Synthesis of endogenous and exogenous chiral photochromic dye and liquid crystal application of endogenous and exogenous chiral photochromic dye

Abstract

The invention provides synthesis of an endogenous and exogenous chiral photochromic dye and liquid crystal application of the endogenous and exogenous chiral photochromic dye. The steric hindrance type diarylethene is used as a matrix, endogenous chirality and exogenous chirality are integrated into a single molecule for the first time, and the endogenous and exogenous chiral dynamic optical switch based on the steric hindrance type diarylethene is provided. The binaphthol is obtained by determining whether the binaphthol is bridged or not, changing the bridging length of the binaphthol and introducing side chain alkyl to change the molecular structure. The synthesized RBNBT series molecules have the characteristics of high thermal stability and strong fatigue resistance, and two different diastereoisomers, namely (R, M, R)-RBNBT series molecules and (R, P, R)-RBNBT series molecules, can be formed through chiral resolution.

Description

Technical Field

[0001] This invention belongs to the field of photochromic dyes and relates to the preparation and application of a class of endogenous and exogenous chiral photoswitches, specifically to the preparation and application of an endogenous and exogenous chiral dynamic photoswitch based on sterically hindered diarylethene. Background Technology

[0002] Traditional diarylethylene ring-opening derivatives, due to the rapid rotation of the side chains, result in a pair of racemic derivatives upon ring closure. Therefore, chirality control in traditional diarylethylene is generally achieved by modifying with additional chiral groups. However, external chiral groups often exhibit asymmetric inductive effects during photocyclization reactions, forming a pair of diastereomers with opposite chiral centers. This makes chiral separation difficult for subsequent research.

[0003] Stereohedral diarylethylene uses benzodithiadiazole as the olefin bridge and benzothiophene as the side-chain aryl group. Due to the steric hindrance effect of the benzothiophene side chain, not only can the parallel and antiparallel isomers p-BBTE and ap-BBTE be separated, but further separation using chiral columns can also reveal its chiral isomers. P-ap -BBTE and M-ap -BBTE, the corresponding chiral isomers of the closed-loop body are denoted as (R,R)-c-BBTE and (S,S)-c-BBTE, respectively. This is a photoresponsive intrinsic chiral switch with excellent thermal stability and fatigue resistance.

[0004] In recent years, there has been a constant stream of research on endogenous and exogenous chirality, but there are very few studies on the interaction between endogenous and exogenous chirality in materials that possess both. There is a large gap in this area of ​​research. Therefore, it is of great significance to explore stimulus-responsive photoswitching molecules containing interactions between different types of chiral molecules. Summary of the Invention

[0005] This invention addresses the aforementioned problems by providing a class of photochromic dyes containing both intrinsic and extrinsic chirality, which achieve dynamic light switching through the interaction between intrinsic and extrinsic chirality.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, this invention provides a class of dynamic photoswitching molecules containing both intrinsic and extrinsic chirality. Using sterically hindered diarylethylene as a matrix, this invention, for the first time, integrates intrinsic and extrinsic chirality into a single molecule, providing a class of dynamic photoswitches based on sterically hindered diarylethylene with both intrinsic and extrinsic chirality. The molecular structure is altered by determining whether binaphthol is used for bridging, changing the bridging length of binaphthol, and introducing side-chain alkyl groups. The general structural formula of the provided dynamic photoswitches based on sterically hindered diarylethylene with both intrinsic and extrinsic chirality is shown in Formula I below:

[0008]

[0009] (I)

[0010] In Equation I, n = 0, 1, 2, 3, or 4.

[0011] R1, R2, R3, R4 are selected from Any one of them.

[0012] The preferred structure is as follows:

[0013]

[0014] .

[0015] In this ap-RBNBT series of molecules, the endogenous chirality P and M cancel each other out, while the exogenous chirality R-binaphthol remains, and the ap-RBNBT series of molecules as a whole still retains chiral characteristics.

