Metal N-heterocyclic carbene macrocyclic compound serving as supramolecular carrier and preparation method of metal N-heterocyclic carbene macrocyclic compound

Abstract

The invention belongs to the field of preparation of new materials, and particularly relates to a metal N-heterocyclic carbene macrocyclic compound serving as a supramolecular carrier and a preparation method of the metal N-heterocyclic carbene macrocyclic compound. The structural formula of the metal N-heterocyclic carbene macrocyclic compound is as shown in a formula I or a formula II: # imgabs0. According to the method disclosed by the invention, the metal N-heterocyclic carbene macrocyclic compound is prepared by reacting a biimidazole onium salt compound with metal, and the metal N-heterocyclic carbene macrocyclic compound with different cavity sizes is obtained by adjusting the number of n in the structural formula; the compound can be used as a supramolecular carrier, forms a supramolecular compound system with matched guest molecules, and is expected to be applied to the aspects of subject-guest recognition, drug delivery, biological materials, confinement catalysis, organic metal rotaxane and the like.

Description

Technical Field

[0001] The invention belongs to the field of new material preparation, and specifically relates to a metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier and a preparation method thereof. Background Art

[0002] Molecular recognition is the basis of supramolecular chemistry research. By studying the selective binding between the host and the guest, we can obtain a host-guest complex with high stability and selectivity. Compared with non-cyclic hosts, macrocyclic hosts are easier to achieve highly selective binding to guests. Therefore, in the field of host-guest chemistry research, the construction of new host macrocycles has always led the development of host-guest chemistry.

[0003] For a long time, supramolecular chemists have used various efficient organic reactions to construct a large number of macrocyclic hosts, such as cucurbiturils, cyclodextrins, calixarene and pillararene. Many macrocyclic hosts show unique guest selectivity, and the study of their host-guest chemistry has greatly enriched and opened up new areas of supramolecular chemistry research. However, these macrocyclic compounds have more or less problems such as low synthesis yield, poor solubility, strong rigid structure that makes it difficult to change the host shape to adapt to the size of the guest molecule, and difficulty in modifying the host structure. Furthermore, through the important structural characteristics of the guest molecule (such as molecular size or volume), forward design of the host molecule should be more conducive to obtaining a host-guest system with practical application potential. As such, the design of a variety of host molecules and the corresponding host-guest chemistry research are issues or challenges that need to be paid attention to and solved at this stage.

[0004] In the field of nitrogen heterocyclic carbene chemistry, the metal-carbene bond with stable coordination and adjustable ligand structure are used to construct complex and functionally controllable supramolecular assembly structures. In recent years, a variety of metal supramolecular assembly structures have been constructed based on nitrogen heterocyclic carbene primitives, including metal macrocycles, metal molecular squares, metal columns, metal clusters, metal interlocking structures, and functional porous materials (see Chem. Rev. 2018, 118, 9587; Chem. Soc. Rev. 2021, 50, 13559; Sci China Chem. 2024, 67, 1510). At present, these metal supramolecular assembly structures have laid the foundation for host-guest chemistry, nanoreactors, drug delivery, and chemical sensing due to their high yield, good solubility, unique structural features, and adjustable confined cavities.

[0005] Up to now, most of the research reports on the relevant metal nitrogen heterocyclic carbene framework are limited to traditional linear or planar ligands, and the design and regulation of the ligand angle are still incomplete. The structure of the prepared metal nitrogen heterocyclic carbene compound is relatively simple and the internal cavity is limited, which greatly limits its functional application research (see Chem. Rev. 2018, 118, 9587; J. Am. Chem. Soc. 2023, 145, 7692). In addition, the research on metal nitrogen heterocyclic assemblies to directly induce the construction of complex molecular topological structures or drive structural transformations between assemblies through molecular recognition or stimulus response is very limited, but it is necessary (see Angew. Chem. Int. Ed. 2022, 61, e202206788; Chem. Eur. J. 2023, 29, e202300209). Summary of the invention

[0006] The object of the present invention is to provide a metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier and a preparation method thereof.

