Aza carbene metal complex based on hexa carbon helicene skeleton, intermediate and preparation method thereof

Abstract

The present application relates to the technical field of synthetic chemistry, in particular to a kind of nitrogen heterocyclic carbene metal complex based on six-membered carbon helicene skeleton, intermediate and preparation method thereof. The present application takes 2,7-dimethylnaphthalene as starting material, and a series of reactions are carried out to synthesize bidentate carbon six helicene imidazolium salt compound, i.e. intermediate of nitrogen heterocyclic carbene metal complex based on six-membered carbon helicene skeleton. The intermediate is combined with silver oxide to synthesize nitrogen heterocyclic carbene metal silver complex based on six-membered carbon helicene skeleton. The nitrogen heterocyclic carbene metal silver complex based on six-membered carbon helicene skeleton is reacted with tetrahydrothiophene gold (I) chloride to obtain nitrogen heterocyclic carbene metal gold complex based on six-membered carbon helicene skeleton. Two kinds of nitrogen heterocyclic carbene metal complexes based on six-membered carbon helicene skeleton enrich the types of helicene-based nitrogen heterocyclic carbene metal complexes, and promote the application of helicene-based nitrogen heterocyclic carbene metal complexes in the field of optoelectronics.

Description

Technical Field

[0001] The present invention relates to the technical field of synthetic chemistry, and in particular to an azacarbene metal complex based on a six-membered carbon helicene skeleton, an intermediate and a preparation method thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

[0003] Since the first metal-N-heterocyclic carbene complex was reported in 1968, metal N-heterocyclic carbene (NHC) chemistry has developed extensively. The unique electronic and steric effects of N-heterocyclic carbenes on metal centers have led to the widespread application of metal-N-heterocyclic carbene complexes in catalysis, biomedicine, and materials science. To date, although many metal-N-heterocyclic carbene compounds have been reported, they have primarily focused on simple structures such as organometallic rings, molecular cylinders, and molecular tweezers, which are constructed simply by binding bidentate, tridentate, or polydentate N-heterocyclic carbene ligands to metal ions.

[0004] Helicenes are a class of non-planar helical molecules typically composed of multiple aromatic or heteroaromatic rings fused in ortho positions. Due to their unique twisted structure, these molecules have important applications in materials science, molecular recognition, and asymmetric catalysis. While a series of helicene-based nitrogen-carbene metal complexes have been published, their relatively simple structures have limited their application in various fields. Summary of the Invention

[0005] In order to overcome the above problems, the present invention provides an azacarbene metal complex based on a six-membered carbon helicene skeleton, an intermediate and a preparation method thereof.

[0006] In order to achieve the above technical objectives, the present invention adopts the following technical solutions:

[0007] In the first aspect of the present invention, there is provided an intermediate of an azacarbene metal complex based on a six-membered carbon helicene skeleton, the structural formula of which is shown in Formula I.

[0008]

[0009] The second aspect of the present invention provides a method for preparing the intermediate of the above-mentioned azacarbene metal complex based on a six-membered carbon helicene skeleton, comprising:

[0010] Compound 1 was synthesized from 2,7-dimethylnaphthalene in the presence of a brominating agent; Compound 1 underwent an Arbuzov reaction with triethyl phosphite to synthesize Compound 2; Compound 2 underwent condensation with p-bromobenzaldehyde to synthesize Compound 3; Compound 3 underwent photoaddition reaction with propylene oxide and elemental iodine to synthesize Compound 4; Compound 4 underwent a substitution reaction with imidazole under alkaline conditions to synthesize Compound 5; Compound 5 underwent a reaction with 1-bromobutane to synthesize Compound 6; Compound 6 underwent an ion exchange reaction with ammonium hexafluorophosphate to synthesize an intermediate of an azacarbene metal complex based on a six-membered carbon helicene skeleton;

[0011] Reaction route:

[0012]

[0013] The third aspect of the present invention provides the use of the intermediate of the above-mentioned azacarbene metal complex based on a six-membered carbon helicene skeleton in the preparation of an azacarbene metal complex based on a six-membered carbon helicene skeleton.

[0014] The fourth aspect of the present invention provides an azacarbene metal complex based on a six-membered carbon helicene skeleton, the structural formula of which is shown in Formula II or Formula III.

[0015]

[0016] The R groups in formula II or III are the same, both being n-butyl groups (nBu).

[0017] The fifth aspect of the present invention provides a method for preparing the above-mentioned azacarbene metal complex based on a six-membered carbon helicene skeleton, comprising:

[0018] The intermediate of the azacarbene metal complex based on a six-membered carbon helicene skeleton described in the first aspect is reacted with silver oxide to obtain the azacarbene metal complex based on a six-membered carbon helicene skeleton as shown in Formula II;

[0019] The azacarbene metal complex based on a six-membered carbon helicene skeleton shown in formula II is reacted with tetrahydrothiophene gold chloride to obtain the azacarbene metal complex based on a six-membered carbon helicene skeleton shown in formula III.

