N, P isomeric cuprous tetra-coordinated compound based on bipyridino phenazine ligand as well as preparation method and application of N, P isomeric cuprous tetra-coordinated compound

Abstract

The invention discloses an N, P isomeric cuprous tetra-coordinated compound based on a bipyridino phenazine ligand as well as a preparation method and application of the N, P isomeric cuprous tetra-coordinated compound, and the compound is a [Cu (PP) (NN)] PF6 isomeric metal complex and has a structure as shown in a formula 1 or a formula 2. The metal complex adopts an isomeric nitrogen and phosphorus four-coordination structure, and the isomeric complex can absorb in a visible light region and can realize dehydrogenation cross coupling and other reactions through photocatalysis. According to the preparation method of the metal complex, the metal complex can be prepared with high yield through simple organic synthesis, the raw materials are easy to obtain, the cost is low, and the material prepared through the preparation method of the metal complex can be used for replacing current common precious metal complexes such as ruthenium, iridium and platinum.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal-organic coordination compounds, and particularly relates to a preparation method and application of an N,P-isomeric copper(I) tetracoordination compound based on a dipyridophenazine ligand. Background Art

[0002] Noble metals such as iridium and rhodium are often used in the field of organic electronics. However, they are costly, scarce, difficult to mine and refine, have low economic efficiency, poor sustainability, are toxic and harmful, and cause environmental pollution. These defects have led researchers to turn their attention to transition metals that are abundant, inexpensive, and environmentally friendly. In recent years, copper has been widely used in many fields such as organic fuels and photosensitive batteries. In the past three decades, luminescent materials have developed rapidly, from traditional fluorescence, phosphorescence, and triplet-triplet annihilation (TTA) materials to the era of the third-generation thermally activated delayed fluorescence (TADF) materials. Copper has a special electronic structure that is conducive to electron migration and transport, has high electrical conductivity, and can improve the efficiency and response speed of optoelectronic devices. Copper(I) complexes have ideal optoelectronic properties and can achieve efficient luminescence through the thermally activated delayed fluorescence mechanism, making them suitable for thermally activated delayed fluorescence (TADF) materials. Currently, copper is widely used in OLED materials. It can be seen that copper has great potential to replace noble metals such as iridium and platinum.

[0003] In the prior art, there are mainly two design strategies for [Cu(P^P)(N^N)]PF6 isomeric complexes: one is to increase the conjugation degree of imine ligands to enhance the light capture ability, thereby improving the luminescence quantum yield; the other is to use a diphosphine ligand with strong chelating properties and good rigidity to replace the monophosphine ligand, which can reduce the possibility of ligand dissociation and distortion and inhibit non-radiative quenching. Currently, most TADF-type [Cu(P^P)(N^N)]PF6 isomeric complexes have phenanthroline as the diazine ligand, and the research on extending the conjugation degree of imine ligands is much less than that of phenanthroline, which greatly limits the development of TADF-type copper complexes.

[0004] Therefore, a preparation method and application of an N,P-isomeric copper(I) tetracoordination compound based on a dipyridophenazine ligand are urgently needed to be proposed. Summary of the Invention

[0005] To solve the defects existing in the prior art, the present invention provides a preparation method and application of an N,P-isomeric copper(I) tetracoordination compound based on a dipyridophenazine ligand.

[0006] To solve the above technical problems, the present invention provides the following technical solutions:

[0007] The first object of the present invention is to provide an N,P isomeric copper(I) tetracoordinated compound based on a dipyridophenazine ligand, and the compound is an [Cu(P^P)(N^N)]PF6 isomeric metal complex having the structure of Formula 1 or Formula 2:

[0008]

[0009] Wherein, R1 is selected from substituted or unsubstituted C6-C 48 aryl, substituted or unsubstituted C4-C 48 heteroaryl.

