Photo-controlled endo-chiral diarylethene supramolecular cage and preparation method thereof

Abstract

The application discloses a light-controlled endogenous chiral diarylethene supramolecular cage, which is obtained by self-assembly of a bidentate diarylethene pyridine ligand and a compound containing a divalent metal palladium ion; the structural general formula of the bidentate diarylethene pyridine ligand is as follows: The application provides a preparation method of the light-controlled endogenous chiral diarylethene supramolecular cage, in which, after one metal palladium ion loses two nitrate radicals, the metal palladium ion is coordinated with nitrogen atoms on four pyridines, the whole process is relatively simple, and finally, the target product is formed under the influence of a self-correction behavior in supramolecular self-assembly driven by thermodynamics.

Description

Technical Field

[0001] This invention belongs to the field of supramolecular chemistry technology, specifically, it relates to a light-controlled endogenous chiral diarylethene supramolecular cage and its preparation method. Background Technology

[0002] Coordination metal cages are a class of three-dimensional cage-like molecules formed by the coordination of organic units and metal ions. They possess precise structures, nanoscale confined cavities, and convenient synthesis, and have wide applications in guest separation and recognition, catalysis, and drug delivery. In recent years, the functionalization of supramolecular cages has gradually become a research hotspot in this field, and a series of molecular cages with novel structures and functions have been developed, greatly expanding the application prospects of supramolecular cages.

[0003] Photovoltaic energy, a clean energy source, has attracted widespread attention from researchers due to its advantages such as high efficiency, renewability, and high spatiotemporal controllability. Diarylethylene molecules are a product of human exploration of nature and the development of photovoltaic energy. As a functional light switch, diarylethylene compounds can undergo reversible photoisomerization reactions under ultraviolet and visible light irradiation, accompanied by changes in physical and chemical properties. Therefore, they have important application value in information storage, molecular logic gates, and supramolecular assembly systems. However, traditionally, due to the free rotation of the aryl groups on both sides, most reported diarylethylene molecules are achiral, which greatly limits their application prospects in the field of functionalized chiral supramolecular cages.

[0004] Introducing pre-designed chiral diarylethene ligands into supramolecular metal cage systems will greatly expand the development of light-controlled self-assembled supramolecular cage materials, enabling reversible control of the chiral signal of the metal cage. Summary of the Invention

[0005] The purpose of this invention is to provide a light-controlled endogenous chiral diarylethene supramolecular cage to solve the technical problem of existing metal cages lacking dynamic chiral control.

[0006] Another object of the present invention is to provide a method for preparing the light-controlled endogenous chiral diarylethene supramolecular cage.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] The first aspect of the present invention provides a light-controlled endogenous chiral diarylethylene supramolecular cage, wherein the light-controlled endogenous chiral diarylethylene supramolecular cage is obtained by self-assembly of a bidentate diarylethylene pyridine ligand and a compound containing a divalent palladium ion.

[0009] The general structural formula of the bidentate diarylvinylpyridine ligand is:

[0010]

[0011] R1 is selected from: The general structural formula of the compound containing divalent palladium ions is:

[0012]

[0013] R is selected from NO3, Cl, and CH3COO.

[0014] Preferably, the bidentate diarylvinylpyridine ligand is selected from one of the following structures:

[0015]

[0016] The compound containing divalent palladium ions is selected from palladium nitrate, palladium chloride, and palladium acetate. The structure of the light-controlled endogenous chiral diarylethene supramolecular cage is selected from one of the following structures:

[0017]

[0018] A second aspect of the present invention provides a method for preparing the light-controlled endogenous chiral diarylethene supramolecular cage, comprising the following steps:

[0019] A bidentate diarylethylenepyridine ligand and a compound containing divalent palladium ions are dissolved in an organic solvent at a molar ratio of (1-5):1 (preferably (1-2):1, most preferably 1.5:1, 2:1), and sonicated until completely dissolved. The mixture is then reacted at a temperature of 40-80°C (preferably 50°C) for 1-12 hours (preferably 5-7 hours, more preferably 6 hours) to obtain the light-controlled endogenous chiral diarylethylene supramolecular cage.

[0020] The organic solvent is selected from DMSO.

