:

[0119] Au7: Yield: 58 mg (61%, yellow solid).

[0120] 1H NMR(500MHz,CDCl3)δ / ppm 7.91–7.75(m,2H),7.62(m,3H),7.46(m,4H),7.29(m,3H),7.19(d,J=8.7Hz,1H),7.09(m,1H) ,6.98(m,1H),6.86(m,1H),6.79(d,J=1.5Hz,1H),6.70(d,J=1.5Hz,1H),6.38(d,J=8.2,1H);

[0121] HRMS(EI):m / z Calcd.for C 41 H 19 AuF4N2O2[M + ]:844.1048,found:844.1079.

[0122] The luminophores obtained in Examples 1 to 7 were subjected to photophysical characterization, and the results are shown in Table 1:

[0123] Table 1

[0124] Table 1 shows the photophysical characterization data of luminophores Au1 to Au6 in PMMA film, mCP or toluene, which shows that Au1 to Au6 all exhibit short luminescence lifetime (less than 3 μs) and high radiation decay rate (k r In 10 5 s -1 This is due to the TADF luminescence characteristics of these chiral gold (III) compounds. Au7 also exhibits the above-mentioned photophysical properties in PMMA and has TADF luminescence characteristics. In addition, Au4 and Au6 emit deep red and near-infrared light in toluene. According to the energy gap law, the smaller the energy gap, the faster the non-radiative transition rate. Therefore, the excited states of Au4 and Au6, deep red and near-infrared luminescent materials, will be mainly dominated by non-radiative transitions, resulting in a lower corresponding luminescence quantum yield.

[0125] Spectral measurements were performed on the luminophores of Examples 1 to 3, as shown in Figures 1 to 2. Figure 1 is a TADF spectrum of luminophores Au1 to Au3 measured in a PMMA film; Figure 2 is a TADF spectrum of luminophores Au1 to Au3 measured in toluene. It can be seen from Figures 1 to 2 that the TADF spectra of Au1 to Au3 in PMMA films or toluene all show structureless and broad peak curves, which are different from the fine structure luminescence spectra presented by related phosphorescent gold (III) compounds, because their phosphorescence comes from the excited state of the π-π* characteristic in the main triple ligand.

[0126] Spectral measurements were performed on the luminophores of Examples 4 to 6, as shown in Figures 3 to 4. Figure 3 is a TADF spectrum of luminophores Au4 to Au6 measured in PMMA film or mCP; Figure 4 is a TADF spectrum of luminophores Au4 to Au6 measured in toluene. It can be seen from Figures 3 to 4 that the TADF spectra of Au4 to Au6 in PMMA film or toluene all show structureless and broad peak curves, which are different from the fine structure luminescence spectra presented by related phosphorescent gold (III) compounds, because their phosphorescence comes from the excited state of the π-π* characteristic in the main triple ligand.

[0127] The luminophore of Example 7 was measured spectra, as shown in FIG5 . FIG5 is a spectrum of the luminophore Au7 measured in PMMA film and toluene, respectively. As shown in FIG5 , Au7 exhibits a structureless and broad peak curve in both PMMA film and toluene. However, the luminescence lifetime of Au7 in toluene is as long as 21 microseconds, and the radiation decay rate constant is estimated to be 5.7×10 3 s -1 , which is much lower than the radiation decay rate of Au1 to Au6. This is due to the presence of two mutually fused benzene rings in the chiral ligand of Au7, reflecting that the difference in chiral ligands affects the phosphorescence properties of the excited state of the gold (III) compound Au7 in toluene, indicating that Au7 has partial phosphorescence properties.

[0128] The asymmetry factor analysis of the luminescent material Au4 of Example 4 was performed using toluene as the medium. The results are shown in Table 2.

[0129] Table 2

[0130] The absorption spectra of Au4 and Au4-enantiomers were measured in toluene, as shown in Figure 6. Figure 6 shows the absorption spectra of Au4 and Au4-enantiomers measured in toluene. As shown in Figure 6, enantiomers are related to the dichroism of circularly polarized light, that is, the different absorption of left-handed light and right-handed light.