[0010] Preferably, the phosphorus ligand in the metal complex is selected from one of the following structures:

[0011]

[0012] Preferably, R1 in the metal complex is selected from one of the following structures:

[0013]

[0014] Preferably, the metal complex has any of the following structures:

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022] The second object of the present invention is to provide a preparation method of an N,P isomeric copper(I) tetracoordinated compound based on a dipyridophenazine ligand, comprising the following steps:

[0023] Step 11: Reacting the bidentate nitrogen ligand 1,10-phenanthroline-5,6-dione with 4-bromo-o-phenylenediamine to generate an extended conjugated bidentate nitrogen ligand A;

[0024] Step 12: Performing a Suzuki coupling reaction on ligand A and R1 to obtain a bidentate nitrogen ligand B (two synthetic routes are provided here, and the catalysts, solvents, temperature, and time required for the two routes are different. When the reaction yield is low, another route can be tried for the reaction);

[0025] Step 13: Ligand B undergoes a coordination reaction with the bidentate phosphorus ligand XantPhos / POP / Binap to obtain the metal complex shown in Formula 1.

[0026] Preferably, the synthetic route of the metal complex is as follows:

[0027]

[0028] The third object of the present invention provides a preparation method of an N,P isomeric copper(I) tetracoordinated compound based on a dipyridophenazine ligand, including the following steps:

[0029] Step 21: React the bidentate nitrogen ligand 1,10-phenanthroline-5,6-dione with a diamine to generate the extended conjugated bidentate nitrogen ligand C;

[0030] Step 22: Ligand C undergoes a Suzuki coupling reaction with R1 to obtain the bidentate nitrogen ligand D;

[0031] Step 23: Ligand D undergoes a coordination reaction with the bidentate phosphorus ligand XantPhos / POP / Binap to obtain the metal complex shown in Formula 2.

[0032] Preferably, the synthetic route of the metal complex of Formula 2 is as follows:

[0033]

[0034] The fourth object of the present invention provides an application of an N,P isomeric copper(I) tetracoordinated compound based on a dipyridophenazine ligand. The [Cu(P^P)(N^N)]PF6 isomeric complex is used as a photocatalyst in the field of photocatalytic synthesis.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The present invention provides a novel [Cu(P^P)(N^N)]PF6 isomeric complex with TADF characteristics, which can be used as a substitute for precious metal complexes to promote photocatalytic organic synthesis.

[0037] The metal complex provided by the present invention adopts an isomeric nitrogen and phosphorus tetracoordinated structure, which can be prepared in high yield through simple organic synthesis, and the raw materials are easily available and the cost is low. Description of the Drawings

[0038] Figure 1 Absorption spectrum of [Cu(DMACDPPZ)(POP)]PF6 in a 1×10 -4 M tetrahydrofuran solution in Example 2;

[0039] Figure 2Absorption spectrum of [Cu(DPADPPZ)(POP)]PF6 in a tetrahydrofuran solution with a concentration of 1×10 -4 M in Example 2;

[0040] Figure 3 Absorption spectrum of [Cu(DMACDPPZ)(Binap)]PF6 in a 1,4-dioxane solution with a concentration of 1×10 -4 M in Example 2;

[0041] Figure 4 Absorption spectrum of [Cu(DPADPPZ)(Binap)]PF6 in a 1,4-dioxane solution with a concentration of 1×10 -4 M in Example 2;

[0042] Figure 5 Absorption spectrum of [Cu(DPADPPZ)(XantPhos)]PF6 in a 1,4-dioxane solution with a concentration of 1×10 -4 M in Example 2;

[0043] Figure 6 Emission spectrum of [Cu(DPADPPZ)(POP)]PF6 prepared in Example 2 doped with 2% in a PMMA film;

[0044] Figure 7 Emission spectrum of [Cu(DMACDPPZ)(XantPhos)]PF6 prepared in Example 2 doped with 2% in a PMMA film;