[0021] The preparation method of the bidentate diarylvinylpyridine ligand includes the following steps:

[0022]

[0023] The compound BBTE-Br, a pyridine-containing compound, and an aqueous solution of K2CO3 are dissolved in an organic solvent. Tetraphenylphosphine palladium is then rapidly added to the solvent. The molar ratio of the compound BBTE-Br, the pyridine-containing compound, K2CO3, and tetraphenylphosphine palladium is 1:(1-15):(10-110):(0.1-4) (preferably 1:(5-11):(45-100):(0.2-3), and most preferably 1:5:48.4:0.2 or 1:10.1:100:2.25). The reaction is carried out under nitrogen protection at a temperature of 60-90°C (preferably 75°C) for 1-48 hours (preferably 12 hours or 24 hours) to obtain an intermediate.

[0024] The intermediate was chirally separated to obtain the bidentate diarylvinylpyridine ligand.

[0025] The pyridine-containing compound is selected from pyridine 3-borate,

[0026] The organic solvent is selected from THF.

[0027] The chiral separation was performed using a preparative liquid chromatography column (CHIRALPAK IC (IC00CE-BO005) or CHIRALPAK IG (IG00CE-UC011)), with a mobile phase of DCM / EtOAc / DEA = 80 / 20 / 0.1 (v / v / v), a flow rate of 1.0 ml / min, and a detection light source wavelength of 254 nm or 214 nm.

[0028] A third aspect of the present invention provides the application of the aforementioned light-controlled endogenous chiral diarylethene supramolecular cage in the preparation of photochromic materials, photoresponsive materials, fluorescent probes, chiral modulated materials, and organic light-emitting materials.

[0029] By adopting the above technical solution, the present invention has the following advantages and beneficial effects:

[0030] The present invention provides a method for preparing a light-controlled endogenous chiral diarylethylene supramolecular cage. In this preparation process, a palladium ion loses two nitrate ions and then coordinates with four nitrogen atoms on pyridine. The entire process is relatively simple, and the target product is ultimately formed under the influence of the self-correction behavior during thermodynamically driven supramolecular self-assembly. The present invention effectively solves the problem of poor solubility of bidentate diarylethylene pyridine ligands in DMSO solution by chiral separation of the bidentate diarylethylene pyridine ligands.

[0031] The method for preparing light-controlled endogenous chiral diarylethene supramolecular cages provided by this invention is a highly efficient one-pot synthesis method, which makes the coordination of bidentate diarylethene pyridine ligands and divalent palladium metal ions more efficient and precise, obtains the target product of quantitative conversion, and reduces mismatch phenomenon in the self-assembly process.

[0032] The photocontrolled endogenous chiral diarylethene supramolecular cage provided by this invention possesses a well-defined molecular structure, nanoscale chiral cavities, and photochromic properties. The advantage of this photocontrolled endogenous chiral diarylethene supramolecular cage lies in introducing chiral diarylethene building blocks into a metal cage-like complex, thereby enabling the metal cage to acquire excellent photoresponse properties. Furthermore, the chiral environment of the metal cage can be photocontrolled, reversibly, and specifically modulated using ultraviolet and visible light. Attached Figure Description

[0033] Figure 1 This is a schematic diagram of the hydrogen NMR spectrum of the intermediate ap-PY.

[0034] Figure 2 This is a schematic diagram of the single crystal structure of the intermediate ap-PY.

[0035] Figure 3 This is a schematic diagram of the 1H NMR spectrum of compound M-PY.

[0036] Figure 4 This is a schematic diagram of the hydrogen NMR spectrum of compound P-PY.

[0037] Figure 5 This is a schematic diagram of the chiral high-performance liquid chromatography (HPLC) spectrum of compound M-PY.

[0038] Figure 6 This is a schematic diagram of the chiral high-performance liquid chromatography (HPLC) spectrum of compound P-PY.

[0039] Figure 7 This is a schematic diagram of the 1H NMR spectrum of the diarylethene supramolecular cage M-MOC1.

[0040] Figure 8 This is a high-resolution mass spectrometry diagram of the diarylethylene supramolecular cage M-MOC1.

[0041] Figure 9 This is a schematic diagram of the 1H NMR spectrum of compound M-BPY.

[0042] Figure 10 This is a schematic diagram of the 1H NMR spectrum of the diarylethene supramolecular cage M-MOC2.