[0007] The implementation process of the present invention is as follows:

[0008] A metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier, the structural formula of the compound is shown in Formula I or Formula II:

[0009]

[0010] Where n is 4 or 6, M is Ag or Au,

[0011] X is any one of PF6, SF6, BF4, ClO4 or NO3,

[0012] L is selected from Any one of

[0013] Among them, R1 is selected from any one of an alkyl group with a carbon number of 1-6, a halogen group, a hydrogen group, a carbonyl group or a hydroxyl group, R2 is selected from any one of a hydrogen group, an amino group, or a carboxyl group, n1 is 1 to 5, Ar is selected from a phenyl group or a substituted phenyl group, and the substituent is selected from any one of an alkyl group with a carbon number of 1-6, an alkoxy group with a carbon number of 1-6, and a halogen group.

[0014] The preparation method of the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier uses a bisimidazolium salt compound and silver oxide as raw materials, N,N-dimethylformamide as solvent, and heats the reaction in the dark to obtain the Ag4L4 type metal nitrogen heterocyclic carbene macrocyclic compound.

[0015] The preparation method of the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier uses a bisimidazolium salt compound, silver oxide and pyrene as raw materials, N,N-dimethylformamide as solvent, and heats the reaction in the dark to obtain the Ag6L6 type metal nitrogen heterocyclic carbene macrocyclic compound.

[0016] The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier comprises the following steps:

[0017] (1) using a bisimidazolium salt compound and silver oxide as raw materials, using N,N-dimethylformamide as solvent, heating and light-shielding to obtain a Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound;

[0018] (2) Using Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound and pyrene as raw materials and N,N-dimethylformamide as solvent, Ag6L6-type metal nitrogen heterocyclic carbene macrocyclic compound was prepared by reaction at room temperature in the dark.

[0019] The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier comprises the following steps:

[0020] (1) using a bisimidazolium salt compound and silver oxide as raw materials, using N,N-dimethylformamide as solvent, heating and light-shielding to obtain a Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound;

[0021] (2) Using Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound and tetrahydrothiophene gold chloride as raw materials and N,N-dimethylformamide as solvent, Au6L6-type metal nitrogen heterocyclic carbene macrocyclic compound was prepared by reaction at room temperature in the dark.

[0022] Further, the bisimidazolium salt compound is selected from

[0023] Any one of

[0024] Wherein, X is any one of PF6, SF6, BF4, ClO4 or NO3, R1 is selected from any one of an alkyl group having 1-6 carbon atoms, a halogen group, a hydrogen group, a carbonyl group or a hydroxyl group, R2 is selected from any one of a hydrogen group, an amino group or a carboxyl group, n1 is 1 to 5, Ar is selected from a phenyl group or a substituted phenyl group, and the substituent is selected from any one of an alkyl group having 1-6 carbon atoms, an alkoxy group having 1-6 carbon atoms, and a halogen group.

[0025] Furthermore, the molar ratio of the bisimidazolium salt compound to silver oxide is 1:1.1 to 1:2.4; the temperature of the heating and light-shielding reaction is 90° C., and the reaction time is 6 to 12 hours.

[0026] Furthermore, the molar ratio of the bisimidazolium salt compound, silver oxide and pyrene is 1:1.1:0.5 to 1:2.2:1.1; the temperature of the heating and light-shielding reaction is 90° C., and the reaction time is 6 to 12 hours.

[0027] Furthermore, the molar ratio of the Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound to pyrene is 1:2 to 1:4, and the reaction time at room temperature in the dark is 2 to 10 minutes.

[0028] Furthermore, the molar ratio of the Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound and tetrahydrothiophene gold chloride is 0.025:0.1 to 0.03:0.1, and the reaction time at room temperature in the dark is 18 to 24 hours.

[0029] Positive effects of the present invention:

[0030] (1) The metal nitrogen heterocyclic carbene macrocyclic compound of the present invention has a "V"-shaped coordination angle ligand and a linear coordinated metal ion, breaking through the limitations of traditional linear and planar ligand molecular structures, and preparing a metal supramolecular assembly structure with adjustable internal hydrophobic cavity size.

[0031] (2) The method of the present invention has the characteristics of simple synthesis, easy availability of raw materials, easy operation, high synthesis yield, good product uniformity and good stability.