[0045] Figure 8 Emission spectrum of the solid powder of [Cu(DMACDPPZ)(POP)]PF6 prepared in Example 2. Detailed implementation mode

[0046] The preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0047] For those not specifying specific experimental steps or conditions in the examples, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments not specifying the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0048] The present invention provides a preparation method of an N,P isomeric copper(I) tetracoordination compound based on a dipyridophenazine ligand, including the following steps:

[0049] Step 1: React the bidentate nitrogen ligand 1,10-phenanthroline-5,6-dione with a diamine to generate the extended conjugated bidentate nitrogen ligand A or C;

[0050] Step 2: React ligand A or C with R1 through a Suzuki coupling reaction to obtain the bidentate nitrogen ligand B or D;

[0051] Step 3: React ligand B or D with the bidentate phosphorus ligand XantPhos / POP / Binap through a coordination reaction to obtain the compound shown in the structure of Formula 1 or Formula 2.

[0052] Example 1: Preparation of intermediates.

[0053] 1) Preparation of the intermediate dipyridophenazine ligand DPPZ(1). The synthesis route is as follows:

[0054]

[0055] Under a nitrogen atmosphere, 1,10-phenanthroline-5,6-dione (2.3 g, 10 mmol), 4-bromo-o-phenylenediamine (1.9 g, 10 mmol) and 60 mL of dry acetic acid solution were heated to 120 °C and refluxed for 24 h. After the reaction was stopped, it was cooled to room temperature, ice water was added, and filtration was carried out to obtain a gray solid. After washing the filter cake with ice water several times, it was placed in a vacuum dryer for drying to obtain a gray solid (yield 94%).

[0056] 2) Preparation of the intermediate DMAC-DPPZ(2). The synthesis route is as follows:

[0057]

[0058] The intermediate DPPZ (1.1 g, 3 mmol), 9,9-dimethylacridine (0.6 g, 3 mmol), tris(dibenzylideneacetone)dipalladium (0.092 g, 0.1 mmol), bis(2-diphenylphosphinophenyl)ether (0.054 g, 0.1 mmol) and cesium carbonate (3.9 g, 12 mmol) were dissolved in 40 mL of dry xylene mixed solution and heated to 110 °C under a nitrogen atmosphere and refluxed for 24 h. After the reaction was completed, water and dichloromethane were added to the cooled mixture. The organic layer was separated, dried over magnesium sulfate, concentrated in vacuo, and purified by column chromatography (dichloromethane / methanol = 80:1) and then crystallized to obtain an orange-red solid (yield 54%).

[0059] 3) Preparation of the intermediate DPA-DPPZ(3). The synthesis route is as follows:

[0060]

[0061] Intermediate DPPZ (1.92 g, 5.33 mmol), 4-(diphenylamino)phenylboronic acid pinacol ester (2.38 g, 6.41 mmol), tetrakis(triphenylphosphine)palladium (0.116 g, 0.1 mmol), potassium carbonate (1.47 g, 10.6 mmol), were heated to reflux at 105 °C for 12 h in a nitrogen atmosphere after dissolving in 50 mL of 1,4-dioxane and 50 mL of aqueous solution. After the reaction was completed, water and dichloromethane were added to the cooled mixture, the organic layer was separated, dried over magnesium sulfate, concentrated in vacuo, purified by column chromatography (dichloromethane / petroleum ether = 1:1), and then crystallized to obtain a dark red solid (yield 68%).

[0062] 4) Preparation of intermediate Cz-DPPZ (4). The synthetic route is as follows:

[0063]

[0064] Intermediate DPPZ (1.1 g, 3 mmol), carbazole (0.5 g, 3 mmol), tris(dibenzylideneacetone)dipalladium (0.092 g, 0.1 mmol), bis(2-diphenylphosphinophenyl)ether (0.054 g, 0.1 mmol) and cesium carbonate (3.9 g, 12 mmol), were heated to reflux at 110 °C for 24 h in a nitrogen atmosphere after dissolving in 40 mL of dry xylene mixed solution. After the reaction was completed, water and dichloromethane were added to the cooled mixture, the organic layer was separated, dried over magnesium sulfate, concentrated in vacuo, purified by column chromatography (dichloromethane / methanol = 80:1), and then crystallized to obtain a yellow solid (yield 62%).