[0020] The sixth aspect of the present invention provides an intermediate of the nitrogen carbene metal complex based on a six-membered carbon helicene skeleton described in the first aspect and the use of the nitrogen carbene metal complex based on a six-membered carbon helicene skeleton described in the fourth aspect in the preparation of optoelectronic devices.

[0021] The beneficial effects of the present invention are:

[0022] The present invention provides two azacarbene metal complexes based on a six-membered carbon helicene skeleton. Using 2,7-dimethylnaphthalene as a starting material, a bidentate carbon hexahelicene imidazolium salt compound, i.e., an intermediate of the azacarbene metal complex based on a six-membered carbon helicene skeleton, is synthesized through a series of reactions. This intermediate is reacted with silver oxide to synthesize an azacarbene metal silver complex based on a six-membered carbon helicene skeleton. The azacarbene metal silver complex based on a six-membered carbon helicene skeleton is then reacted with tetrahydrothiophene gold chloride to obtain an azacarbene metal gold complex based on a six-membered carbon helicene skeleton. The intermediate of the azacarbene metal complex based on a six-membered carbon helicene skeleton and the two azacarbene metal complexes based on a six-membered carbon helicene skeleton in the present invention all have ultraviolet absorption and fluorescence emission capabilities, and therefore have great application potential in optoelectronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The accompanying drawings, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0024] Figure 1 is the H NMR spectrum of compound 2;

[0025] Figure 2 is the C NMR spectrum of compound 2;

[0026] Figure 3 is the H NMR spectrum of compound 5;

[0027] Figure 4 is the C NMR spectrum of compound 5;

[0028] Figure 5 is the H NMR spectrum of compound 7;

[0029] Figure 6 is the C NMR spectrum of compound 7;

[0030] Figure 7 Schematic diagram of the single crystal structure of the nitrogen-carbene metal silver complex based on the six-membered carbon helicene skeleton;

[0031] Figure 8 Schematic diagram of the single crystal structure of the nitrogen-carbene metal gold complex based on the six-membered carbon helicene skeleton; Figure 9 Ultraviolet absorption images of the intermediate of nitrogen carbene metal complex based on six-membered carbon helicene skeleton, nitrogen carbene metal silver complex based on six-membered carbon helicene skeleton, and nitrogen carbene metal gold complex based on six-membered carbon helicene skeleton;

[0032] Figure 10These are the fluorescence emission images of the intermediate of the nitrogen carbene metal complex based on the six-membered carbon helicene skeleton, the nitrogen carbene metal silver complex based on the six-membered carbon helicene skeleton, and the nitrogen carbene metal gold complex based on the six-membered carbon helicene skeleton. DETAILED DESCRIPTION

[0033] It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0034] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0035] The first typical embodiment of the present invention provides an intermediate of an azacarbene metal complex based on a six-membered carbon helicene skeleton, the structural formula of which is shown in Formula I.

[0036]

[0037] A second typical embodiment of the present invention provides a method for preparing an intermediate of the above-mentioned azacarbene metal complex based on a six-membered carbon helicene skeleton, comprising:

[0038] Compound 1 was synthesized from 2,7-dimethylnaphthalene in the presence of a brominating agent; Compound 1 underwent an Arbuzov reaction with triethyl phosphite to synthesize Compound 2; Compound 2 underwent condensation with p-bromobenzaldehyde to synthesize Compound 3; Compound 3 underwent photoaddition reaction with propylene oxide and elemental iodine to synthesize Compound 4; Compound 4 underwent a substitution reaction with imidazole under alkaline conditions to synthesize Compound 5; Compound 5 underwent a reaction with 1-bromobutane to synthesize Compound 6; Compound 6 underwent an ion exchange reaction with ammonium hexafluorophosphate to synthesize an intermediate of an azacarbene metal complex based on a six-membered carbon helicene skeleton;

[0039] Reaction route:

[0040]

[0041] In one or more embodiments, the method for synthesizing Compound 1 from 2,7-dimethylnaphthalene under the action of a brominating agent comprises:

[0042] Under anhydrous and oxygen-free conditions, 2,7-dimethylnaphthalene, N-bromosuccinimide and dibenzoyl peroxide were dispersed in benzene, respectively, and heated under reflux with stirring to react and synthesize compound 1.

[0043] Preferably, the molar ratio of 2,7-dimethylnaphthalene, N-bromosuccinimide and dibenzoyl peroxide is 1:1.8-2.5:0.04-0.06, preferably 1:2.2:0.05.

[0044] Preferably, the concentration of 2,7-dimethylnaphthalene in benzene is 0.05 to 0.07 mol / L, preferably 0.064 mol / L.

