Chiral gold (III) compound as well as preparation method and application thereof

Abstract

The invention relates to the field of organic light-emitting materials, in particular to a chiral gold (III) compound and a preparation method and application thereof. The chiral gold (III) compound provided by the invention presents thermally activated delayed fluorescence, and has relatively short luminescence lifetime and relatively high decay rate. As the performance of the organic light-emitting diode is closely related to the light-emitting life of the chiral gold (III) compound, the organic light-emitting diode prepared based on the compound disclosed by the invention can show better device performance, such as higher external quantum efficiency and reduction of efficiency roll-off under actual high-brightness use. Besides, the chiral gold (III) compound provided by the invention belongs to a circularly polarized luminescent material, the enantiomer of the chiral gold (III) compound can respectively emit levorotatory circularly polarized light and dextrorotatory circularly polarized light with certain intensity through experimental detection, and the circularly polarized luminescent material also has potential application value in the wide fields of planar 3D display, optical storage, optical sensors, optical anti-counterfeiting and the like.

Description

Technical Field

[0001] The invention relates to the field of organic luminescent materials, in particular to chiral gold (III) compounds, preparation methods and applications thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a display and lighting technology that has been widely used in recent years, and are mainly used in the display screens of electronic products, such as mobile phones, televisions, and laptops. Since the luminescent materials in OLEDs have a great impact on the performance of the device, it is of great significance to develop high-performance, low-cost, and widely produced luminescent materials. Luminescent materials are generally divided into two types: phosphorescence and fluorescence. In general, the molecules of ordinary fluorescent materials are excited, and the electrons transition from the ground state S0 to the singlet excited state (S1 state), and then return to the ground state through the radiation decay process to emit fluorescence. OLEDs using ordinary fluorescent materials have a theoretical internal quantum efficiency (IQE) of only about 25% because the triplet excitons are not utilized. However, in phosphorescent metal complexes, the heavy metal atom effect increases the intersystem crossing (ISC) rate, and the molecules cross from the singlet excited state (S1 state) to the triplet excited state (T1 state) through the intersystem crossing process, and then return from the T1 state to the S0 ground state through radiation to emit phosphorescence. OLEDs using phosphorescent materials can effectively utilize singlet and triplet excitons to achieve an IQE of 100%. Since the radiative transition from the T1 state to the ground state S0 is spin-forbidden, the phosphorescent metal complex has a relatively low radiative decay rate, and thus a longer luminescence lifetime. The longer the luminescence lifetime, the more RISC and self-quenching consumption, resulting in lower quantum efficiency. The external quantum efficiency EQE of the corresponding OLED device will also show efficiency roll-off as the luminescence brightness increases. Therefore, OLED devices tend to require luminescent materials with higher quantum efficiency, shorter luminescence lifetime, and higher radiative decay rate.

[0003] Thermally activated delayed fluorescence (TADF) materials are a new generation of luminescent materials. This type of material has a sufficiently small energy difference between the S1 state and the T1 state (△E ST ). In OLED applications, TADF materials can be thermally activated by the heat of the surrounding environment, and effectively utilize triplet excitons through the reverse intersystem crossing (RISC) process, prompting triplet excitons to be converted into singlet excitons, emitting delayed fluorescence. Therefore, OLEDs using TADF materials can effectively utilize singlet and triplet excitons, and can also achieve 100% IQE. Chiral gold (III) compounds can be directly applied to circularly polarized electroluminescent devices, so related devices do not need to use polarizers, thereby simplifying the manufacturing process and the structure of display equipment. The use of chiral gold (III) compounds that exhibit TADF can further improve the device performance of circularly polarized-organic light-emitting diodes.