[0065] 5) Preparation of intermediate TRZ-DPPZ. The synthetic route is as follows:

[0066]

[0067] Intermediate DPPZ (1.1 g, 3 mmol), phenoxazine (0.55 g, 3 mmol), tris(dibenzylideneacetone)dipalladium (0.092 g, 0.1 mmol), bis(2-diphenylphosphinophenyl)ether (0.054 g, 0.1 mmol) and cesium carbonate (3.9 g, 12 mmol), were heated to reflux at 110 °C for 24 h in a nitrogen atmosphere after dissolving in 40 mL of dry xylene mixed solution. After the reaction was completed, water and dichloromethane were added to the cooled mixture, the organic layer was separated, dried over magnesium sulfate, concentrated in vacuo, purified by column chromatography (dichloromethane / methanol = 80:1), and then crystallized to obtain a purplish red solid (yield 42%).

[0068] Example 2: Preparation of the complex.

[0069] 1) Preparation of the complex [Cu(DMACDPPZ)(XantPhos)]PF6. The synthetic route is as follows:

[0070]

[0071] Place the 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene compound (0.1157 g, 0.2 mmol) and copper(II) tetraethylcyanohexafluorophosphate (0.0754 g, 0.2 mmol) in a 100 mL two-necked flask. Add 25 mL of ultra-dry dichloromethane thereto and stir the reaction mixture at room temperature for 1 h. Then add the intermediate DMAC-DPPZ (0.0979 g, 0.2 mmol) and stir for 1 h. Filter the resulting suspension and collect the filtrate. Then remove the organic solvent by rotary evaporation to obtain the crude product, and purify it by recrystallization from dichloromethane / ether to obtain an orange-red product (yield 82%).

[0072] 2) Preparation of the complex [Cu(DPADPPZ)(XantPhos)]PF6. The synthetic route is as follows:

[0073]

[0074] Place the 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene compound (0.1157 g, 0.2 mmol) and copper(II) tetraethylcyanohexafluorophosphate (0.0754 g, 0.2 mmol) in a 100 mL two-necked flask. Add 25 mL of ultra-dry dichloromethane thereto and stir the reaction mixture at room temperature for 1 h. Then add the intermediate DPA-DPPZ (0.1051 g, 0.2 mmol) and stir for 1 h. Filter the resulting suspension and collect the filtrate. Then remove the organic solvent by rotary evaporation to obtain the crude product, and purify it by recrystallization from dichloromethane / ether to obtain a red product (yield 86%).

[0075] 3) Preparation of the complex [Cu(CzDPPZ)(XantPhos)]PF6. The synthetic route is as follows:

[0076]

[0077] Place the 4,5-bis(diphenylphosphino)-9,9-dimethyloxanthene compound (0.1157 g, 0.2 mmol) and copper(II) tetraethylcyanoaurate(III) hexafluorophosphate (0.0754 g, 0.2 mmol) in a 100 mL two-necked flask. Add 25 mL of ultradry dichloromethane thereto and stir the reaction mixture at room temperature for 1 h. Then add the intermediate Cz-DPPZ (0.1051 g, 0.2 mmol) and stir for 1 h. Filter the resulting suspension and collect the filtrate. Then remove the organic solvent by rotary evaporation to obtain the crude product, and purify it by recrystallization from dichloromethane / ether to obtain a yellow product (yield 79%).