[0043] Figure 11 This is a high-resolution mass spectrometry diagram of the diarylethylene supramolecular cage M-MOC2.

[0044] Figure 12 This is a schematic diagram of the UV-Vis absorption spectrum of the diarylethylene supramolecular cage M-MOC1.

[0045] Figure 13 This is a schematic diagram of the UV-Vis absorption spectrum of the diarylethylene supramolecular cage M-MOC2.

[0046] Figure 14 This is a schematic diagram of the fluorescence spectrum of the diarylethylene supramolecular cage M-MOC1.

[0047] Figure 15 This is a schematic diagram of the fluorescence spectrum of the diarylethylene supramolecular cage M-MOC2.

[0048] Figure 16 This is a schematic diagram of the circular dichroism signal modulation of the diarylethylene supramolecular cage M-MOC1.

[0049] Figure 17This is a schematic diagram of the circular dichroism signal modulation of the diarylethylene supramolecular cage M-MOC2. Detailed Implementation

[0050] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0051] Example 1

[0052] The preparation method of the diarylethylene supramolecular cage includes the following steps:

[0053] The first step, the preparation method of the intermediate BBTE-Br, includes the following steps:

[0054]

[0055] In a 250 mL three-necked flask, compound BBTE (500 mg, 1.0 mmol), liquid bromine (2 mL, 38 mmol), and dichloromethane (75 mL) were added sequentially. The reaction was carried out at room temperature in the dark for 24 h. After the reaction was completed, the solution was introduced into 200 mL of saturated sodium sulfite solution for extraction. The organic phase was dried over anhydrous sodium sulfate and concentrated. The solvent was then evaporated. No purification was required, and the reaction proceeded directly to the next step.

[0056] The second step, the preparation method of the intermediate ap-PY, includes the following steps:

[0057]

[0058] In a 250 mL three-necked flask, compound BBTE-Br (800 mg, 1.24 mmol), pyridine 3-borate (766 mg, 6.23 mmol), 30 mL of K₂CO₃ (8.34 g, 60 mmol) aqueous solution, and 90 mL of THF were added sequentially. Tetraphenylphosphine palladium (300 mg, 0.26 mmol) was then rapidly added, and the reaction was carried out at 75 °C for 24 h under nitrogen protection. After concentrating the solvent, dichloromethane (50 mL) was added, followed by washing with water (25 mL × 2). The organic phase was dried over anhydrous sodium sulfate and concentrated, then subjected to silica gel column chromatography (eluent: DCM / MeOH = 50 / 1, v / v) to obtain 187 mg of yellow powder, the intermediate ap-PY, with an antiparallel configuration (confirmed by NMR and single-crystal structure analysis), yielding 23.3%. Figure 1 This is a schematic diagram of the hydrogen NMR spectrum of the intermediate ap-PY. Figure 2 This is a schematic diagram of the single-crystal structure of the intermediate ap-PY. ap-PY: 1H NMR (400MHz, CDCl3, ppm): δ8.90 (s, 2H), 8.59 (d, 2H, J = 4.0Hz), 7.98 (s, 2H), 7.93 (d, 2H, J = 8.0Hz), 7.50 (d, 2H, J = 8.4Hz), 7.38 (d, 2H, J1 = 4.8Hz, J2 = 4.8Hz), 7.23 (s, 2H), 2.01 (s, 6H).

[0059] Step 3, chiral decomposition of intermediate ap-PY:

[0060]

[0061] Intermediate ap-PY was separated using a preparative liquid chromatography column (CHIRALPAK IC(IC00CE-BO005)). The mobile phase was DCM / EtOAc / DEA = 80 / 20 / 0.1 (v / v / v), and the flow rate was 1.0 mL / min. The detection wavelength was 254 nm. A pair of enantiomers were obtained and named compounds M-PY and P-PY, respectively.

[0062] Figure 3 This is a schematic diagram of the 1H NMR spectrum of compound M-PY. Figure 4 This is a schematic diagram of the 1H NMR spectrum of compound P-PY. The EE value, determined by HPLC, is 99.8%. Figure 5 This is a schematic diagram of the chiral high-performance liquid chromatography (HPLC) spectrum of compound M-PY. Figure 6 This is a schematic diagram of the chiral high-performance liquid chromatography (HPLC) spectrum of compound P-PY. The ee value measured by HPLC is 99.6%.