[0016] In a second aspect, the present invention provides a method for synthesizing the above-mentioned dynamic optical switch RBNBT series molecules containing endogenous and exogenous chirality, the synthetic route of which is as follows:

[0017]

[0018] The specific preparation steps are as follows:

[0019] (1) R-naphthol and 1,4-dibutane halogen substitutes are added to a reaction vessel that has been dried at high temperature (such as flame) in a molar ratio of 1:2~6. Then carbonate and aprotic polar organic solvent are added. After the reaction is completed under inert gas protection and refluxed at 80°C, a pale yellow solid is obtained by silica gel column chromatography.

[0020] (2) Add the product of step (1) and anhydrous aprotic polar organic solvent to the reaction vessel that has been dried at high temperature, cool to -79°C, and slowly add n-butyllithium; after stirring for a certain period of time, add 1,2-dihalogen-substituted tetrachloroethane dissolved in the same aprotic polar organic solvent, the amount of which is 1 to 4 times that of the product of step 1. After the reaction is complete at low temperature, move to room temperature, monitor the reaction on a TLC plate, add a small amount of water to quench the butyllithium, and separate by silica gel column chromatography to obtain a white solid;

[0021] (3) The product of step (2) and tetrahydroxydiboron were added to a three-necked flask that had been dried at high temperature in a molar ratio of 1:3.5. Then potassium acetate, X-Phos, Xphos Pd G2 and methanol were added in sequence. The reaction solution was concentrated by reflux at 80°C under nitrogen protection and separated by silica gel column chromatography to obtain a white solid.

[0022] (4) In a single-necked flask, the product of step (3) and the BBTE-2 halogenated product were dissolved in an aprotic polar organic solvent at a molar ratio of 2 to 4.5:1. An aqueous solution of carbonate was then added. Under a nitrogen atmosphere, tetraphenylphosphine palladium (5 wt%) was added and the mixture was refluxed at 75 °C. After the reaction was completed by TLC monitoring, the reaction solution was concentrated and the final product was obtained by silica gel column chromatography.

[0023] The preferred technical solutions for the above two steps are as follows:

[0024] In step (1), the 1,4-dibutane halogenated derivative is selected from 1,4-diiodobutane, 1,4-dibromobutane or 1,4-dichlorobutane, preferably 1,4-diiodobutane;

[0025] The carbonate is selected from any one of potassium carbonate, sodium carbonate, and magnesium carbonate;

[0026] The aprotic polar organic solvent is selected from any one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran, with N,N-dimethylformamide being preferred;

[0027] The inert gas is selected from nitrogen or argon.

[0028] In step (2), the anhydrous aprotic polar organic solvent is selected from any one of anhydrous N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran, preferably anhydrous tetrahydrofuran;

[0029] The amount of n-butyllithium is 2-4 times that of the product from step 1;

[0030] The stirring time should be 40-60 minutes, preferably 45 minutes;

[0031] 1,2-Dihalogen-substituted tetrachloroethane is selected from 1,2-dibromotetrachloroethane, 1,2-dichlorotetrachloroethane, or 1,2-diiodotetrachloroethane;

[0032] The low-temperature reaction temperature is -75℃, and the reaction time is about 1 hour.

[0033] In step (3), the molar ratio of the product from step (2), potassium acetate, X-Phos, Xphos Pd G2, and methanol is 1:3:0.01:0.005:50.

[0034] In step (4), the BBTE-2 halogenated derivative is selected from BBTE-2Cl or BBTE-2Br;

[0035] The aprotic polar organic solvent is selected from any one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran, preferably tetrahydrofuran;

[0036] The carbonate is selected from any one of potassium carbonate, sodium carbonate, and magnesium carbonate, and the concentration is 2 mol / L.

[0037] The optimal reflux reaction time at 75℃ is 8 hours.

[0038] Preferably, the above method further includes a chiral separation step, using a chiral column of CHIRALPAK IC (IC00CE-WF029), a mobile phase of Hexane / DCM / DEA = 60 / 40 / 0.1, a flow rate of 1.0 ml / min, and a detection light source wavelength of 254 nm, which forms a pair of diastereomers after separation.