[0078] 4) Preparation of the complex [Cu(DMACDPPZ)(POP)]PF6. The synthetic route is as follows:

[0079]

[0080] Place bis(2-diphenylphosphinoethyl) ether (0.0884 g, 0.2 mmol) and copper(II) tetraethylcyanoaurate(III) hexafluorophosphate (0.0754 g, 0.2 mmol) in a 100 mL two-necked flask. Add 25 mL of ultradry dichloromethane thereto and stir the reaction mixture at room temperature for 1 h. Then add the intermediate DMAC-DPPZ (0.0979 g, 0.2 mmol) and stir for 1 h. Filter the resulting suspension and collect the filtrate. Then remove the organic solvent by rotary evaporation to obtain the crude product, and purify it by recrystallization from dichloromethane / ether to obtain a red product (yield 89%).

[0081] 5) Preparation of the complex [Cu(DPADPPZ)(POP)]PF6. The synthetic route is as follows:

[0082]

[0083] Place bis(2-diphenylphosphinoethyl) ether (0.0884 g, 0.2 mmol) and copper(II) tetraethylcyanoaurate(III) hexafluorophosphate (0.0754 g, 0.2 mmol) in a 100 mL two-necked flask. Add 25 mL of ultradry dichloromethane thereto and stir the reaction mixture at room temperature for 1 h. Then add the intermediate DPA-DPPZ (0.1051 g, 0.2 mmol) and stir for 1 h. Filter the resulting suspension and collect the filtrate. Then remove the organic solvent by rotary evaporation to obtain the crude product, and purify it by recrystallization from dichloromethane / ether to obtain a dark red product (yield 89%).

[0084] 6) Preparation of the complex [Cu(DMACDPPZ)(Binap)]PF6. The synthetic route is as follows:

[0085]

[0086] 1,1'-Binaphthalene-2,2'-bis(diphenylphosphine) (0.0884 g, 0.2 mmol) and copper(II) tetraethylcyanoaurate(III) hexafluorophosphate (0.0754 g, 0.2 mmol) were placed in a 100 mL two-necked flask. 25 mL of ultra-dry dichloromethane was added thereto, and the mixture was stirred at room temperature for 1 h. Intermediate DMAC-DPPZ (0.0979 g, 0.2 mmol) was added and stirred for 1 h. The suspension after the reaction was filtered and the filtrate was collected. Then the organic solvent was removed by rotary evaporation to obtain a crude product, which was purified by recrystallization from dichloromethane / ether to obtain an orange-red product (yield 87%).

[0087] 7) Preparation of complex [Cu(DPADPPZ)(Binap)]PF6. The synthetic route is as follows:

[0088]

[0089] 1,1'-Binaphthalene-2,2'-bis(diphenylphosphine) (0.0884 g, 0.2 mmol) and copper(II) tetraethylcyanoaurate(III) hexafluorophosphate (0.0754 g, 0.2 mmol) were placed in a 100 mL two-necked flask. 25 mL of ultra-dry dichloromethane was added thereto, and the mixture was stirred at room temperature for 1 h. Intermediate DPA-DPPZ (0.1051 g, 0.2 mmol) was added and stirred for 1 h. The suspension after the reaction was filtered and the filtrate was collected. Then the organic solvent was removed by rotary evaporation to obtain a crude product, which was purified by recrystallization from dichloromethane / ether to obtain a dark red product (yield 89%).

[0090] Testing and characterization of the complex: The absorption and emission spectra of the complex solution in this example were tested (the results are shown in Figures 1 to 8 ), where the solution was a tetrahydrofuran solution or a 1,4-dioxane solution, and the concentration of the complex in the tetrahydrofuran solution was 1×10 -5 mol L -1 , and the concentration in the 1,4-dioxane solution was 1×10 -5 mol L -1 .

[0091] Application Example 1: Photocatalytic reductive dehalogenation reaction.