[0004] CN111349106A "Alkyne gold (III) complex and light-emitting device" describes the implementation scheme that is most similar to the present invention, but the gold (III) complex disclosed therein is not a chiral material, cannot emit circularly polarized light and cannot be used in circularly polarized electroluminescent devices. It can be seen that although the gold (III) complex in the prior art can exhibit thermally activated delayed fluorescence (TADF), has a short luminescence lifetime and a high decay rate (kr is 10 5 s -1 range), but they do not have chirality, cannot emit circularly polarized light and cannot be used in circularly polarized electroluminescent devices. Summary of the invention

[0005] In view of this, the purpose of the present invention 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, which can exhibit thermally activated delayed fluorescence, has a higher luminescence quantum yield and decay rate, and a shorter luminescence lifetime.

[0006] The present invention provides a chiral gold (III) compound, the structure of which is shown in formula (I):

[0007]

[0008] 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;

[0009] A is a chiral group having a structure of formula (Ia);

[0010]

[0011] 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;

[0012] The Aj, Ar and the N to which they are connected form a ring or no ring;

[0013] 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 12C6~C 12 Aryl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted heterocyclic amine substituted C6~C 12 Any of aryl, substituted or unsubstituted phenyl;

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

[0015] The inventors of the present application 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 A in its formula, i.e., the chiral group of the structure represented by formula (Ia), and can emit circularly polarized luminescent material and exhibit thermally activated delayed fluorescence, with a higher luminescence quantum yield and decay rate, and a shorter 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 benzene rings fused, partial phosphorescence will occur in a toluene solution. In order to achieve the best 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 dibenzoheterocyclic substituted phenyl, substituted or unsubstituted dibenzoheterocyclic 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]

[0019] 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;

[0020] The R 13Any 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.

[0021] Specifically, the Ph a and Ph b The N to which it is connected and the benzene ring connected to the N are not simultaneously 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 The connected benzene rings form a ring; in some embodiments, the heteroatom of the present invention is preferably selected from O or S.

[0022] Specifically, the Ph a and Ph b and the N to which they are connected directly form a ring or form a ring through C, N, O or S: the Ph 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.

[0023] In some embodiments, A in formula (Ia) is selected from one of the structures of formula (II-1) to formula (II-12):

[0024]

[0025] In other embodiments of the present invention, the structure of A is specifically as shown in formula (III);

[0026]

[0027] In formula (III), R 14 and R 15 independently selected from any one of a substituted or unsubstituted alkyl ether group, a 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 20Alkyl ether group, preferably C1~C 10 Alkyl ether group, more preferably C1-C5 alkyl ether group, more preferably methane ether group;

[0028] The Z is a heteroatom; in some embodiments, the Z is preferably O or S;

[0029] The R 14 and R 15 Not at the same time as hydrogen.

[0030] In some embodiments, A is selected from one of the structures of formula (III-1) to formula (III-11):

[0031]

[0032] In the chemical structural formula disclosed in the present invention, the bold or dotted groups represent the non-planarity caused by steric hindrance.

[0033] 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;

[0034] Furthermore, in the chiral gold (III) compound of the present invention, R1 to R 11 independently selected from substituted or unsubstituted C6 to 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;

[0035] 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; 11is selected from C1-C6 alkyl-substituted phenyl groups; R 12 is selected from substituted or unsubstituted C1-C5 alkyl ether or hydrogen;

[0036] 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; R 12 Selected from methane ether or hydrogen.

[0037] In some embodiments of the present invention, the chiral gold (III) compound of the present invention is:

[0038]

[0039]

[0040]

[0041] In the chemical structural formula disclosed in the present invention, the bold or dotted groups represent the non-planarity caused by steric hindrance.

[0042] The chiral gold (III) compound provided by the present invention exhibits thermally activated delayed fluorescence, has a shorter luminescence lifetime, and a higher decay rate, belongs to a circularly polarized luminescence material, can emit left-handed and right-handed circularly polarized light of a certain intensity, respectively, and can be applied to circularly polarized electroluminescent devices (CP-OLEDs).