[0063] M-PY: 1 H NMR (400MHz, CDCl3, ppm): δ8.90 (s, 2H), 8.59 (d, 2H, J = 4.0Hz), 7.98 (s, 2H), 7.93 (d, 2H, J = 8.0Hz), 7.50 (d, 2H, J = 8.4Hz), 7.38 (d, 2H, J1 = 4.8Hz, J2 = 4.8Hz), 7.23 (s, 2H), 2.01 (s, 6H).

[0064] P-PY: 1 H NMR (400MHz, CDCl3, ppm): δ8.90 (s, 2H), 8.59 (d, 2H, J = 4.0Hz), 7.98 (s, 2

[0065] H),7.93(d,2H,J=8.0Hz),7.50(d,2H,J=8.4Hz),7.38(d,2H,J1=4.8Hz,J2=4.8Hz),7.23(s,2H),2.01(s,6H).

[0066] The fourth step, the preparation method of the diarylethylene supramolecular cage, includes the following steps:

[0067] Compound M-PY (10.4 mg, 16.0 μmol) and palladium nitrate (2.6 mg, 8.0 μmol) were placed in a sample vial at once, and 1000 μL of DMSO solution was added. The mixture was sonicated until completely dissolved, and stirred at 50 °C in the dark for 6 hours. After the reaction was complete, 10 mL of isopropyl acetate was added, resulting in a pale yellow precipitate. This precipitate was dissolved in DMSO, and recrystallized three times with isopropyl acetate to obtain 11.8 mg of a yellow powder, namely diarylethene supramolecular cage M-MOC1, with a yield of 97.7%. Figure 7 This is a schematic diagram of the 1H NMR spectrum of the diarylethene supramolecular cage M-MOC1. Figure 8 This is a high-resolution mass spectrometry diagram of the diarylethylene supramolecular cage M-MOC1. 1 H NMR (400Hz, DMSO-d6, 293K): δ [ppm] 9.72 (s, 8H), 9.52 (d, J = 5.2Hz, 8H), 8.48 (d, J = 7.6Hz, 8H), 8.06 (s, 8H), 7.91 (t, J=6.0Hz,8H),7.8(d,J=8.0Hz,8H),7.69(d,J=8.4Hz,8H),1.95(s,24H).HRMS-ESI(m / z):Calcd.for[Pd2(oL)4-4NO3 - ] 4+ 694.0005,found694.0051;[Pd2(oL)4-NO3 - ] 3+ 946.0160, found 946.0107; [Pd2(oL)4-2NO3 - ] 2+ 1450.0222, found 1450.0135.

[0068]

[0069] Example 2

[0070] The preparation method of the diarylethylene supramolecular cage includes the following steps:

[0071] The first step, the preparation method of intermediate M2, includes the following steps:

[0072]

[0073] In a 500 mL three-necked flask, compound M1 (2.68 g, 8.61 mmol), 3-pyridineboronic acid (0.95 g, 8.01 mmol), and palladium catalyst Pd(PPh3)4 (92 mg, 0.08 mmol) were added. After purging with nitrogen for protection, a 2 mol·L⁻¹ solution was added. -1 A solution of potassium carbonate (120 mL) and tetrahydrofuran (250 mL) was reacted at 75 °C for 12 hours. After the reaction was complete, the solvent was removed, and the mixture was extracted with dichloromethane, dried, and then separated by column chromatography to give 1.52 g of white powder intermediate M2, with a yield of 72.1%. 1 HNMR (400MHz, CDCl3, 293K): δ [ppm] 3.98 (s, 3H), 7.04 (d, J = 1.2Hz, 1H), 7.06 (d, J = 1.2Hz, 1H), 7.37 ( m,1H),7.63(d,J=8.0Hz,1H),7.85(m,1H),8.62(dd,J1=4.2Hz,J2=1.6Hz,1H),8.83(d,J=1.6Hz,1H).