[0092] The synthetic route is as follows:

[0093]

[0094] [Cu(DMACDPPZ)(POP)]PF6 (10.3 mg, 0.05 mmol) and 4-chlorobiphenyl (188 mg, 1.00 mmol) were placed in an oven-dried vial. The vial was evacuated under high vacuum, backfilled with argon, and sealed with a rubber septum. Then, acetonitrile (10 mL) and iPr2NET (1.74 mL, 10.00 mmol) were added, and the reaction mixture was stirred for 68 h under green LED irradiation. The mixture was filtered through a pad (rinsed with EtOH) and concentrated under reduced pressure. The residue was then purified by flash chromatography on silica gel (petroleum ether) to afford the biphenyl as a white solid.

[0095] Application Example 2: Photocatalytic C-N coupling reaction.

[0096] 2-1 Photocatalytic realization of the C-N coupling of indole and 4-bromobenzonitrile, and its synthetic route is shown as follows:

[0097]

[0098] [Cu(DMACDPPZ)(POP)]PF6 (6.1 mg, 0.05 mmol), indole (29.3 mg, 0.25 mmol), 4-bromobenzonitrile (69.1 g, 0.38 mmol), and potassium tert-butoxide (42.6 mg, 1.5 eq) were placed in an oven-dried vial. The vial was evacuated under high vacuum, backfilled with argon, and sealed with a rubber septum. Then, dimethyl sulfoxide (4 mL) was added, and the reaction mixture was stirred for 24 h under green LED irradiation. After completion of the reaction, it was cooled to room temperature, diluted with ethyl acetate, washed with saturated ammonium chloride, dried over Na2SO4, filtered, and concentrated in vacuo. The resulting organic residue was purified by preparative thin-layer chromatography (ethyl acetate: petroleum ether = 1:10) to afford the product as a pale yellow oil.

[0099] 2-2 Photocatalytic realization of the C-N coupling of benzimidazole and 4-bromobenzonitrile, and its synthetic route is shown as follows:

[0100]

[0101] [Cu(DMACDPPZ)(POP)]PF6 (6.1 mg, 0.05 mmol), benzimidazole (29.5 mg, 0.25 mmol), 4-bromobenzonitrile (69.1 g, 0.38 mmol) and potassium tert-butoxide (42.6 mg, 1.5 eq) were placed in an oven-dried vial. The vial was evacuated under high vacuum, backfilled with argon, and sealed with a rubber septum. Then dimethyl sulfoxide (4 mL) was added, and the reaction mixture was stirred for 24 h under green LED irradiation. After completion of the reaction, it was cooled to room temperature, diluted with ethyl acetate, washed with saturated ammonium chloride, dried over Na2SO4, filtered, and concentrated in vacuo. The resulting organic residue was purified by preparative thin-layer chromatography (ethyl acetate: petroleum ether = 1:10) to give the product as a pale yellow oil.

[0102] Example 3

[0103] To achieve the above object, the present invention is realized by the following technical solutions: A preparation method of an N,P-isomeric copper(I) tetracoordination compound based on a pyrazino[2,3-f][1,10]phenanthroline ligand, comprising the following steps:

[0104] 1) Preparation of the intermediate pyrazino[2,3-f][1,10]phenanthroline DPQ (6), and its synthetic route is as follows:

[0105]

[0106] Under a nitrogen atmosphere, 1,10-phenanthroline-5,6-dione (2.3 g, 10 mmol) and diamine (1.9 g, 10 mmol) were added batchwise to 90 mL of water and 10 mL of 95% ethanol solution, and heated at 180 °C for 24 h under atmospheric pressure. After completion of the reaction, the reaction solution was cooled to room temperature, and needle-like crystals precipitated. It was filtered, rinsed with cold ethanol solution, suction-filtered, and dried (yield 74%).