[0043] 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 shown in formula (IV) and an aryl acetylene ligand having a structure shown in formula (V);

[0044]

[0045] X in the structure [Au(C^N^C)X] of formula (IV) of the present invention is selected from F, Cl or Br, preferably selected from Cl. R1 to R 11 and R1 to R 11 Same, no more elaboration.

[0046] In the aryl acetylene ligand of the structure shown in formula (V) of the present invention, R 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 a triisopropylsilyl group or a trimethylsilyl group. 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.

[0047] Specifically, the chiral gold (III) compound is prepared from components including [Au(C^N^C)X] of the structure shown in formula (IV), an aryl acetylene ligand of the structure shown in formula (V), a base, a catalyst, and an optional protecting group removing agent. More specifically, the preparation method of the chiral gold (III) compound of the present invention comprises: reacting [Au(C^N^C)X] of the structure shown in formula (IV), an aryl acetylene ligand of the structure shown in formula (V), a base, a catalyst, and an optional protecting group removing agent in an organic solvent under a protective gas atmosphere to obtain a chiral gold (III) compound.

[0048] 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) 16 When the aryl acetylene ligand R in the structure shown in formula (V) is 16 When 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).

[0049] 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.

[0050] In certain 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 [Au(C^N^C)X] of the structure shown in formula (IV) and the triisopropylsilane-protected aryl acetylene ligand of the structure shown in 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], the triisopropylsilane-protected aryl acetylene ligand, triethylamine, tetra-n-butylammonium fluoride and CuI is 1:1:1.5:1.5:0.1.

[0051] 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 aromatic acetylene ligand of the structure shown in 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 shown in 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], unprotected aromatic acetylene ligand, triethylamine and CuI is 1:1:1.1:1.1.

[0052] 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 shown in formula (IV) and the triisopropylsilane-protected aryl acetylene ligand of the structure shown in 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], the triisopropylsilane-protected aryl acetylene ligand, triethylamine, tetra-n-butylammonium fluoride and CuI is 1:1:1.5:1.5:0.1.

[0053] The present invention provides the use of the chiral gold (III) compound as 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.

[0054] The present invention also provides an organic electroluminescent device, comprising an anode, a cathode and a light-emitting layer disposed between the anode and the cathode, wherein the light-emitting layer comprises the chiral gold (III) compound or the chiral gold (III) compound prepared by the above-mentioned 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.

[0055] 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 shorter luminescence lifetime, and a higher 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 belongs to 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. The circularly polarized luminescent material also has potential application value in a wide range of fields such as planar 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 value 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 efficiency reached 11.2~18.1% respectively. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 TADF spectra of luminophores Au1 to Au3 measured in PMMA film;

[0057] Figure 2 TADF spectra of luminophores Au1 to Au3 measured in toluene;

[0058] Figure 3 TADF spectra of luminophores Au4 to Au6 measured in PMMA films or mCP;

[0059] Figure 4 TADF spectra of luminophores Au4 to Au6 measured in toluene;

[0060] Figure 5 Spectra of luminophore Au7 measured in PMMA film and toluene respectively;

[0061] Figure 6 is the absorption spectrum of Au4 and Au4-enantiomer measured in toluene;

[0062] Figure 7 TADF spectra of Au4 and Au4-enantiomer measured in toluene;

[0063] Figure 8 is the TADF spectrum of Au6-enantiomer measured in toluene;

[0064] Fig. 9 The electroluminescence spectrum of the light-emitting device based on the luminescent body Au4;

[0065] Fig.10 This is a test diagram of the external quantum efficiency of a light-emitting device based on the luminescent body Au4;

[0066] Fig.11 This is a brightness test chart of a light-emitting device based on the luminous body Au4;

[0067] Fig.12 is a current density diagram of a light-emitting device based on luminescent body Au4;

[0068] Fig.13 The electroluminescence spectrum of the light-emitting device based on the luminescent body Au5;

[0069] Fig.14 This is a test diagram of the external quantum efficiency of a light-emitting device based on the luminescent body Au5;

[0070] Fig.15 This is a brightness test chart of a light-emitting device based on the luminous body Au5;