[0045] Preferably, the temperature for heating under reflux and stirring is 90 to 110° C., preferably 100° C.; the time for heating under reflux and stirring is 10 to 15 h, preferably 12 h.

[0046] In one or more embodiments, the method for synthesizing compound 2 by reacting compound 1 with triethyl phosphite to form an Arbuzov reaction comprises:

[0047] Compound 1 was dispersed in triethyl phosphite, and the mixture was heated under reflux and stirred to react to synthesize compound 2.

[0048] Preferably, the molar ratio of compound 1 to triethyl phosphite is 1:3.5-5, preferably 1:4.

[0049] Preferably, the temperature for heating under reflux and stirring is 120-150° C., preferably 130° C.; the time for heating under reflux and stirring is 5-8 h, preferably 6 h.

[0050] In one or more embodiments, the method for synthesizing compound 3 by condensing compound 2 with p-bromobenzaldehyde comprises:

[0051] Under anhydrous and oxygen-free conditions, compound 2, p-bromobenzaldehyde and sodium hydride were dispersed in anhydrous tetrahydrofuran, and heated and stirred to react to synthesize compound 3.

[0052] Preferably, the molar ratio of compound 2, p-bromobenzaldehyde and sodium hydride is 1:2.5-3.5:7-10, preferably 1:3:8.

[0053] Preferably, the concentration of compound 2 in anhydrous tetrahydrofuran is 0.05 to 0.12 mol / L, preferably 0.0117 mol / L.

[0054] Preferably, the temperature for heating and stirring is 40 to 60° C., preferably 50° C.; and the time for heating and stirring is 6 to 8 hours, preferably 6 hours.

[0055] In one or more embodiments, the method for synthesizing compound 4 by photoaddition reaction of compound 3 with propylene oxide and elemental iodine comprises:

[0056] Compound 3, propylene oxide and iodine were dispersed in toluene respectively, and reacted under high-pressure mercury lamp to synthesize compound 4.

[0057] Preferably, the molar ratio of compound 3, propylene oxide and elemental iodine is 1:600-800:2.5-4, preferably 1:715:3.

[0058] Preferably, the wavelength of the high-pressure mercury lamp is 365 nm.

[0059] Preferably, the illumination time is 20 to 30 hours, preferably 24 hours.

[0060] In one or more embodiments, compound 4 undergoes a substitution reaction with imidazole under alkaline conditions to synthesize compound 5, comprising:

[0061] Under anhydrous and oxygen-free conditions, compound 4, imidazole, copper oxide and anhydrous potassium carbonate were dispersed in anhydrous dimethyl sulfoxide, respectively, and heated and stirred to react to synthesize compound 5.

[0062] Preferably, the molar ratio of compound 4, imidazole, copper oxide and anhydrous potassium carbonate is 1:14-18:0.8-1.2:14-18, preferably 1:16:1:16.

[0063] Preferably, the concentration of compound 4 in anhydrous dimethyl sulfoxide is 0.04 to 0.06 mol / L, preferably 0.05 mol / L.

[0064] Preferably, the temperature for heating and stirring is 140 to 160° C., preferably 150° C.; and the time for heating and stirring is 40 to 60 h, preferably 48 h.

[0065] In one or more embodiments, the reaction of compound 5 and 1-bromobutane to synthesize compound 6 includes:

[0066] Compound 5 and 1-bromobutane were dispersed in N,N-dimethylformamide (DMF), and heated and stirred to react to synthesize compound 6.

[0067] Preferably, the molar ratio of compound 5 to 1-bromobutane is 1:18 to 22, preferably 1:20.

[0068] Preferably, the concentration of compound 5 in N,N-dimethylformamide is 8.3-10 g / L, preferably 10 g / L.

[0069] Preferably, the temperature for heating and stirring is 100-120° C., preferably 110° C.; the time for heating and stirring is 20-30 h, preferably 24 h.

[0070] In one or more embodiments, the method for synthesizing an intermediate of an azacarbene metal complex based on a six-membered carbon helicene skeleton by an ion exchange reaction between compound 6 and ammonium hexafluorophosphate comprises:

[0071] Compound 6 and ammonium hexafluorophosphate were dispersed in methanol and stirred at room temperature to react to synthesize an intermediate of an azacarbene metal complex based on a six-membered carbon helicene skeleton.

[0072] Preferably, the molar ratio of compound 6 to ammonium hexafluorophosphate is 1:6 to 10, preferably 1:8.

[0073] Preferably, the concentration of ammonium hexafluorophosphate in methanol is 0.03 to 0.05 mol / L, preferably 0.04 mol / L.

[0074] Preferably, the stirring reaction time at room temperature is 7 to 10 hours, preferably 8 hours.

[0075] A third typical embodiment of the present invention provides the use of the intermediate of the above-mentioned azacarbene metal complex based on a six-membered carbon helicene skeleton in the preparation of an azacarbene metal complex based on a six-membered carbon helicene skeleton.