[0107] 2) Preparation of the intermediate DMAC-DPQ (7), and its synthetic route is as follows:

[0108]

[0109] Intermediate DPQ (0.933 g, 3 mmol), 9,9-dimethylacridine (0.6 g, 3 mmol), tris(dibenzylideneacetone)dipalladium (0.092 g, 0.1 mmol), bis(2-diphenylphosphinophenyl)ether (0.054 g, 0.1 mmol) and cesium carbonate (3.9 g, 12 mmol) were dissolved in 40 mL of dry xylene in a nitrogen atmosphere and heated to 110 °C for reflux for 24 h. After the reaction was completed, water and dichloromethane were added to the cooled mixture. The organic layer was separated, dried over magnesium sulfate, concentrated in vacuo and purified by column chromatography (dichloromethane / methanol = 80:1) and then crystallized (yield 49%).

[0110] 3) Preparation of intermediate DPA-DPQ (8), and its synthesis route is as follows:

[0111]

[0112] Intermediate DPQ (1.66 g, 5.33 mmol), 4-(diphenylamino)phenylboronic acid pinacol ester (2.38 g, 6.41 mmol), tetrakis(triphenylphosphine)palladium (0.116 g, 0.1 mmol), potassium carbonate (1.47 g, 10.6 mmol) were dissolved in 50 mL of 1,4-dioxane and 50 mL of aqueous solution in a nitrogen atmosphere and heated to 105 °C for reflux for 12 h. After the reaction was completed, water and dichloromethane were added to the cooled mixture. The organic layer was separated, dried over magnesium sulfate, concentrated in vacuo and purified by column chromatography (dichloromethane / petroleum ether = 1:1) and then crystallized. (Yield 57%)

[0113] Example 4: Preparation of the complex.

[0114] 1) Preparation of complex [Cu(DMACDPQ)(POP)]PF6, and its synthesis route is as follows:

[0115]

[0116] Bis(2-diphenylphosphino)ethyl]ether (0.0884 g, 0.2 mmol) and copper(II) tetracyanoethylene hexafluorophosphate (0.0754 g, 0.2 mmol) were placed in a 100 mL two-necked flask, 25 mL of ultradry dichloromethane was added thereto, and the mixture was stirred at room temperature for 1 h. Intermediate DMAC-DPQ (0.0879 g, 0.2 mmol) was added and stirred for 1 h. The suspension after the reaction was filtered and the filtrate was collected. Then the organic solvent was removed by rotary evaporation to obtain the crude product, and the product was purified by recrystallization with dichloromethane / ether (yield 77%).

[0117] 2) Preparation of the complex [Cu(DPADPQ)(POP)]PF6, and its synthetic route is as follows:

[0118]

[0119] Bis(2-diphenylphosphino)ethyl] ether (0.0884 g, 0.2 mmol) and copper(II) tetrakis(acetonitrile)hexafluorophosphate (0.0754 g, 0.2 mmol) were placed in a 100 mL two-necked flask. 25 mL of ultra-dry dichloromethane was added thereto, and the mixture was stirred at room temperature for 1 h. Intermediate DPA-DPQ (0.0951 g, 0.2 mmol) was added and stirred for 1 h. The suspension after the reaction was filtered and the filtrate was collected. Then the organic solvent was removed by rotary evaporation to obtain the crude product, and the product was purified by recrystallization from dichloromethane / ether (yield 81%).

[0120] 3) Preparation of the complex [Cu(DMACDPQ)(XantPhos)]PF6, and its synthetic route is as follows:

[0121]

[0122] 4,5-Bis(diphenylphosphino)-9,9-dimethyloxanthene compound (0.1157 g, 0.2 mmol) and copper(II) tetrakis(acetonitrile)hexafluorophosphate (0.0754 g, 0.2 mmol) were placed in a 100 mL two-necked flask. 25 mL of ultra-dry dichloromethane was added thereto, and the mixture was stirred at room temperature for 1 h. Intermediate DMAC-DPQ (0.0879 g, 0.2 mmol) was added and stirred for 1 h. The suspension after the reaction was filtered and the filtrate was collected. Then the organic solvent was removed by rotary evaporation to obtain the crude product, and the product was purified by recrystallization from dichloromethane / ether (yield 83%).