[0071] Fig.16 is a current density diagram of a light-emitting device based on luminescent body Au5;

[0072] Fig.17 The electroluminescence spectrum of the light-emitting device based on the luminescent body Au6;

[0073] Fig.18 This is a test diagram of the external quantum efficiency of a light-emitting device based on the luminescent body Au6;

[0074] Fig.19 This is a brightness test chart of a light-emitting device based on the luminous body Au6;

[0075] Fig. 20 The current density diagram of the light-emitting device based on the luminescent body Au6. DETAILED DESCRIPTION

[0076] 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 article and appropriately improve the process parameters to achieve the above. It should be particularly 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 of this article without departing from the content, spirit and scope of the present invention to achieve and apply the technology of the present invention.

[0077] All luminescence lifetime tests of the present invention were conducted on the instrument "Quanta Ray GCR 150-10 pulsed Nd:YAG laser system" (laser wavelength: 355nm); at a fixed luminescence wavelength, the decay of luminescence intensity with time was observed, and the luminescence lifetime was measured according to Formula 1. Finally, the luminescence lifetime was measured using Origin software to fit the exponential decay.

[0078] 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.

[0079] Radiative decay rate constant (k r ) is calculated as shown in Formula 2:

[0080] k r =Φ / τFormula 2; in Formula 2, the luminescence quantum yield is Φ and the luminescence lifetime is τ.

[0081] The luminescence quantum yield was measured using an instrument “Hamamatsu C11347 Quantaurus-QY Absolute PLquantum yields measurement system”.

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

[0083] Example 1

[0084]

[0085] (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.

[0086] (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.

[0087] (3) Finally, Et2O is added to a proper amount of CH2Cl2 solution containing the complex for recrystallization to obtain the luminescent body Au1;

[0088] The structural formula of the luminescent body Au1 is The yield, appearance, hydrogen nuclear magnetic resonance spectrum and high-resolution mass spectrum data of the luminescent body Au1 are as follows:

[0089] Au1: Yield: 61 mg (62%, yellow solid).

[0090] 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);

[0091] HR-MS(EI):m / z calcd.for[C 39 H 21 AuF4N2O4] + [M] + :854.1097,found:854.1093.

[0092] Example 2

[0093]

[0094] (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.

[0095] (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.

[0096] (3) Finally, Et2O is added to a proper amount of CH2Cl2 solution containing the complex for recrystallization to obtain the luminescent body Au2;

[0097] The structural formula of the luminescent body Au2 is The yield, appearance, hydrogen nuclear magnetic resonance spectrum and high-resolution mass spectrum data of the luminescent body Au2 are as follows:

[0098] Au2: Yield: 69 mg (63%, yellow solid).

[0099] 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);

[0100] HR-MS(EI):m / z calcd.for[C 41 H 21 AuF4N2O6] + [M] + :910.0996,found:910.0987.

[0101] Example 3

[0102]

[0103] (1) Under argon protection, the aryl acetylene ligand (1 eqiuv.), 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.

[0104] (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.

[0105] (3) After the reaction, water is added to quench the reaction and a crude substance is precipitated. After filtering the crude substance, it is washed with water, EtOH and CH2Cl2 respectively. The obtained product is insoluble in most solvents, and the luminescent body Au3 is obtained;

[0106] The structural formula of the luminescent body Au3 is The yield, appearance and high-resolution mass spectrometry data of the luminophore Au3 are as follows:

[0107] Au3: Yield: 43 mg (55%, yellow solid).

[0108] HR-MS(ESI):m / z calcd.for[C 45 H 26 AuF4N2] + ,[M+H] + :867.1692,found:867.1671.

[0109] Example 4

[0110]

[0111] (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.

[0112] (2) After the reaction, the solvent is evaporated under reduced pressure, and the resulting crude material is purified by silica gel column chromatography to obtain luminescent material Au4; the structural formula of the luminescent material Au4 is The yield, appearance, hydrogen nuclear magnetic resonance spectrum and high-resolution mass spectrum data of the luminescent body Au4 are as follows:

[0113] Au4: Yield: 67 mg (68%, yellow solid).