[0076] A fourth typical embodiment of the present invention provides an azacarbene metal complex based on a six-membered carbon helicene skeleton, the structural formula of which is shown in Formula II or Formula III.

[0077]

[0078] The R groups in formula II or formula III are the same, both being n-butyl groups (nBu).

[0079] A fifth typical embodiment of the present invention provides a method for preparing the above-mentioned azacarbene metal complex based on a six-membered carbon helicene skeleton, comprising:

[0080] The intermediate of the azacarbene metal complex based on a six-membered carbon helicene skeleton described in the first aspect is reacted with silver oxide to obtain the azacarbene metal complex based on a six-membered carbon helicene skeleton as shown in Formula II;

[0081] The azacarbene metal complex based on a six-membered carbon helicene skeleton shown in formula II is reacted with tetrahydrothiophene gold chloride to obtain the azacarbene metal complex based on a six-membered carbon helicene skeleton shown in formula III.

[0082] In one or more embodiments, the method of reacting the intermediate of the azacarbene metal complex based on the six-membered carbon helicene skeleton described in the first aspect with silver oxide to obtain the azacarbene metal complex based on the six-membered carbon helicene skeleton shown in Formula II comprises:

[0083] Under anhydrous and oxygen-free conditions, the intermediate of the azacarbene metal complex based on the six-membered carbon helicene skeleton described in the first aspect and silver oxide are dispersed in anhydrous acetonitrile, and the reaction is heated and stirred under light-proof conditions to obtain the azacarbene metal complex based on the six-membered carbon helicene skeleton shown in Formula II.

[0084] Preferably, the molar ratio of the intermediate of the azacarbene metal complex based on the six-membered carbon helicene skeleton to silver oxide is 1:2-3, preferably 1:2.5.

[0085] Preferably, the concentration of the intermediate of the azacarbene metal complex based on a six-membered carbon helicene skeleton in anhydrous acetonitrile is 0.25 to 0.32 mmol / L, preferably 0.29 mmol / L.

[0086] Preferably, the temperature for heating and stirring is 70 to 100° C., preferably 80° C.; the time for heating and stirring is 20 to 30 h, preferably 24 h.

[0087] In one or more embodiments, the method of reacting the azacarbene metal complex based on the six-membered carbon helicene skeleton shown in Formula II with tetrahydrothiophene gold chloride to obtain the azacarbene metal complex based on the six-membered carbon helicene skeleton shown in Formula III includes:

[0088] Under anhydrous and oxygen-free conditions, an azacarbene metal complex based on a six-membered carbon helicene skeleton as shown in formula II and tetrahydrothiophene gold chloride are dispersed in anhydrous acetonitrile, and the reaction is stirred at room temperature in the dark to obtain an azacarbene metal complex based on a six-membered carbon helicene skeleton as shown in formula III.

[0089] Preferably, the molar ratio of the azacarbene metal complex based on the six-membered carbon helicene skeleton shown in Formula II to tetrahydrothiophene gold chloride is 1:2-3, preferably 1:2.4.

[0090] Preferably, the concentration of the azacarbene metal complex based on a six-membered carbon helicene skeleton shown in Formula II in anhydrous acetonitrile is 0.8 to 1.2 mmol / L, preferably 0.95 mmol / L.

[0091] Preferably, the stirring reaction time at room temperature is 20 to 30 hours, preferably 24 hours.

[0092] The sixth typical embodiment of the present invention provides an intermediate of the nitrogen carbene metal complex based on a six-membered carbon helicene skeleton described in the first aspect and the use of the nitrogen carbene metal complex based on a six-membered carbon helicene skeleton described in the fourth aspect in the preparation of optoelectronic devices.

[0093] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0094] Example 1

[0095] Preparation of compound 1:

[0096] Under anhydrous and oxygen-free conditions, 2,7-dimethylnaphthalene (1.0 g, 6.4 mmol, 1.0 equiv.), N-bromosuccinimide (2.51 g, 14.1 mmol, 2.2 equiv.), dibenzoyl peroxide (77.5 mg, 0.32 mmol, 0.05 equiv.), and 50 mL of benzene were added to a 100 mL Schlenk flask and stirred under reflux at 100°C for 12 h. After the reaction, the mixture was cooled to room temperature and filtered. The filtrate was then subjected to a rotary evaporator to remove the solvent. A trace amount of chloroform was added to dissolve the mixture, and a large amount of n-hexane was added to precipitate the precipitate. The precipitate was recrystallized at -18°C, filtered, and dried. The product was washed with ether and dried in vacuo to obtain 730 mg of a white solid powder with a yield of 72.6%. 1 HNMR (400MHz, CDCl3): δ=7.82 (d, J=9.1Hz, 2H), 7.52 (d, J=9.1Hz, 2H), 7.29 (s, 2H), 4.65ppm (s, 4H).