[0123] 4) Preparation of the complex [Cu(DMACDPQ)(Binap)]PF6, and its synthetic route is as follows:

[0124]

[0125] 1,1'-Binaphthalene-2,2'-bis(diphenylphosphine) (0.0884 g, 0.2 mmol) and copper(II) tetrakis(acetonitrile)hexafluorophosphate (0.0754 g, 0.2 mmol) were placed in a 100 mL two-necked flask. 25 mL of ultra-dry dichloromethane was added thereto, and the mixture was stirred at room temperature for 1 h. Intermediate DMAC-DPQ (0.0879 g, 0.2 mmol) was added and stirred for 1 h. The suspension after the reaction was filtered and the filtrate was collected. Then the organic solvent was removed by rotary evaporation to obtain the crude product, and the product was purified by recrystallization from dichloromethane / ether (yield 86%).

[0126] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An N,P-isomeric copper(I) tetracoordination compound based on a dipyridophenazine ligand, characterized in that, The compound is a [Cu(P^P)(N^N)]PF6 isomeric metal complex, which has the structure of Formula 1 or Formula 2: Among them, R1 is selected from substituted or unsubstituted C6-C 48 aryl, substituted or unsubstituted C4-C 48 heteroaryl.

2. The N,P-isomeric copper(I) tetracoordination compound based on dipyridophenazine ligand according to claim 1, characterized in that, The phosphorus ligand in the metal complex is selected from one of the following structures:

3. The N,P isomeric copper(I) tetracoordination compound based on dipyridophenazine ligand according to claim 1, characterized in that, R1 in the metal complex is selected from one of the following structures:

4. The N,P-isomeric copper(I) four-coordinate compound based on a dipyridophenazine ligand according to claim 1, wherein The metal complex has any of the following structures:

5. A preparation method of an N,P isomeric copper(I) tetracoordination compound based on a dipyridino-phenazine ligand as described in any one of claims 1-4, characterized in that, It includes the following steps: Step 11: React the bidentate nitrogen ligand 1,10-phenanthroline-5,6-dione with 4-bromo-o-phenylenediamine to generate the extended conjugated bidentate nitrogen ligand A; Step 12: Ligand A and R1 undergo a Suzuki coupling reaction to obtain the bidentate nitrogen ligand B; Step 13: Ligand B undergoes a coordination reaction with the bidentate phosphorus ligand XantPhos / POP / Binap to obtain the metal complex shown in Formula 1.

6. The preparation method of the N,P isomeric copper(I) tetracoordination compound based on dipyrido[3,2-a:2',3'-c]phenazine ligand according to claim 5, characterized in that, The synthetic route of the metal complex is as follows: Route 1 Route 2 7. A preparation method of an N,P isomeric copper(I) tetracoordination compound based on a dipyridino-phenazine ligand as described in any one of claims 1-4, characterized in that, It includes the following steps: Step 21: React the bidentate nitrogen ligand 1,10-phenanthroline-5,6-dione with a diamine to generate the extended conjugated bidentate nitrogen ligand C; Step 22: Ligand C and R1 undergo a Suzuki coupling reaction to obtain the bidentate nitrogen ligand D; Step 23: Ligand D undergoes a coordination reaction with the bidentate phosphorus ligand XantPhos / POP / Binap to obtain the metal complex shown in Formula 2 through a coordination reaction.

8. The preparation method of the N,P isomeric copper(I) tetracoordination compound based on dipyridophenazine ligand according to claim 7, characterized in that, The synthetic route of the metal complex of Formula 2 is as follows:

9. Use of an N,P-isomeric copper(I) tetracoordination compound based on a dipyridophenazine ligand as described in any one of claims 1-4, characterized in that, The [Cu(P^P)(N^N)]PF6 isomeric complex is applied as a photocatalyst in the field of photocatalytic synthesis.

Images