[0039] The prepared dynamic optical switching molecule RBNBT series, after chiral column separation, was used as a chiral dopant molecule and mixed with nematic commercial liquid crystal TEB 300 in the following proportions. R, M, R )-RBNBT series: 1~2 wt%, TEB 300: 98~99 wt%; R, P, R RBNBT series: 1~2 wt%, TEB 300: 98~99 wt%. The liquid crystal mixture was filled into a vertical alignment cell using a capillary tube and observed using a polarizing microscope. Its liquid crystal performance was studied by observing the disappearance and reproduction of fingerprint texture and changes in pitch.

[0040] The results showed that, R, M, R )-RBNBTPB exhibits a trend of increasing pitch under ultraviolet light irradiation, indicating a decrease in its helical twisting force and a redshift in its wavelength band. R, P, R-RBNBTPB shows the opposite trend, exhibiting a decreasing pitch under ultraviolet light, indicating increased helical twisting force and a blue shift in the wavelength. R, M, R )- RBNBT and ( R, M, R )-RBNBTPB, ( R, P, R )- RBNBT and ( R, P, R )-RBNBTPB each exhibit the same changes, and all show chiral inversion.

[0041] Therefore, in a third aspect, the present invention provides the application of the above-mentioned dynamic light-switching molecules containing endogenous and exogenous chirality in the preparation of photochromic dyes, and particularly in the preparation of liquid crystal materials.

[0042] In a fourth aspect, the present invention provides a liquid crystal material containing the aforementioned dynamic light-switching molecule with intrinsic and extrinsic chirality.

[0043] Preferably, the dynamic light-switching molecules containing endogenous and exogenous chirality are chiralized and then mixed with nematic commercial liquid crystal TEB 300 in a ratio of 1~2wt%: 98~99wt% to form the liquid crystal material.

[0044] In a fifth aspect, the present invention provides a liquid crystal device comprising the liquid crystal material described above.

[0045] The role and effect of invention

[0046] The dynamic optical switch synthesized in this invention integrates intrinsic and extrinsic chirality into a single molecule, and for the first time studies the interaction between the two, filling a research gap.

[0047] The dynamic optical switch synthesized in this invention, containing both intrinsic and extrinsic chirality, exhibits high stability and high fatigue resistance.

[0048] The dynamic optical switch containing intrinsic and extrinsic chirality synthesized in this invention, after chiral separation, and the resulting (R, M, R)-RBNBT series molecules and (R, P, R)-RBNBT series molecules, when mixed with commercial nematic liquid crystal TEB 300, all exhibited different liquid crystal phenomena. Attached Figure Description

[0049] Figure 1 It is the final product ap -Schematic diagram of the 1H NMR spectrum of RBNBT.

[0050] Figure 2 It is the final product ap - Schematic diagram of high-resolution mass spectrometry for RBNBT.

[0051] Figure 3 It is the final product ap -Schematic diagram of the 1H NMR spectrum of RBNBTB.

[0052] Figure 4 It is the final product ap - Schematic diagram of high-resolution mass spectrometry of RBNBTB.

[0053] Figure 5 It is a chiral separation product ( R, M, R Schematic diagram of the 1H NMR spectrum of RBNBTB.

[0054] Figure 6 It is a chiral separation product ( R, M, R )- Schematic diagram of high-resolution mass spectrometry of RBNBTB.

[0055] Figure 7 It is a chiral resolution product ( R, P, R Schematic diagram of the 1H NMR spectrum of RBNBTB.

[0056] Figure 8 It is a chiral resolution product ( R, P, R )- Schematic diagram of high-resolution mass spectrometry of RBNBTB.

[0057] Figure 9 yes ap -RBNBTB, ( R, M, R )- RBNBTB and ( R, P, R )- Schematic diagram of chiral liquid phase analysis of RBNBTB.

[0058] Figure 10 It is the final product ap -Schematic diagram of the 1H NMR spectrum of RBNBTPB.