[0032] (3) The metal nitrogen heterocyclic carbene macrocyclic compound of the present invention has an irregular cylindrical region with a large middle cavity and a small opening. Due to the influence of the flexible external alkyl chain on the bisimidazolium salt compound, the metal supramolecular assembly can adaptively adjust the size of the cavity opening to accommodate guest molecules with different structural types and molecular size volumes, thereby forming a stable host-guest complex.

[0033] (4) The metal nitrogen heterocyclic carbene macrocyclic compounds of the present invention can be used to adjust the number of n in formula I or the structure of formula II to obtain metal supramolecular assemblies with different cavity sizes, and can be used as supramolecular carriers to form stable host-guest complexes with matching guest molecules, and are expected to be applied in host-guest recognition, drug delivery, biomaterials, confined catalysis, and organometallic rotaxanes. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic compound 3 prepared in Example 1 1 H NMR spectrum, where * indicates N,N-dimethylformamide;

[0035] Figure 2 The Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic compound 3 prepared in Example 1 13C NMR spectrum, where * indicates N,N-dimethylformamide;

[0036] Figure 3 This is a high-resolution mass spectrum of the Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic compound 3 prepared in Example 1;

[0037] Figure 4 The single crystal structure diagram of the Ag6L6 type nitrogen heterocyclic silver carbene macrocyclic compound 4 prepared in Example 2, wherein (a) the hexagonal mosaic structure of the Ag6L6 type nitrogen heterocyclic silver carbene macrocyclic compound 4, (b) the two-dimensional dense honeycomb structure of the Ag6L6 type nitrogen heterocyclic silver carbene macrocyclic compound 4, Ag is rose red; N is blue; C is light gray; P is orange; F is green; and the pyrene molecule is dark green;

[0038] Figure 5 The Au6L6 type nitrogen heterocyclic gold carbene macrocyclic compound 5 prepared in Example 4 1 H NMR spectrum, where * indicates N,N-dimethylformamide;

[0039] Figure 6 The Au6L6 type nitrogen heterocyclic gold carbene macrocyclic compound 5 prepared in Example 4 13 C NMR spectrum, where * indicates N,N-dimethylformamide;

[0040] Figure 7 Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic host-guest complex prepared in Example 36 The single crystal structure diagram, Ag is rose red; N is blue; C is light gray; O is red;

[0041] Figure 8 The Au6L6 type nitrogen heterocyclic gold carbene macrocyclic host-guest complex prepared in Example 37 of 13 C NMR spectrum, where * indicates N,N-dimethylformamide;

[0042] Fig. 9 The Au6L6 type nitrogen heterocyclic gold carbene macrocyclic host-guest complex prepared in Example 38 of 13 C NMR spectrum, where * represents N,N-dimethylformamide. DETAILED DESCRIPTION

[0043] The present invention will be further described below in conjunction with the embodiments.

[0044] Example 1 Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic compound

[0045] The structure of the target product Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic compound 3 is shown below:

[0046]

[0047] The preparation method of the Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic compound comprises the following steps:

[0048] (1) Preparation of Compound 1

[0049]

[0050] 1,2-diaminobutane (4mL, 40mmol) and 2 drops of glacial acetic acid were added to 80mL of methanol. At 0°C, 37% formaldehyde solution (3.76mL, 44mmol) and 40% glyoxal solution (2.85mL, 22mmol) were slowly added to the solution, respectively, and stirred at room temperature for 7 days. After the reaction was completed, the solvent was removed by distillation under reduced pressure, the organic phase was extracted with dichloromethane, and the solvent was dried to obtain a light yellow solid. The light yellow solid was washed with glacial acetone to finally obtain a white solid 1. 1 H NMR (400MHz, CDCl3): δ = 4.15 (s, 2H), 3.44 (d, J = 3.9Hz, 2H), 3.28 (d, J = 3.9Hz, 2H), 2.80-2.71 (m, 4H), 2.67-2.56 (m, 4H), 1.77-1.68 (m, 8H) ppm.