[0097] Example 2

[0098] Preparation of compound 2:

[0099] Compound 1 (1.0 g, 3.18 mmol, 1.0 equiv.) and triethyl phosphite (2.1 g, 12.7 mmol, 4.0 equiv.) were added to a 50 mL Schlenk flask and stirred under reflux at 130°C for 6 h. Upon completion of the reaction, the excess triethyl phosphite was removed by vacuum distillation to yield 1.57 g of a yellow oily liquid with a yield of 84.8%. 1 H NMR (400MHz, CDCl3): δ = 7.76 (d, J = 8.4Hz, 2H), 7.69 (s, 2H), 7.41 (d, J = 8.4Hz, 2H),4.07-3.95(m,8H),3.33(s,2H),3.27(s,2H),1.23ppm(t,J=7.06Hz,12H).13 C{ 1 H} NMR (100MHz, CDCl3): δ = 132.4, 130.1, 128.6, 127.1, 126.8, 61.0, 33.4, 32.1, 15.3ppm.

[0100] The H NMR spectrum of compound 2 is shown in Figure 1 As shown, the NMR carbon spectrum is as follows Figure 2 shown.

[0101] Example 3

[0102] Preparation of compound 3:

[0103] Under anhydrous and oxygen-free conditions, compound 2 (0.5 g, 1.17 mmol, 1.0 equiv.) was dissolved in 10 mL of anhydrous tetrahydrofuran and added to a 100 mL Schlenk flask. p-Bromobenzaldehyde (650 mg, 3.51 mmol, 3.0 equiv.) was then dissolved in 20 mL of anhydrous tetrahydrofuran and added to the reaction flask. The reaction was heated and stirred at 50°C for 10 min. A solution of sodium hydride (224.1 mg, 9.34 mmol, 8.0 equiv.) in tetrahydrofuran was then added to the reaction flask. The reaction was continued at 50°C for 6 h, during which time a precipitate gradually formed. Upon completion of the reaction, deionized water was slowly added to neutralize the excess sodium hydride, generating bubbles. After the bubbles subsided, a large amount of deionized water was added, the mixture was filtered, drained, and dried under vacuum. 423.1 mg of a yellow solid powder was obtained with a yield of 73.9%. 1 HNMR (400MHz, CDCl3): δ = 7.64-7.53 (m, 4H), 7.52-7.41 (m, 2H), 7.32 (d, J = 8.0Hz, 4H), 7.18 (d, J = 8.0Hz, 4H), 6.72-6.63ppm (m, 4H).

[0104] Example 4

[0105] Preparation of compound 4

[0106] Compound 3 (20 mg, 0.04 mmol, 1.0 equiv.) was added to a 100 mL photoreaction tube, followed by 50 mL of toluene and stirring for 10 minutes. Iodine (30 mg, 0.12 mmol, 3.0 equiv.), 2 mL of propylene oxide (28.6 mmol), and 40 mL of toluene were then added. The photoreaction tube was illuminated under a 365 nm high-pressure mercury lamp for 24 hours. After the reaction, excess iodine was removed with saturated anhydrous sodium sulfite solution, causing the solution to change from red to light yellow. The organic phase was then extracted and collected, the toluene solvent removed by vacuum distillation, and the mixture was filtered, drained, and dried under vacuum to yield 18 mg of a yellow solid powder with a yield of 90.7%. 1 H NMR (400MHz, CDCl3): δ=8.06-7.90(m,8H),7.74(d,J=8.5Hz,2H),7.71(d,J=2.0Hz,2H),7.39(dd,J=8.5,2.0Hz,2H).

[0107] Example 5

[0108] Preparation of compound 5:

[0109] Under anhydrous and oxygen-free conditions, compound 4 (50 mg, 0.1 mmol, 1.0 equiv.) was dissolved in 2 mL of anhydrous dimethyl sulfoxide (DMSO) and placed in a 10 mL Schlenk tube. Imidazole (112.0 mg, 1.63 mmol, 16.0 equiv.), copper oxide (8.18 mg, 0.1 mmol, 1.0 equiv.), and anhydrous potassium carbonate (227.4 mg, 1.65 mmol, 16.0 equiv.) were then added to the reaction tube. The reaction was incubated at 150°C for 48 h, during which time the solution turned from a pale yellow, clear solution to a black, turbid solution. After completion of the reaction, the solution was cooled to room temperature, and a large amount of deionized water was added. The solution was filtered and drained, and the product was extracted with dichloromethane. The solution was concentrated to 1 mL, and a large amount of n-hexane was added to precipitate the solution. The precipitate was filtered and dried under vacuum to yield 30.4 mg of a black solid powder with a yield of 64.5%. 1 H NMR (400MHz, CDCl3): δ = 8.11-8.02 (m, 10H), 7.74 (d, J = 2.0Hz, 2H), 7.31 (dd, J = 8.5, 2.0Hz, 2H), 6.97 (s, 2H), 6.91 (s, 2H), 6.56 (s, 2H). 13 C{ 1H}NMR (100MHz, CDCl3): δ=139.4,135.7,134.4,133.7,132.5,131.0,130.3,129 .9,128.3,127.9,127.8,127.5,127.1,123.8,121.0,120.1,118.3ppm.ESI-TOF MS:m / z=461.1772(calcd for 1 + :461.1706).