[0131] The TADF spectra of Au4 and Au4-enantiomers were measured in toluene, as shown in Figure 7. Figure 7 shows the TADF spectra of Au4 and Au4-enantiomers measured in toluene. As shown in Figure 7, the enantiomers can emit left-handed and right-handed circularly polarized light of a certain intensity, respectively.

[0132] The TADF spectrum of the Au6-enantiomer was measured in toluene, as shown in Figure 8. As shown in Figure 8, the enantiomers can emit left-handed and right-handed circularly polarized light of a certain intensity.

[0133] Example 8

[0134] The light-emitting device was prepared according to the device structure: ITO / PEDOT:PSS / PVK(20nm) / Au4:PVK:OXD-7(40nm) / TPBi(40nm) / LiF(1.2nm) / Al(100nm), wherein the doping concentration of Au4 was 4wt / wt%, 8wt / wt%, 12wt / wt% and 16wt / wt%, respectively, and 4 light-emitting devices based on the luminescent body Au4 were prepared.

[0135] The performance data of the light-emitting device based on the luminescent body Au4 prepared above are shown in Table 3 and Figures 9 to 12, wherein Figure 9 is an electroluminescence spectrum diagram of the light-emitting device based on the luminescent body Au4, Figure 10 is an external quantum efficiency test diagram of the light-emitting device based on the luminescent body Au4, Figure 11 is a brightness test diagram of the light-emitting device based on the luminescent body Au4, and Figure 12 is a current density diagram of the light-emitting device based on the luminescent body Au4.

[0136] Table 3

[0137] Example 9

[0138] The light-emitting device was prepared according to the device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / mCBP (10nm) / Au5:mCBP (20nm) / PPF (10nm) / TmPyPb (40nm) / LiF (1.2nm) / Al (100nm), wherein the doping concentration of Au5 was 0.5wt / wt%, 1wt / wt% and 2wt / wt%, respectively, and three light-emitting devices based on the luminescent body Au5 were prepared.

[0139] The performance data of the light-emitting device based on the luminescent body Au5 prepared above are shown in Table 4 and Figures 13 to 16, wherein Figure 13 is an electroluminescence spectrum diagram of the light-emitting device based on the luminescent body Au5, Figure 14 is an external quantum efficiency test diagram of the light-emitting device based on the luminescent body Au5, Figure 15 is a brightness test diagram of the light-emitting device based on the luminescent body Au5, and Figure 16 is a current density diagram of the light-emitting device based on the luminescent body Au5.

[0140] Table 4

[0141] Example 10

[0142] The light-emitting device was prepared according to the device structure: ITO / HAT-CN (5nm) / TAPC (40nm) / TCTA (10nm) / Au6:TCTA:TPBi (20nm) / TPBi (40nm) / LiF (1.2nm) / Al (100nm), wherein the doping concentration of Au6 was 1wt / wt%, 2wt / wt% and 3wt / wt%, respectively, and three light-emitting devices based on the luminescent body Au6 were prepared.

[0143] The performance data of the light-emitting device based on the luminescent body Au6 prepared above are shown in Table 5 and Figures 17 to 20, wherein Figure 17 is an electroluminescence spectrum diagram of the light-emitting device based on the luminescent body Au6, Figure 18 is an external quantum efficiency test diagram of the light-emitting device based on the luminescent body Au6, Figure 19 is a brightness test diagram of the light-emitting device based on the luminescent body Au6, and Figure 20 is a current density diagram of the light-emitting device based on the luminescent body Au6.

[0144] Table 5

[0145] The performance data of the light emitting devices based on the luminous bodies Au4 to Au6 in the above-mentioned embodiments 8 to 10 show that the luminous bodies Au4 to Au6 can show better device performance. -2 ), the external quantum efficiency is effectively improved by 11.2~18.1%, and the efficiency roll-off is reduced. This is attributed to the higher radiation decay rate (k r In 10 5 s -1 within the scope).