[0051] (2) Preparation of the bisimidazolium salt compound 2-PF6

[0052]

[0053] Compound 1 (502.3 mg, 2.26 mmol) and N-bromosuccinimide (802.8 mg, 4.51 mmol) were added to 10 mL of ethylene glycol dimethyl ether and stirred at room temperature for 3 hours in a dark place. After the reaction was completed, the light beige solid 2-Br was obtained by filtration at room temperature. Subsequently, the solid compound 2-Br and ammonium hexafluorophosphate (3.67 g, 22.53 mmol) were added to 10 mL of methanol and stirred at room temperature for 6 hours. After the reaction was completed, the solid was collected by filtration at room temperature, washed with a large amount of water, and dried to obtain an off-white solid compound 2-PF6, 687.2 mg. Yield: 60%. 1 H NMR (400MHz, DMSO-d6): δ = 8.98 (s, 2H), 6.65 (s, 2H), 3.94-3.83 (m, 14H), 3.65-3.56 (m, 4H), 2.10-1.97 (m, 4H), 1.94-1.81 (m, 4H,) ppm.

[0054] (3) Preparation of Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic compound 3

[0055]

[0056] Under nitrogen atmosphere, the bisimidazolium salt compound 2-PF6 (50.4 mg, 0.10 mmol) and silver oxide (55.6 mg, 0.24 mmol) were added to 3 mL N, N-dimethylformamide and reacted at 90 ° C for 12 hours under light-proof conditions. After the reaction was completed, it was cooled to room temperature, centrifuged to separate the solid, and 50 mL of ether was added to precipitate a light brown solid precipitate. The solid was collected by filtration and vacuum dried to obtain the Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic compound 3, 38.4 mg, yield: 83%, which 1 H NMR spectra Figure 1 ,That 13 CNMR images Figure 2 Its high-resolution mass spectrum is shown in Figure 3 .

[0057] 1 H NMR (400MHz, DMSO-d6): δ = 6.20 (s, 8H, Ha), 4.04-3.90 (br, 16H, Hc / c′), 3.66-3. 56(br,16H,Hc / c′),2.08-1.95(br,16H,Hd / d′),1.90-1.73(br,16H,Hd / d′)ppm. 13 C NMR (100MHz, DMSO-d6): δ = 203.3 (Cb), 82.1 (Ca), 50.2 (Cc), 26.5 (Cd) ppm. ESI-MS (positives): m / z = 483.0745 (calcd for [3-3PF6] 3+ 483.0652),m / z=797.0999(calcd for[3-2PF6] 2+ 797.0801).

[0058] Example 2 Ag6L6 type nitrogen heterocyclic silver carbene macrocyclic compound

[0059] The structure of the target product Ag6L6-type nitrogen heterocyclic silver carbene macrocyclic compound 4 is shown below:

[0060]

[0061] The preparation method of the Ag6L6 type nitrogen heterocyclic silver carbene macrocyclic compound comprises the following steps:

[0062] The preparation methods and parameters of steps (1)-(3) of this embodiment are the same as those of steps (1)-(3) of Example 1 and are not described again here.

[0063] (4) Preparation of Ag6L6-type nitrogen heterocyclic silver carbene macrocyclic compound 4

[0064]

[0065] Under nitrogen atmosphere, the Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic compound 3 (92.4 mg, 0.05 mmol) and pyrene (41.2 mg, 0.20 mmol) prepared in step (3) were added to 3 mL of N,N-dimethylformamide and stirred at room temperature for 10 minutes under light-proof conditions. After the reaction was completed, isopropyl ether vapor was slowly diffused into the reaction solution for several days to obtain a crystal of the Ag6L6 type nitrogen heterocyclic silver carbene macrocyclic compound 4, 44.9 mg, with a yield of 40%. The single crystal structure is shown in FIG. Figure 4 .

[0066] Example 3 Ag6L6 type nitrogen heterocyclic silver carbene macrocyclic compound

[0067] The structure of the target product Ag6L6-type nitrogen heterocyclic silver carbene macrocyclic compound 4 is shown below:

[0068]

[0069] The preparation method of the Ag6L6 type nitrogen heterocyclic silver carbene macrocyclic compound comprises the following steps:

[0070] The preparation methods and parameters of steps (1) and (2) of this embodiment are the same as those of steps (1) and (2) of embodiment 1 and are not described again here.