[0074] The second step, the preparation method of intermediate M3, includes the following steps:

[0075]

[0076] In a 100 mL three-necked flask that has been dehydrated and deoxygenated, compound M2 (526.5 mg, 2.02 mmol) and ultra-dry tetrahydrofuran (THF) (30 mL) were added. The mixture was cooled to -78 °C and stirred until fully dissolved. Under nitrogen protection, a 2.5 mol·L⁻¹ solution was added dropwise. -1 A solution of n-butyllithium (0.9 mL, 2.25 mmol) was prepared. After reacting at low temperature for 55 minutes, trimethyl borate (0.34 mL, 3 mmol) was added dropwise, and the mixture was slowly heated to room temperature and allowed to stand overnight to obtain a tetrahydrofuran solution of M3. This solution was directly added to the next reaction without purification.

[0077] The third step is the synthesis of compound M-BPY:

[0078]

[0079] Add BBTE-Br (128.1 mg, 0.20 mmol) to a 100 mL three-necked flask at a concentration of 2 mol·L⁻¹. -1A potassium carbonate aqueous solution (10 mL) and palladium catalyst Pd(PPh3)4 (517 mg, 0.45 mmol) were added under nitrogen protection, followed by the addition of a tetrahydrofuran solution (30 mL) containing intermediate M3 (500 mg, 2.02 mmol). The reaction was heated to 75 °C and carried out for 12 hours. After the reaction was completed, the THF solution was removed, and the mixture was extracted with DCM (100 mL × 3) and dried. The solvent was concentrated, and the mixture was separated by column chromatography (dichloromethane:methanol = 100:1). The solvent was then evaporated to dryness, yielding 102.5 mg of a yellow solid powder, namely compound o-BPY, with a yield of 61.1%.

[0080] Step 4, chiral decomposition of intermediate o-BPY:

[0081]

[0082] Compound o-BPY was chirally resolved using a preparative liquid chromatography column (CHIRALPAK IG (IG00CE-UC011)). The mobile phase was DCM / EtOAc / DEA = 80 / 20 / 0.1 (v / v / v), and the flow rate was 1.0 mL / min. The detection wavelength was 214 nm. A pair of enantiomers were obtained and named compounds M-BPY and P-BPY, respectively. Figure 9 This is a schematic diagram of the 1H NMR spectrum of compound M-BPY. 1 H NMR (400MHz, DMSO-d6, 293K): δ [ppm] 2.11 (s, 6H), 3.90 (s, 6H), 7.38-5.53 (m, 12H), 8.01 (s,2H),8.18(d,J=8.0Hz,2H),8.61(dd,J1=4.8Hz,J2=1.6Hz,2H),9.01(d,J=2.0Hz,2H).

[0083] The fifth step, the preparation method of the diarylethylene supramolecular cage, includes the following steps:

[0084] Compound M-BPY (10.2 mg, 12.0 μmol) and palladium nitrate (2.6 mg, 8.0 μmol) were placed in a sample vial at once, and DMSO solution (1000 μL) was added. The mixture was sonicated until completely dissolved, and stirred at 50 °C in the dark for 6 hours. After the reaction was complete, isopropyl acetate (10 mL) was added, and a pale yellow precipitate was formed. The precipitate was redissolved with DMSO, and recrystallized three times with isopropyl acetate to obtain 11.1 mg of yellow powder, namely diarylethene supramolecular cage M-MOC2, with a yield of 95.7%. Figure 10 This is a schematic diagram of the 1H NMR spectrum of the diarylethene supramolecular cage M-MOC2. Figure 11 This is a high-resolution mass spectrometry diagram of the diarylethylene supramolecular cage M-MOC2.

[0085] M-MOC2: 1 H NMR (400Hz, DMSO-d6, 293K): δ [ppm] 9.93 (s, 8H), 9.42 (d, J = 5.6Hz, 8H), 8.57 (d, J = 8.0Hz, 8H), 8.08 (s, 8H), 7.91 (t, J = 6.4Hz), 7.64 (d, J1 = 8.0Hz ,J2=3.2Hz,8H),7.52(d,J=8.4Hz),7.44(d,J=8.8Hz,8H),7.39(d,8H,),3.77(s,24H),1.96(s,24H).HRMS-ESI(m / z):Calcd.for[Pd2(oL)4-4NO3 - ] 4+ 906.0995, found 906.1051; [Pd2(oL)4-NO3 - ] 3+ 1228.7954, found 1229.1279; [Pd2(oL)4-2NO3 - ] 2+ 1874.1850, found 1874.1838.