[0146] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A chiral gold (III) compound, characterized in that Its structure is shown in formula (I): In formula (I), R1 to R 11 R is independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, halogen, deuterium or hydrogen; 12 is selected from substituted or unsubstituted alkyl ether, deuterium or hydrogen; A is a chiral group having a structure of formula (Ia); In formula (Ia), Aj and Ar are independently connected to N and R in formula (I) 12 The connected benzene rings are fused into a ring through heteroatoms or are not cyclic; The Aj, Ar and the N to which they are connected form a ring or no ring; The Aj and Ar are independently selected from substituted or unsubstituted alkyl ether substituted C6~C 12 Aryl, substituted or unsubstituted heterocyclic condensed C6~C 12 Aryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenylamino substituted C6~C 12 C6~C 12 Aryl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted heterocyclic amine substituted C6~C 12 Any of aryl, substituted or unsubstituted phenyl; The Aj and Ar are not unsubstituted phenyl groups at the same time.

2. The chiral gold (III) compound according to claim 1, characterized in that In formula (Ia), Aj and Ar are independently selected from any one of substituted or unsubstituted alkyl ether substituted phenyl, substituted or unsubstituted dioxo six-membered heterocyclic fused phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted diphenylamino substituted phenyl, substituted or unsubstituted dibenzoheterocyclic substituted phenyl, substituted or unsubstituted dibenzoheterocyclic substituted biphenyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted heterocyclic amino substituted phenyl, and unsubstituted phenyl.

3. The chiral gold (III) compound according to claim 2, characterized in that The structure of A is specifically shown in formula (II): In formula (II), the Ph a and Ph b are all phenyl groups, the Ph a and Ph b N and R in formula (I) to which they are connected are not simultaneously 12 The connected benzene rings are fused into a ring through heteroatoms, and the Ph a and Ph b and the N to which they are connected form a ring directly or through C, N, O or S; The R 13 Any one selected from substituted or unsubstituted diphenylamino, substituted or unsubstituted dibenzoheterocyclyl, substituted or unsubstituted dibenzoheterocyclyl-substituted phenyl, substituted or unsubstituted heterocyclicamino-substituted phenyl, a substituted or unsubstituted dioxo six-membered heterocyclyl fused to the benzene ring to which it is connected, a substituted or unsubstituted benzofuranyl fused to the benzene ring to which it is connected, a substituted or unsubstituted benzothiophenyl fused to the benzene ring to which it is connected, and a substituted or unsubstituted benzocycloalkyl fused to the benzene ring to which it is connected.

4. The chiral gold (III) compound according to claim 3, characterized in that The A is selected from one of the structures of formula (II-1) to formula (II-12):

5. The chiral gold (III) compound according to claim 2, characterized in that The structure of A is specifically shown in formula (III); In formula (III), R 14 and R 15 independently selected from any one of substituted or unsubstituted alkyl ether, hydrogen, a substituted or unsubstituted dioxo six-membered heterocyclic group fused to the benzene ring to which it is connected, a substituted or unsubstituted benzofuranyl fused to the benzene ring to which it is connected, and a substituted or unsubstituted benzothiophenyl group fused to the benzene ring to which it is connected; The Z is a heteroatom; The R 14 and R 15 Not at the same time as hydrogen.

6. The chiral gold (III) compound according to claim 5, characterized in that The A is selected from one of the structures of formula (III-1) to formula (III-11):

7. The chiral gold (III) compound according to claim 1, characterized in that The chiral gold (III) compound is:

8. The method for preparing a chiral gold (III) compound according to any one of claims 1 to 7, characterized in that it is prepared from components including [Au(C^N^C)X] having a structure represented by formula (IV) and an aryl acetylene ligand having a structure represented by formula (V): In formula (IV), X is selected from F, Cl or Br; In formula (V), R 16 is selected from H or a protecting group.

9. The preparation method according to claim 8, characterized in that: The molar ratio of [Au(C^N^C)X] to the aryl acetylene ligand is 1:1 to 1.

5.

10. Use of the chiral gold (III) compound according to any one of claims 1 to 7 in an organic electronic device, wherein the organic electronic device is an organic electroluminescent device, a luminescent electrochemical cell or a chemical sensor.

11. An organic electroluminescent device, characterized in that: comprising an anode, a cathode and a light-emitting layer disposed between the anode and the cathode; The light-emitting layer comprises the chiral gold (III) compound according to any one of claims 1 to 7 or the chiral gold (III) compound prepared by the preparation method according to any one of claims 8 to 9.

12. The organic electroluminescent device according to claim 11, characterized in that: The invention comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode which are stacked.

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