[0110] The H NMR spectrum of compound 5 is shown in Figure 3 As shown, the NMR carbon spectrum is as follows Figure 4 shown.

[0111] Example 6

[0112] Preparation of compound 6

[0113] Compound 5 (50 mg, 0.11 mmol, 1.0 equiv.) was dissolved in 5 mL of DMF and added to a 100 mL Schlenk tube. 1-Bromobutane (297.5 mg, 2.17 mmol, 20.0 equiv.) was added and the reaction was allowed to proceed at 110°C for 24 h, during which the color of the mixture changed from light yellow to brown-black. Upon completion of the reaction, the DMF was concentrated to 1 mL, and a large amount of ethyl acetate was added to precipitate the solution, which was then filtered to obtain compound 6.

[0114] Example 7

[0115] Preparation of intermediates of azacarbene metal complexes based on a six-membered carbon helicene skeleton:

[0116] 80 mg of compound 6 synthesized in Example 6 was dissolved in 20 mL of methanol, and ammonium hexafluorophosphate (141.6 mg, 0.87 mmol, 8.0 equiv.) was added. The reaction was stirred at room temperature for 8 h, during which time a gray-black precipitate was produced. The precipitate was filtered and dried. The product was washed with ether and water and dried in vacuo to obtain 46.1 mg of a black solid powder with a yield of 48.9%. 1 H NMR (400MHz, CD3CN): δ=8.29-8.15(m,10H),8.02(s,2H),7.74-7.71(m,2H),7.49(m,2H),7.40(d,J=1.6Hz,2 H),6.79(d,J=1.6Hz,2H),4.11(t,J=7.2Hz,4H),1.85-1.76(m,4H),1.39-1.27(m,4H),0.99(t,J=7.2Hz,6H). 13 C{ 1H}NMR (100MHz, CD3CN): δ=135.0,134.7,133.9,133.1,132.7,131.1,130.20,130.16,129.8,12 9.1,128.3,127.1,124.1,122.9,122.5,121.5,50.8,32.2,19.9,13.6ppm.HRMS(ESI,positive ions):m / z=719.2725(calcd for 1 + :719.2733).

[0117] The H NMR spectrum of the intermediate of the nitrogen carbene metal complex based on the six-membered carbon helicene skeleton is as follows Figure 5 As shown, the NMR carbon spectrum is as follows Figure 6 shown.

[0118] Example 8

[0119] Synthesis of azacarbene metal silver complexes based on a six-membered carbon helicene skeleton:

[0120] Under anhydrous and oxygen-free conditions, an intermediate of an azacarbene metal complex based on a six-membered carbon helicene skeleton (50 mg, 0.058 mmol, 1.0 equiv.) was dissolved in 20 mL of anhydrous acetonitrile. AgO (33.4 mg, 0.15 mmol, 2.5 equiv.) was then added to the solution and stirred at 80°C for 24 h in the dark. After the reaction, the solution was cooled to room temperature and allowed to settle. The supernatant was then aspirated and concentrated to 2 mL in the dark. A large amount of ether was added to precipitate a gray solid. The solid was collected by filtration, washed with ether, and dried to give 37.2 mg of a gray solid powder in an 83.8% yield. ESI-TOF MS: m / z = 1050.3825 (calcd for 1 + =1050.3627).

[0121] The single crystal structure of the nitrogen-carbene metal silver complex (Formula II) based on the six-membered carbon helicene skeleton is as follows: Figure 7 shown.

[0122] Example 9

[0123] Synthesis of azacarbene metal gold complex (i.e., Formula III) based on a six-membered carbon helicene skeleton:

[0124] Under anhydrous and oxygen-free conditions, a silver azacarbene complex based on a six-membered carbon helicene skeleton (30 mg, 0.019 mmol, 1.0 equiv.) was dissolved in 20 mL of anhydrous acetonitrile. Tetrahydrothiophene gold chloride (15.0 mg, 0.047 mmol, 2.4 equiv.) was then added to the solution. The mixture was stirred at room temperature in the dark for 24 h. After the reaction was complete, the supernatant was aspirated and concentrated to 2 mL in the dark. A large amount of ether was added to precipitate a light gray solid. The solid was collected by filtration, washed with ether, and dried to give 26.4 mg of a light gray solid powder in a 78.9% yield. ESI-TOF MS: m / z = 769.2317 (calcd for 2 + =769.2600).