[0086]

[0087] Example 3

[0088] Photoresponse performance testing of diarylethylene supramolecular cage M-MOC1

[0089] The diarylene ethylene supramolecular cage M-MOC1 prepared in Example 1 was dissolved in analytical grade dimethyl sulfoxide to prepare 5×10 -6 Solution M. Take 3000 μL of the above solution and transfer it to an optical quartz cuvette (10 × 10 mm) to test the change in its absorption spectrum under ultraviolet light excitation. Figure 12 This is a schematic diagram of the UV-Vis absorption spectrum of the diarylethene supramolecular cage M-MOC1. Initially, the open-ring M-MOC1 solution is colorless, corresponding to no absorption in the visible light region. Under UV light induction at 313 nm, the solution changes from colorless to red, and a new peak forms in the visible light region (460-640 nm), corresponding to the formation of the closed-ring metal cage. During the photoinduced absorption spectrum change, a clear isoabsorption point can be observed at 323 nm, indicating that after five photoisomerization cycles under alternating UV and visible light irradiation, the absorption intensity of M-MOC1 at 545 nm does not change significantly, indicating excellent fatigue resistance.

[0090] Example 4

[0091] Photoresponse performance testing of diarylethylene supramolecular cage M-MOC2

[0092] The diarylene ethylene supramolecular cage M-MOC2 prepared in Example 2 was dissolved in analytical grade dimethyl sulfoxide to prepare 5×10 -6 Solution M. Take 3000 μL of the above solution and transfer it to an optical quartz cuvette (10 × 10 mm) to test the change in its absorption spectrum under ultraviolet light excitation. Figure 13 This is a schematic diagram of the UV-Vis absorption spectrum of the diarylethene supramolecular cage M-MOC2. Initially, the open-ring M-MOC2 solution is colorless. Under UV irradiation at 313 nm, the solution changes from colorless to red, and the absorption peaks at 290 and 315 nm decrease simultaneously. A broad absorption peak is formed in the 400-640 nm range, corresponding to the formation of the closed-ring. Notably, a distinct isoabsorption point is formed at 345 nm, which is due to the addition of conjugated benzene ring structures. The figure shows the fatigue resistance test of M-MOC2. Under alternating irradiation with UV light (λ = 313 ± 10 nm) and visible light (λ > 510 nm), the absorbance of M-MOC2 did not change significantly after five photoisomerization cycles, indicating its excellent fatigue resistance.

[0093] Example 5

[0094] Fluorescence spectral modulation of diarylethene supramolecular cage M-MOC1

[0095] The diarylene ethylene supramolecular cage M-MOC1 prepared in Example 1 was dissolved in analytical grade dimethyl sulfoxide to prepare 5×10 -6 Solution M. Take 3000 μL of the above solution and transfer it to an optical quartz cuvette (10 × 10 mm) to test its fluorescence spectrum change under ultraviolet light (λ = 324 nm) excitation. Figure 14 This is a schematic diagram of the fluorescence spectrum of the diarylethylene supramolecular cage M-MOC1. After excitation at its isoabsorption point wavelength, the fluorescence emission peak is located near 544 nm. When excited with 313 nm ultraviolet light, a significant fluorescence quenching phenomenon occurs, attributed to the transformation from the yellow-green fluorescent open-ring state to the non-fluorescent closed-ring state. Under alternating irradiation with ultraviolet light (λ = 313 ± 10 nm) and visible light (λ > 510 nm), the diarylethylene supramolecular cage M-MOC1 exhibits reversible fluorescence modulation properties.

[0096] Example 6

[0097] Fluorescence spectral modulation of diarylethylene supramolecular cage M-MOC2

[0098] The diarylene ethylene supramolecular cage M-MOC2 prepared in Example 2 was dissolved in analytical grade dimethyl sulfoxide to prepare 5×10 -6Solution M. Take 3000 μL of the above solution and transfer it to an optical quartz cuvette (10 × 10 mm) to test its fluorescence spectrum change under ultraviolet light (λ = 344 nm) excitation. Figure 15 This is a schematic diagram of the fluorescence spectrum of the diarylethylene supramolecular cage M-MOC2. After excitation at its isoabsorption point wavelength, the fluorescence emission peak is near 545 nm. When excited with 313 nm ultraviolet light, a significant fluorescence quenching phenomenon occurs upon ring closure, accompanied by a 55 nm redshift in the emission wavelength. Under alternating irradiation with ultraviolet light (λ = 313 ± 10 nm) and visible light (λ > 510 nm), the diarylethylene supramolecular cage M-MOC2 exhibits reversible fluorescence modulation properties.