[0059] Figure 11 It is the final product ap - Schematic diagram of high-resolution mass spectrometry for RBNBTPB.

[0060] Figure 12 yes ap -RBNBTB, (R, M, R)-RBNBTB and ( R, P, R )- Schematic diagram of the circular dichroism test of RBNBTB.

[0061] Figure 13 yes( R,M, R Pitch variation of )-RBNBTPB under ultraviolet and visible light irradiation.

[0062] Figure 14 yes( R,P, R Pitch variation of )-RBNBTPB under ultraviolet and visible light irradiation.

[0063] Figure 15yes( R, M, R )-RBNBTB chiral reversal direction determination diagram.

[0064] Figure 16 yes( R, P, R )-RBNBTB chiral reversal direction determination diagram. Detailed Implementation

[0065] The following embodiments further illustrate the present invention and should not be construed as limiting the invention. The embodiments do not include a detailed description of conventional methods, which are well known to those skilled in the art and described in numerous publications.

[0066] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as are familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention, and the preferred embodiments and materials described in the specific implementation are for illustrative purposes only.

[0067] Unless otherwise specified, the experimental methods described in the following examples are generally performed under standard conditions or as recommended by the manufacturer.

[0068] Example 1

[0069] Preparation of the final product RBNBT:

[0070]

[0071] In a 200 mL single-necked flask, BBTE-2Br (267 mg, 0.42 mmol), M3 (645.4 mg, 1.52 mmol), K2CO3 (3.5 g, 25.2 mmol), Pd(PPh3)4 (75 mg, 0.0648 mmol), THF (39 mL), and H2O (13 mL) were added sequentially. The mixture was refluxed at 75 °C for 10 h under nitrogen protection. After the reaction was completed by TLC monitoring, the reaction solution was concentrated. The mixture was extracted with DCM (40 mL × 3), and the organic phase was dried over anhydrous sodium sulfate and separated by silica gel column chromatography (DCM) to obtain 415.3 mg of a red powder solid, with a yield of 91.6%. Figure 1 It is the final product ap -Schematic diagram of the 1H NMR spectrum of RBNBT. Figure 2 It is the final product ap - Schematic diagram of high-resolution mass spectrometry for RBNBT. ap - RBNBT : 1H NMR (400 MHz, CDCl3, ppm) δ: 2.12 (s, 3 H, -CH3), 2.18 (s, 3 H, -CH3), 5.32 (dd, J1= 16.0 Hz, J2= 3.5 Hz, 2 H, -CH2-), 5.51 (d, J = 3.3 Hz, 2 H, -CH2-), 7.21 (d, J = 8.4 Hz, 2 H, benzothiophene-H), 7.29 - 7.36 (m, 4 H, phenyl-H), 7.44 - 7.52 (m, 9 H, phenyl-H), 7.54 (d,J = 3.6 Hz, 1 H, phenyl-H), 7.58 (d, J = 8.6 Hz, 2 H, benzothiophene-H), 7.96 (dd, J1= 10.2 Hz, J2= 4.8 Hz, 6 H, phenyl-H), 8.05 (s, 2 H, benzothiophene-H), 8.06 (s, 1 H, phenyl-H), 8.08 (s, 1 H, phenyl-H). HRMS-ESI (m / z): [M+Na] + Calculated for C 66 H 38 O4N4NaS4, 1101.1668; found, 1101.1661.