[0071] (3) Preparation of Ag6L6-type nitrogen heterocyclic silver carbene macrocyclic compound 4

[0072]

[0073] Under nitrogen atmosphere, the bisimidazolium salt compound 2-PF6 (50.1 mg, 0.10 mmol) prepared in step (2), silver oxide (50.7 mg, 0.22 mmol) and pyrene (21.7 mg, 0.11 mmol) were added to 3 mL of N,N-dimethylformamide and reacted at 90°C for 12 hours under light-proof conditions. After the reaction was completed, the mixture was cooled to room temperature, centrifuged and the solid was separated. After slowly diffusing isopropyl ether vapor into the solution for several days, the crystals of Ag6L6-type nitrogen heterocyclic silver carbene macrocyclic compound 4 were obtained, 24.2 mg, with a yield of 43%.

[0074] Example 4 Au6L6-type nitrogen heterocyclic gold carbene macrocyclic compound

[0075] The structure of the target product Au6L6-type nitrogen heterocyclic gold carbene macrocyclic compound 5 is shown below:

[0076]

[0077] The preparation method of the Au6L6 type nitrogen heterocyclic gold carbene macrocyclic compound comprises the following steps:

[0078] The preparation methods and parameters of steps (1)-(3) of this embodiment are the same as those of steps (1)-(3) of Example 1 and are not described again here.

[0079] (4) Preparation of Au6L6-type nitrogen heterocyclic gold carbene macrocyclic compound 5

[0080]

[0081] Under nitrogen atmosphere, the Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic compound 3 (46.4 mg, 0.025 mmol) prepared in step (3) and tetrahydrothiophene gold chloride (32.3 mg, 0.10 mmol) were added to 3 mL N, N-dimethylformamide and reacted at room temperature for 24 hours under light-proof conditions. After the reaction was completed, the solid was separated by centrifugal sedimentation, 50 mL of ether was added, and a light purple solid precipitate was precipitated. The solid was collected by filtration and vacuum dried to obtain the corresponding Au6L6 type nitrogen heterocyclic gold carbene macrocyclic compound 5, 47.8 mg, yield: 87%, which 1 H NMR spectra Figure 5 ,That 13 C NMR spectra Figure 6 .

[0082] 1 H NMR (400MHz, DMSO-d6): δ = 6.28 (s, 8H, Ha), 4.22-4.01 (br, 16H, Hc / c′), 3.67-3. 54(br,16H,Hc / c′),2.09-1.94(br,16H,Hd / d′),1.94-1.77(br,16H,Hd / d′)ppm. 13 C NMR (100MHz, DMSO-d6): δ = 203.1 (Cb), 81.7 (Ca), 49.5 (Cc), 26.0 (Cd) ppm. ESI-MS (positives): m / z = 527.1137 (calcdfor [5-5PF6] 5+ 527.1359),m / z=695.1381(calcd for[5-4PF6] 4+ 695.1611).

[0083] Example 5 Preparation of Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic compound

[0084] The preparation method and parameters of steps (1)-(3) of this embodiment are the same as those of steps (1)-(3) of Example 1, except that in step (3), the molar ratio of the bisimidazolium salt compound 2-PF6 and silver oxide is 1:1.1, and the reaction is carried out at 90°C for 6 hours in the dark.

[0085] Example 6 Ag6L6-type nitrogen heterocyclic silver carbene macrocyclic compound

[0086] The preparation method and parameters of steps (1)-(3) of this embodiment are the same as those of steps (1)-(3) of Example 3, except that: in step (3), the molar ratio of the bisimidazolium salt compound 2-PF6, silver oxide and pyrene is 1:1.1:0.5; and the reaction is carried out at 90°C for 6 hours in the dark.

[0087] Example 7 Ag6L6-type nitrogen heterocyclic silver carbene macrocyclic compound

[0088] The preparation method and parameters of steps (1)-(4) of this embodiment are the same as those of steps (1)-(4) of Example 2, except that: in step (4), the molar ratio of Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic compound 3 and pyrene is 1:2, and the reaction time at room temperature in the dark is 2 minutes.

[0089] Example 8 Au6L6-type metal nitrogen heterocyclic carbene macrocyclic compound

[0090] The preparation method and parameters of steps (1)-(4) of this embodiment are the same as those of steps (1)-(4) of Example 4, except that in step (4), the molar ratio of Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic compound 3 and tetrahydrothiophene gold chloride is 0.03:0.1, and the reaction is carried out at room temperature for 18 hours under light-proof conditions.