[0114] 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).

[0115] HRMS(EI):m / z Calcd.for C 57 H 43 AuF6N2O6[M+H] + :1163.2769,found:1163.2712.

[0116] Example 5

[0117]

[0118] (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.

[0119] (2) After the reaction, the solvent is evaporated under reduced pressure, and the obtained crude material is purified by silica gel column chromatography to obtain luminescent body Au5; the structural formula of the luminescent body Au5 is The yield, appearance, hydrogen nuclear magnetic resonance spectrum and high-resolution mass spectrum data of the luminescent body Au5 are as follows:

[0120] Au5: Yield: 61 mg (62%, yellow solid).

[0121] 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).

[0122] HRMS(EI):m / z Calcd.for C 65 H 43 AuF6N2O4[M+H] + :1227.2871,found:1227.2824.

[0123] Example 6

[0124]

[0125] (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.

[0126] (2) After the reaction, the solvent is evaporated under reduced pressure, and the resulting crude material is purified by silica gel column chromatography to obtain luminescent material Au6; the structural formula of the luminescent material Au6 is The yield, appearance, hydrogen nuclear magnetic resonance spectrum and high-resolution mass spectrum data of the luminescent body Au6 are as follows:

[0127] Au6: Yield: 69 mg (63%, yellow solid).

[0128] 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).

[0129] HRMS(EI):m / z Calcd.for C 55 H 41 AuF6N2O4[M+H] + :1105.2714,found:1105.2675.

[0130] Example 7

[0131]

[0132] (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.

[0133] (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.

[0134] (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, hydrogen nuclear magnetic resonance spectrum and high-resolution mass spectrum data of the luminescent body Au7 are as follows:

[0135] Au7: Yield: 58 mg (61%, yellow solid).

[0136] 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);

[0137] HRMS(EI):m / z Calcd.for C 41 H 19 AuF4N2O2[M + ]:844.1048,found:844.1079.

[0138] The luminophores obtained in Examples 1 to 7 were subjected to photophysical characterization, and the results are shown in Table 1:

[0139] Table 1

[0140]

[0141] Table 1 shows the photophysical characterization data of luminophores Au1-Au6 in PMMA film, mCP or toluene, indicating that Au1-Au6 all exhibit a short luminescence lifetime (less than 3 μs) and a high radiation decay rate (k r In 10 5 s -1 In the range of 100 nm, these chiral gold (III) compounds have TADF luminescence characteristics. Au7 also has 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 state of deep red and near-infrared luminescent materials Au4 and Au6 will be mainly dominated by non-radiative transitions, resulting in a low corresponding luminescence quantum yield.

[0142] The luminophores of Examples 1 to 3 were subjected to spectral measurement. Figures 1-2 As shown, Figure 1 TADF spectra of luminophores Au1 to Au3 measured in PMMA film; Figure 2 is the TADF spectrum of luminophores Au1 to Au3 measured in toluene; Figures 1-2It can be seen that the TADF spectra of Au1~Au3 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 originates from the π-π* characteristic excited state in the main triple ligand.

[0143] The luminophores of Examples 4 to 6 were subjected to spectral measurement. Figures 3-4 As shown, Figure 3 TADF spectra of luminophores Au4 to Au6 measured in PMMA films or mCP; Figure 4 is the TADF spectrum of luminophores Au4 to Au6 measured in toluene; Figures 3-4 It can be seen that the TADF spectra of Au4~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 originates from the π-π* characteristic excited state in the main triple ligand.