[0072] Example 2

[0073] Preparation of the final product RBNBTB:

[0074]

[0075] In a 200 mL single-necked flask, BBTE-2Br (267 mg, 0.42 mmol), M6 (583.9 mg, 1.52 mmol), K2CO3 (3.5 g, 25.2 mmol), Pd(PPh3)4 (75 mg, 0.0648 mmol), THF (39 mL), and H2O (13 mL) were added sequentially. The mixture was refluxed at 75 °C for 10 h under nitrogen protection. After the reaction was complete as monitored by TLC, the reaction solution was concentrated. The mixture was extracted with DCM (40 mL × 3), and the organic phase was dried over anhydrous sodium sulfate and separated by silica gel column chromatography (PE:DCM = 1:4) to obtain 421.8 mg of a red powder solid, with a yield of 86.4%. Figure 3 It is the final product ap -Schematic diagram of the 1H NMR spectrum of RBNBTB. Figure 4 This is a high-resolution mass spectrometry diagram of the final product ap-RBNBTB. ap - RBNBTB : 1 H NMR (400 MHz, CDCl3, ppm) δ:1.40-1.59 (m, 4 H, -CH-, Overlapping with H2O), 1.66-1.72 (m, 2 H, -CH-), 1.85-1.98 (m, 2 H, -CH-), 2.16 (s, 3 H, CH3), 2.31 (s, 3 H, -CH3), 3.43-3.63(m, 4 H, -CH-), 4.02 (q, J = 11.5 Hz, 2 H, -CH-), 4.70 (t, J = 11.7 Hz, 2 H,-CH-), 7.02 (s, 1 H, phenyl-H), 7.04 (d, J = 4.5 Hz, 2 H, phenyl-H), 7.07 (s,1 H, phenyl-H), 7.15 (d, J = 2.3 Hz, 1 H, phenyl-H), 7.17-7.23 (m, 5 H,phenyl-H and benzothiophene-H), 7.30-7.38 (m, 4 H, phenyl-H), 7.49 (d, J =1.4 Hz, 1 H, phenyl-H), 7.52-7.55 (m, 2 H, benzothiophene-H), 7.58 (d, J =8.4 Hz, 1 H, phenyl-H), 7.85-7.88 (m, 4 H, phenyl-H), 7.90 (s, 1 H, phenyl-H), 7.95 (s, 3 H, phenyl-H and benzothiophene-H), 7.97 (d, J = 2.8 Hz, 1 H,phenyl-H), 8.03 (s, 1 H, phenyl-H and benzothiophene-H). HRMS-ESI (m / z): [M+Na] + Calculated for C 72 H 50 O4N4S4Na, 1185.2613; found, 1185.2627. [M+K]+ Calcd. forC 72 H 50 O4N4S4K, 1201.2346; found, 1201.2371.

[0076] ap -RBNBTB chiral splitting:

[0077]

[0078] Will ap -RBNBTB was separated into a pair of diastereomers using chiral column chromatography, named ( ). R, M, R )-RBNBTB and ( R, P, R )- RBNBTB. Figure 5 It is a compound ( R, M, R Schematic diagram of the 1H NMR spectrum of RBNBTB. Figure 6 It is a compound ( R, M, R )- Schematic diagram of high-resolution mass spectrometry of RBNBTB. Figure 7 It is a compound ( R, P, R Schematic diagram of the 1H NMR spectrum of RBNBTB. Figure 8 It is a compound ( R, P, R )- Schematic diagram of high-resolution mass spectrometry of RBNBTB. Figure 9 Compounds in order ap -RBNBTB, ( R, M, R )- RBNBTB and ( R, P, R Schematic diagram of the high-performance liquid chromatography (HPLC) spectrum of RBNBTB. The ee value measured by HPLC is greater than 98%.

[0079] Example 3

[0080] Preparation of the final product RNBTPB:

[0081]