[0091] The anion of the bisimidazolium salt compound involved in the method of the present invention can be selected from any one of PF6, SF6, BF4, ClO4 or NO3. The following examples can still prepare the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier of the present invention after replacing the anion of the bisimidazolium salt compound, as shown in Table 1:

[0092] Table 1 Examples of Preparation of Metal Nitrogen Heterocyclic Carbene Macrocyclic Compounds from Bisimidazole Salts of Different Anions

[0093]

[0094]

[0095] The bisimidazolium salt compound of the present invention is selected from

[0096]

[0097] Any one of

[0098] Wherein, X is any one of PF6, SF6, BF4, ClO4 or NO3, R1 is selected from any one of alkyl, halogen, hydrogen, carbonyl or hydroxyl with 1-6 carbon atoms, R2 is selected from any one of hydrogen, amino or carboxyl, n1 is 1-5, Ar is selected from phenyl or substituted phenyl, and the substituent is selected from any one of alkyl, alkoxy and halogen with 1-6 carbon atoms. The following examples can still prepare the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier of the present invention after the structural change of the bisimidazolium salt compound, as shown in Table 2:

[0099] Table 2 Examples of Preparation of Metal Nitrogen Heterocyclic Carbene Macrocyclic Compounds Using Bisimidazole Salts of Different Structures

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] Example 36 Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic compound is used as a supramolecular carrier and assembled with the guest molecule dioxane to form an Ag4L4-type nitrogen heterocyclic silver carbene macrocyclic host-guest complex

[0106] The above Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic host-guest complex The preparation method comprises the following steps: slowly diffusing the guest molecule dioxane into the Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic compound 3 (5.2 mg, 0.003 mmol) prepared in Example 1 for several weeks to obtain the Ag4L4 type nitrogen heterocyclic silver carbene macrocyclic host-guest complex. Crystal, its crystal structure is shown in Figure 7 .

[0107] Example 37 Au6L6-type nitrogen heterocyclic gold carbene macrocyclic compound as supramolecular carrier and guest molecule C 60 Assembled into Au6L6-type nitrogen heterocyclic gold carbene macrocyclic host-guest complex

[0108] The above Au6L6 type nitrogen heterocyclic gold carbene macrocyclic host-guest complex The preparation method comprises the following steps: 60 (8.6 mg, 0.012 mmol) and the Au6L6 type nitrogen heterocyclic gold carbene macrocyclic compound 5 (20.1 mg, 0.006 mmol) prepared in Example 4 were added to 0.6 mL of deuterated dimethyl sulfoxide and reacted at room temperature for 6 hours under light-proof conditions. After the reaction was completed, the solid was separated by centrifugal sedimentation to obtain the Au6L6 type nitrogen heterocyclic gold carbene macrocyclic host-guest complex. Solution, which 13 CNMR images Figure 8 .

[0109] 13 C NMR (100MHz, DMSO-d6): δ = 203.2,142.5 (C 60 ),81.7,49.6,26.0ppm.ESI-MS(positive ions):m / z=535.2982(calcd for[5+C 60 -6PF6] 6+ 525.2863).

[0110] Example 38 Au6L6-type nitrogen heterocyclic gold carbene macrocyclic compound as supramolecular carrier and guest molecule C 70 Assembled into Au6L6-type nitrogen heterocyclic gold carbene macrocyclic host-guest complex

[0111] The guest molecule C 70 (10.4 mg, 0.012 mmol) and the Au6L6 type nitrogen heterocyclic gold carbene macrocyclic compound 5 (20.3 mg, 0.006 mmol) prepared in Example 4 were added to 0.6 mL of deuterated dimethyl sulfoxide and reacted at room temperature for 6 hours under light-proof conditions. After the reaction was completed, the solid was separated by centrifugal sedimentation to obtain the Au6L6 type nitrogen heterocyclic silver carbene macrocyclic host-guest complex. Solution, which 13 C NMR spectra Fig. 9 .

[0112] 13 C NMR (100MHz, DMSO-d6): δ = 203.2,149.9 (C 70 ),147.4(C 70 ),146.7(C 70 ),144.6(C 70 ),130.2(C 70 ),81.7,49.6,26.1ppm.ESI-MS(positive ions):m / z=555.2969(calcdfor[5+C70 -6PF6] 6+ 555.2863),m / z=695.3591(calcd for[5+C 70 -5PF6] 5+ 695.3365).