[0144] The luminophore of Example 7 was subjected to spectral measurement, as shown in FIG. Figure 5 As shown, Figure 5 are the spectra of the luminescent body Au7 measured in PMMA film and toluene respectively; Figure 5 It can be seen that Au7 shows a structureless and broad peak curve in both PMMA film and toluene, but 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~Au6. This is due to the presence of two mutually fused benzene rings in the chiral ligand of Au7. It reflects that the difference in chiral ligands affects the phosphorescence of the excited state of the gold (III) compound Au7 in toluene, indicating that Au7 has partial phosphorescence properties.

[0145] The asymmetric factor analysis was performed on the luminescent body Au4 of Example 4, the medium being toluene, and the results are shown in Table 2;

[0146] Table 2

[0147] Enantiomers <![CDATA[g abs (l / nm) [a] ]]> <![CDATA[g lum (l / nm) [b] ]]> Au4-P1 <![CDATA[7.4×10 -4 (471)]]> <![CDATA[1.0×10 -4 (690)]]>

[0148] The absorption spectra of Au4 and Au4-enantiomer were measured in toluene as Figure 6 As shown, Figure 6 The absorption spectra of Au4 and Au4-enantiomer measured in toluene are shown in Figure 2. Figure 6 It is known that enantiomers involve the dichroism of circularly polarized light, that is, the different absorption of left-handed and right-handed light.

[0149] The TADF spectra of Au4 and Au4-enantiomers were measured in toluene as Figure 7 As shown, Figure 7 TADF spectra of Au4 and Au4-enantiomer measured in toluene. Figure 7 It can be seen that enantiomers can emit left-handed and right-handed circularly polarized light of a certain intensity respectively.

[0150] The TADF spectrum of the Au6-enantiomer was measured in toluene as Figure 8 As shown, Figure 8 The TADF spectrum of Au6-enantiomer measured in toluene. Figure 8 It can be seen that enantiomers can emit left-handed and right-handed circularly polarized light of a certain intensity respectively.

[0151] Example 8

[0152] 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, to obtain 4 light-emitting devices based on the luminescent body Au4.

[0153] 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 As shown, Fig. 9 This is the electroluminescence spectrum of the light-emitting device based on the luminescent body Au4. Fig.10 This is a test diagram of the external quantum efficiency of a light-emitting device based on the luminescent body Au4. Fig.11 This is a brightness test chart of a light-emitting device based on the luminous body Au4. Fig.12 The current density diagram of the light-emitting device based on the luminescent body Au4.

[0154] Table 3

[0155]

[0156]

[0157] Example 9

[0158] 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, to obtain three light-emitting devices based on the luminescent body Au5.

[0159] The performance data of the light-emitting device based on the luminescent body Au5 prepared above are shown in Table 4 and Figures 13-16 As shown, Fig.13 This is the electroluminescence spectrum of the light-emitting device based on the luminescent body Au5. Fig.14 This is a test diagram of the external quantum efficiency of a light-emitting device based on the luminescent body Au5. Fig.15 This is a brightness test chart of a light-emitting device based on the luminescent body Au5. Fig.16 The current density diagram of the light-emitting device based on the luminescent body Au5.

[0160] Table 4

[0161]

[0162] Example 10

[0163] 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, to obtain three light-emitting devices based on the luminescent body Au6.

[0164] The performance data of the light-emitting device based on the luminescent body Au6 prepared above are shown in Table 5 and Figures 17-20 As shown, Fig.17 This is the electroluminescence spectrum of the light-emitting device based on the luminescent body Au6. Fig.18 This is a test diagram of the external quantum efficiency of a light-emitting device based on the luminescent body Au6. Fig.19 This is a brightness test chart of a light-emitting device based on the luminescent body Au6. Fig. 20 The current density diagram of the light-emitting device based on the luminescent body Au6.

[0165] Table 5

[0166]

[0167] 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 present better device performance, and the performance of the light-emitting devices based on the luminous bodies Au4 to Au6 is better than that of the light-emitting devices based on the actual high brightness (1000 cd m -2 ), the external quantum efficiency is effectively increased 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 range).

[0168] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope 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 shown in formula (IV) and an aryl acetylene ligand having a structure shown in 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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