[0082] In a 200 mL single-necked flask, add M sequentially. 11 (500 mg, 0.67 mmol), M 12(918.4 mg, 1.37 mmol), K₂CO₃ (7.45 g, 54.05 mmol), Pd(PPh₃)₄ (156 mg, 0.13 mmol), THF (162 mL), and H₂O (54 mL) were refluxed at 75 °C for 10 h under nitrogen protection. After the reaction was completed by TLC monitoring, the reaction solution was concentrated. Extraction was performed using DCM (40 mL × 3), and the organic phase was dried over anhydrous sodium sulfate and separated by silica gel column chromatography (DCM:PE = 2:1) to give 492.67 mg of red solid, yield 44.2%. ap-RBNBTPB: 1 H NMR (400 MHz, CDCl3, ppm) δ: 0.91(s, 12H, -CH3), 1.36(s, 16 H, -CH2-), 1.67(s, 8 H, -CH2-), 2.13(s, 3 H, -CH3), 2.19(s, 3 H, -CH3), 2.67(t, J = 7.6 Hz, 8 H, -CH2-), 5.35 (dd, J1= 14.8 Hz, J2=3.2 Hz, 2 H, -CH2-), 5.53 (d, J = 3.2 Hz, 2 H, -CH2-), 7.23(s, 1 H, phenyl-H), 7.30 - 7.32 (m, 8 H, benzothiophene-H and phenyl-H), 7.46 - 7.50 (m, 2 H,phenyl-H), 7.54 - 7.72 (m, 19 H, benzothiophene-H and phenyl-H ), 8.03 (dd,J1= 8.8 Hz, J2= 3.6 Hz, 2 H, phenyl-H), 8.09(t, J = 6.0 Hz, 3 H, phenyl-H), 8.14 - 8.17 (m, 5 H, benzothiophene-H and phenyl-H). HRMS-ESI (m / z): [M+Na] + Calculated for C 110 H 94 O4N4NaS4, 1685.6050; found, 1685.6002. Figure 10 This is a schematic diagram of the 1H NMR spectrum of the final product ap-RBNBTPB. Figure 11 This is a high-resolution mass spectrometry diagram of the final product ap-RBNBTPB.

[0083] Example 4

[0084] ap -RBNBTB, ( R, M, R )- RBNBTB and ( R, P, R )- Circular dichroism test of RBNBTB

[0085] Take the molecules obtained in Example 1 ap -RBNBTB, ( R, M, R )- RBNBTB and ( R, P, R )-RBNBTB, dissolved in analytical grade tetrahydrofuran, to prepare a solution of 2×10 -4 25 ml of solution M. Take 100 μL of the prepared solution and 1900 μL of analytical grade tetrahydrofuran and transfer them to an optical quartz glass cuvette to test their CD spectrum. Figure 12 It's M3. ap -RBNBTB, ( R, M, R )-RBNBTB and ( R, P, R The circular dichroism spectral changes of RBNBTB were observed. Based on the CD spectrum of M3, it can be determined that the chiral signal of exogenous chiral binatol is mainly concentrated in the ultraviolet region and is not present in the visible region. Therefore... ap -RBNBTB, ( R, M, R )-RBNBTB and ( R, P, R The chirality of RBNBTB is primarily determined by the signal in the visible light region. R, M, R Taking RBNBTB as an example, under 313nm ultraviolet light, ( R, M, R The solution of RBNBTB exhibits a negative Cotton effect peak in the circular dichroism spectroscopy at 400-600 nm. Based on our previous research on BBTE, we determined that it belongs to the combination of R-configuration binaphthol and M-configuration BBTE. Similarly, ( R, P, R )-RBNBTB belongs to the combination of R-configuration binaphthol and P-configuration BBTE. More interestingly, ( R, M, R )- RBNBTB negative Cotton effect peak ratio at 400-600 nm ( R, P, R The positive Cotton effect peak signal of RBNBTB is relatively low, mainly due to ( R, M, R )- RBNBTB represents an offsetting effect, while ( R, P, R )-RBNBTB is a synergistic effect.

[0086] Example 5

[0087] ( R, M, R )- RBNBTPB and ( R, P, RVerification of liquid crystal modulation of RBNBTPB