[0125] The single crystal structure of the gold complex of nitrogen carbene based on the six-membered carbon helicene skeleton is shown in Figure 2. Figure 8 shown.

[0126] Figure 9 These are the ultraviolet absorption images of the intermediate of nitrogen carbene metal complex based on a six-membered carbon helicene skeleton, the nitrogen carbene metal silver complex based on a six-membered carbon helicene skeleton, and the nitrogen carbene metal gold complex based on a six-membered carbon helicene skeleton.

[0127] Figure 10 These are the fluorescence emission images of the intermediate of the nitrogen carbene metal complex based on the six-membered carbon helicene skeleton, the nitrogen carbene metal silver complex based on the six-membered carbon helicene skeleton, and the nitrogen carbene metal gold complex based on the six-membered carbon helicene skeleton.

[0128] from Figure 9 and Figure 10 As can be seen in the figure, both the intermediate and the metal complex exhibit excellent UV absorption and fluorescence emission capabilities, especially the intermediate of the azacarbene metal complex based on the six-membered carbon helicene skeleton. These properties make the intermediate and the two complexes potentially useful in optoelectronic materials, especially in applications requiring specific light absorption and fluorescence emission properties.

[0129] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A compound based on a six-membered carbon helicene skeleton, characterized in that Its structural formula is shown in Formula I. Formula I.

2. The method for preparing the compound based on the six-membered carbon helicene skeleton according to claim 1, characterized in that: include: 2,7-Dimethylnaphthalene was used to synthesize compound 1 under the action of bromination reagent; Compound 1 reacts with triethyl phosphite to undergo Arbuzov reaction to synthesize compound 2; compound 2 reacts with p-bromobenzaldehyde to condense to synthesize compound 3; compound 3 reacts with propylene oxide and iodine to undergo photoaddition reaction to synthesize compound 4; Compound 4 reacts with imidazole under alkaline conditions to synthesize compound 5; compound 5 reacts with 1-bromobutane to synthesize compound 6; compound 6 reacts with ammonium hexafluorophosphate to undergo ion exchange reaction to synthesize a compound based on a six-membered carbon helicene skeleton; Reaction route: 。 3. The preparation method according to claim 2, wherein The method for synthesizing compound 1 by using 2,7-dimethylnaphthalene under the action of a brominating agent comprises: Under anhydrous and oxygen-free conditions, 2,7-dimethylnaphthalene, N-bromosuccinimide and dibenzoyl peroxide were dispersed in benzene, respectively, and heated under reflux with stirring to react and synthesize compound 1.

4. The preparation method according to claim 3, wherein The molar ratio of 2,7-dimethylnaphthalene, N-bromosuccinimide and dibenzoyl peroxide is 1:(1.8~2.5):(0.04~0.06).

5. The preparation method according to claim 4, wherein The molar ratio of 2,7-dimethylnaphthalene, N-bromosuccinimide and dibenzoyl peroxide is 1:2.2:0.

05.

6. The preparation method according to claim 3, wherein The concentration of 2,7-dimethylnaphthalene in benzene is 0.05~0.07 mol / L.

7. The preparation method according to claim 6, wherein The concentration of 2,7-dimethylnaphthalene in benzene is 0.064 mol / L.

8. The preparation method according to claim 3, wherein The temperature for heating under reflux and stirring is 90~110°C; the time for heating under reflux and stirring is 10~15 h.

9. The preparation method according to claim 8, wherein The temperature of heating under reflux and stirring was 100°C, and the time of heating under reflux and stirring was 12 h.

10. The preparation method according to claim 2, wherein Compound 1 undergoes Arbuzov reaction with triethyl phosphite to synthesize compound 2, comprising: Compound 1 was dispersed in triethyl phosphite, and the mixture was heated under reflux and stirred to react to synthesize compound 2.

11. The preparation method according to claim 10, characterized in that The molar ratio of compound 1 to triethyl phosphite is 1:(3.5~5).

12. The preparation method according to claim 11, characterized in that The molar ratio of compound 1 to triethyl phosphite is 1:

4.

13. The preparation method according to claim 10, wherein The temperature for heating under reflux and stirring is 120~150℃; the time for heating under reflux and stirring is 5~8h.

14. The preparation method according to claim 13, wherein The temperature for heating under reflux and stirring was 130°C, and the time for heating under reflux and stirring was 6 h.

15. The preparation method according to claim 2, wherein The method for synthesizing compound 3 by condensing compound 2 with p-bromobenzaldehyde comprises: Under anhydrous and oxygen-free conditions, compound 2, p-bromobenzaldehyde and sodium hydride were dispersed in anhydrous tetrahydrofuran, and heated and stirred to react to synthesize compound 3.