[0099] Example 7

[0100] Chiral regulation performance test of diarylethylene supramolecular cage M-MOC1

[0101] The diarylene ethylene supramolecular cage M-MOC1 prepared in Example 1 was dissolved in analytical grade dichloromethane to prepare 5×10 -6 Solution M. Take 3000 μL of the above solution and transfer it to an optical quartz cuvette (10 × 10 mm) to test its circular dichroism absorption change under ultraviolet light excitation. Figure 16 This is a schematic diagram of the circular dichroism signal modulation of the diarylethylene supramolecular cage M-MOC1. Its maximum absorption peak appears at 290 nm, and a new peak forms at 330 nm. The photosteady state M-MOC1PSS induced by ultraviolet light demonstrates that within the diarylethylene supramolecular cage M-MOC1, this photoinduced process from intrinsic axial chirality to central carbon chirality remains specific.

[0102] Example 8

[0103] Chiral regulation performance test of diarylethylene supramolecular cage M-MOC2

[0104] The diarylene ethylene supramolecular cage M-MOC2 prepared in Example 2 was dissolved in analytical grade dichloromethane to prepare 5×10 -6 Solution M. Take 3000 μL of the above solution and transfer it to an optical quartz cuvette (10 × 10 mm) to test its circular dichroism absorption change under ultraviolet light excitation. Figure 17 This is a schematic diagram of the circular dichroism signal modulation of the diarylethylene supramolecular cage M-MOC2. It exhibits absorption in the range of 230-440 nm, with a strong absorption peak at 290 nm, corresponding to the absorption bands of the olefin bridge BBT and the side-chain aryl group. The corresponding closed-ring structure formed by UV light demonstrates that the photoinduced process from intrinsic axial chirality to central carbon chirality within the diarylethylene supramolecular cage M-MOC2 is specific and particular.

[0105] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A light-controlled endo-chiral diar yl ethylene supramolecular cage, characterized in that, The structure of the light-controlled endogenous chiral diarylethene supermolecular cage is selected from one of the following structures: ； The preparation method of the light-controlled endogenous chiral diarylethene supermolecular cage comprises the following steps: The bidentate diarylethene pyridine ligand and the compound containing divalent metal palladium ions are dissolved in an organic solvent, and ultrasonic is performed until complete dissolution; the reaction is carried out at a temperature of 40-80℃ for 1-12h to obtain the light-controlled endogenous chiral diarylethene supermolecular cage; The preparation method of the bidentate diarylethene pyridine ligand comprises the following steps: ； The compound BBTE-Br, the pyridine-containing compound, and the aqueous solution of K2CO3 are dissolved in an organic solvent, and then tetrakis triphenylphosphine palladium is quickly added thereto; the molar ratio of the compound BBTE-Br, the pyridine-containing compound, K2CO3, and tetrakis triphenylphosphine palladium is 1:(1-15):(10-110):(0.1-4); the reaction is carried out under nitrogen protection at a temperature of 60-90℃ for 1-48h to obtain an intermediate; The intermediate is chiral split to obtain the bidentate diarylethene pyridine ligand; The bidentate diarylethene pyridine ligand is selected from one of the following structures: ； the pyridine-containing compound is selected from the group consisting of 3-pyridine boronic acid, .

2. The photoresponsive endochiral diarylethene supermolecular cage according to claim 1, wherein The chiral split is performed by using a preparative liquid chromatography column, and the mobile phase is selected from DCM / EtOAc / DEA=80 / 20 / 0.1; the flow rate is 1.0ml / min; and the detection light source wavelength is 254nm or 214nm.

3. Use of the light-controlled endogenous chiral diarylethene supermolecular cage in claim 1 in the preparation of photochromic materials, light-responsive materials, and chiral control materials.

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