[0113] The above contents are further detailed descriptions of the present invention in combination with specific preferred embodiments, and the specific implementation of the present invention cannot be limited to these descriptions. For ordinary technicians in the field to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, which should be regarded as falling within the protection scope of the present invention.

Claims

1. A metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier, characterized in that: The structural formula of the compound is shown in Formula I or Formula II: Where n is 4 or 6, M is Ag or Au, X is any one of PF6, SF6, BF4, ClO4 or NO3, L is selected from Any one of Among them, R1 is selected from any one of an alkyl group with a carbon number of 1-6, a halogen group, a hydrogen group, a carbonyl group or a hydroxyl group, R2 is selected from any one of a hydrogen group, an amino group, or a carboxyl group, n1 is 1 to 5, Ar is selected from a phenyl group or a substituted phenyl group, and the substituent is selected from any one of an alkyl group with a carbon number of 1-6, an alkoxy group with a carbon number of 1-6, and a halogen group.

2. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to claim 1, characterized in that: Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound was prepared by using bisimidazolium salt compound and silver oxide as raw materials and N,N-dimethylformamide as solvent under heating and light-protection.

3. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to claim 1, characterized in that: Ag6L6 metal nitrogen heterocyclic carbene macrocyclic compound was prepared by using bisimidazolium salt compound, silver oxide and pyrene as raw materials and N,N-dimethylformamide as solvent under heating and light-protection.

4. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to claim 1, characterized in that: The steps include: (1) using a bisimidazolium salt compound and silver oxide as raw materials, using N,N-dimethylformamide as solvent, heating and light-shielding reaction to prepare an Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound; (2) Using Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound and pyrene as raw materials and N,N-dimethylformamide as solvent, Ag6L6-type metal nitrogen heterocyclic carbene macrocyclic compound was prepared by reaction at room temperature in the dark.

5. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to claim 1, characterized in that: The steps include: (1) using a bisimidazolium salt compound and silver oxide as raw materials, using N,N-dimethylformamide as solvent, heating and light-shielding reaction to prepare an Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound; (2) Using Ag4L4-type metal nitrogen heterocyclic carbene macrocyclic compound and tetrahydrothiophene gold chloride as raw materials and N,N-dimethylformamide as solvent, Au6L6-type metal nitrogen heterocyclic carbene macrocyclic compound was prepared by reaction at room temperature in the dark.

6. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to any one of claims 2 to 5, characterized in that: The bisimidazolium salt compound is selected from Any one of Wherein, X is any one of PF6, SF6, BF4, ClO4 or NO3, R1 is selected from any one of an alkyl group having 1-6 carbon atoms, a halogen group, a hydrogen group, a carbonyl group or a hydroxyl group, R2 is selected from any one of a hydrogen group, an amino group or a carboxyl group, n1 is 1 to 5, Ar is selected from a phenyl group or a substituted phenyl group, and the substituent is selected from any one of an alkyl group having 1-6 carbon atoms, an alkoxy group having 1-6 carbon atoms, and a halogen group.

7. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to any one of claims 2 to 5, characterized in that: The molar ratio of the bisimidazolium salt compound to silver oxide is 1:1.1 to 1:2.4; the temperature of the heating and light-proof reaction is 90° C., and the reaction time is 6 to 12 hours.

8. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to claim 3, characterized in that: The molar ratio of the bisimidazolium salt compound, silver oxide and pyrene is 1:1.1:0.5 to 1:2.2:1.1; the temperature of the heating and light-proof reaction is 90° C., and the reaction time is 6 to 12 hours.

9. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to claim 4, characterized in that: The molar ratio of the Ag4L4 metal nitrogen heterocyclic carbene macrocyclic compound to pyrene is 1:2 to 1:4, and the reaction time at room temperature in the dark is 2 to 10 minutes.

10. The method for preparing the metal nitrogen heterocyclic carbene macrocyclic compound as a supramolecular carrier according to claim 5, characterized in that: The molar ratio of the Ag4L4 type metal nitrogen heterocyclic carbene macrocyclic compound and tetrahydrothiophene gold chloride is 0.025:0.1-0.03:0.1, and the reaction time at room temperature in the dark is 18-24 hours.

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