16. The preparation method according to claim 15, characterized in that The molar ratio of compound 2, p-bromobenzaldehyde and sodium hydride is 1:(2.5~3.5):(7~10).

17. The preparation method according to claim 16, wherein The molar ratio of compound 2, p-bromobenzaldehyde and sodium hydride is 1:3:

8.

18. The preparation method according to claim 15, wherein The concentration of compound 2 in anhydrous tetrahydrofuran is 0.05~0.12 mol / L.

19. The preparation method according to claim 15, wherein The heating and stirring temperature is 40~60℃; the heating and stirring time is 6~8 hours.

20. The preparation method according to claim 19, wherein The heating and stirring temperature was 50 °C and the heating and stirring time was 6 h.

21. The preparation method according to claim 2, wherein The method for synthesizing compound 4 by photoaddition reaction of compound 3 with propylene oxide and elemental iodine includes: Compound 3, propylene oxide and iodine were dispersed in toluene respectively, and reacted under high-pressure mercury lamp to synthesize compound 4.

22. The preparation method according to claim 21, wherein The molar ratio of compound 3, propylene oxide and elemental iodine is 1:(600~800):(2.5~4).

23. The preparation method according to claim 22, characterized in that The molar ratio of compound 3, propylene oxide and elemental iodine is 1:715:

3.

24. The preparation method according to claim 21, wherein The wavelength of the high-pressure mercury lamp is 365nm.

25. The preparation method according to claim 24, characterized in that The illumination time is 20~30 h.

26. The preparation method according to claim 2, wherein Compound 4 undergoes a substitution reaction with imidazole under alkaline conditions to synthesize compound 5. The reaction includes: Under anhydrous and oxygen-free conditions, compound 4, imidazole, copper oxide and anhydrous potassium carbonate were dispersed in anhydrous dimethyl sulfoxide, respectively, and heated and stirred to react to synthesize compound 5.

27. The preparation method according to claim 26, wherein The molar ratio of compound 4, imidazole, copper oxide and anhydrous potassium carbonate is 1:(14~18):(0.8~1.2):(14~18).

28. The preparation method according to claim 27, wherein The molar ratio of compound 4, imidazole, copper oxide and anhydrous potassium carbonate is 1:16:1:

16.

29. The preparation method according to claim 28, characterized in that The concentration of compound 4 in anhydrous dimethyl sulfoxide was 0.04~0.06 mol / L.

30. The preparation method according to claim 29, wherein The concentration of compound 4 in anhydrous dimethyl sulfoxide was 0.05 mol / L.

31. The preparation method according to claim 26, wherein The heating and stirring temperature is 140~160℃; the heating and stirring time is 40~60 h.

32. The preparation method according to claim 31, wherein The heating and stirring temperature was 150 °C and the heating and stirring time was 48 h.

33. The preparation method according to claim 2, wherein The reaction of compound 5 and 1-bromobutane to synthesize compound 6 includes: Compound 5 and 1-bromobutane were dispersed in N,N-dimethylformamide, and heated and stirred to react to synthesize compound 6.

34. The preparation method according to claim 33, wherein The molar ratio of compound 5 to 1-bromobutane is 1:(18~22).

35. The preparation method according to claim 34, wherein The molar ratio of compound 5 to 1-bromobutane is 1:

20.

36. The preparation method according to claim 33, wherein The concentration of compound 5 in N,N-dimethylformamide was 8.3~10 g / L.

37. The preparation method according to claim 36, wherein The concentration of compound 5 in N,N-dimethylformamide was 10 g / L.

38. The preparation method according to claim 33, wherein The heating and stirring temperature is 100~120℃; the heating and stirring time is 20~30 h.

39. The preparation method according to claim 38, wherein The heating and stirring temperature was 110 °C and the heating and stirring time was 24 h.

40. The preparation method according to claim 2, wherein The method for synthesizing a compound based on a six-membered carbon helicene skeleton by an ion exchange reaction between compound 6 and ammonium hexafluorophosphate comprises: Compound 6 and ammonium hexafluorophosphate were dispersed in methanol and stirred at room temperature to synthesize a compound based on a six-membered carbon helicene skeleton.

41. The preparation method according to claim 40, wherein The molar ratio of compound 6 to ammonium hexafluorophosphate is 1:(6~10).

42. The preparation method according to claim 41, wherein The molar ratio of compound 6 to ammonium hexafluorophosphate is 1:

8.

43. The preparation method according to claim 40, wherein The concentration of ammonium hexafluorophosphate in methanol is 0.03~0.05 mol / L.

44. The preparation method according to claim 43, wherein The concentration of ammonium hexafluorophosphate in methanol is 0.04 mol / L.

45. The preparation method according to claim 40, wherein The reaction time is 7 to 10 h under stirring at room temperature.

46. ​​The preparation method according to claim 45, wherein The reaction time was 8 h under stirring at room temperature.

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