[0088] The liquid crystal mixture is prepared by mixing the following proportions, namely ( R, M, R )-RBNBTPB: 1.008 wt%, TEB 300:98.992 wt%; ( R, P, R )-RBNBTPB: 1.171 wt%, TEB 300: 98.829 wt%. The above mixture was poured into a vertical orientation box using a capillary tube. The change in HTP was determined by the change in pitch before and after illumination, and then the band was adjusted accordingly. Figure 13 yes( R, M, R Pitch variation of )-RBNBTPB under ultraviolet and visible light irradiation. Figure 14 yes( R, P, R Pitch variation of )-RBNBTPB under ultraviolet and visible light irradiation. (wherein, R, M, R )-RBNBTPB exhibits a trend of increasing pitch under ultraviolet light irradiation, indicating a decrease in its helical twisting force and a redshift in its wavelength band. R, P, R -RBNBTPB, on the other hand, exhibits the opposite trend, showing a decreasing pitch under ultraviolet light irradiation, indicating increased helical twisting force and a blue shift in the wavelength range. Subsequent experimental results are consistent with this assessment. R, M, R )- RBNBT and ( R, M, R )-RBNBTPB, ( R, P, R )- RBNBT and ( R, P, R The changes in )-RBNBTPB are the same, and will not be elaborated here.

[0089] Example 6

[0090] ( R, M, R )- RBNBTB and ( R, P, R Chiral inversion verification of RBNBTB

[0091] The liquid crystal mixture, prepared according to the following proportions, was used as a standard with cholesterol oil-based alkenyl carbonate. The chiral reversal direction was determined by observing changes in fingerprint texture before and after illumination. (R, M, R)-RBNBTB: 1.074 wt%, TEB 300: 98.926 wt%; Figure 15 This is a schematic diagram for determining the chiral inversion of (R, M, R)-RBNBTB. (R, P, R)-RBNBTB: 1.174 wt%, TEB 300: 98.826 wt%. Figure 16 This is a schematic diagram for determining the chiral inversion of (R, P, R)-RBNBTB.

[0092] The undescribed parts of this invention are the same as or implemented using existing technology. The applicant declares that this invention is illustrated through the above embodiments, but the invention is not limited to the above detailed methods, i.e., it does not mean that the invention must rely on the above detailed methods to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. A dynamic optical switching molecule containing endogenous and exogenous chirality, characterized in that, Using sterically hindered diarylethene as the matrix, the general structural formula is shown in Formula I below: ， （I） In Equation I, n = 0, 1, 2, 3, or 4. R1, R2, R3, R4 are selected from Any one of them.

2. The dynamic optical switching molecule containing endogenous and exogenous chirality according to claim 1, characterized in that, The specific structure can be selected from any of the following: ， 。 3. The method for preparing the dynamic optical switching molecule containing endogenous and exogenous chirality as described in claim 1 or 2, characterized in that, Includes the following steps: (1) R-naphthol and 1,4-dibutane halogenated products were added to a reaction vessel that had been dried at high temperature. The molar ratio of the two products was 1:2~6. Then carbonate and aprotic polar organic solvent were added. After the reaction was completed under the protection of inert gas and refluxed at 80°C, a pale yellow solid was obtained by silica gel column chromatography. (2) Add the product of step (1) and anhydrous aprotic polar organic solvent to the reaction vessel that has been dried at high temperature, cool to -79°C, and slowly add n-butyllithium; after stirring for a certain period of time, add 1,2-dihalogen-substituted tetrachloroethane dissolved in the same aprotic polar organic solvent, the amount of which is 1 to 4 times that of the product of step 1. After the reaction is complete at low temperature, move to room temperature, monitor the reaction on a TLC plate, add a small amount of water to quench the butyllithium, and separate by silica gel column chromatography to obtain a white solid; (3) The product of step (2) and tetrahydroxydiboron were added to a three-necked flask that had been dried at high temperature in a molar ratio of 1:3.

5. Then potassium acetate, X-Phos, Xphos Pd G2 and methanol were added in sequence. The reaction solution was concentrated by reflux at 80°C under nitrogen protection and separated by silica gel column chromatography to obtain a white solid. (4) In a single-necked flask, the product of step (3) and the BBTE-2 halogenated product were dissolved in an aprotic polar organic solvent at a molar ratio of 2 to 4.5:

1. An aqueous solution of carbonate was then added. Under a nitrogen atmosphere, 5 wt% tetratriphenylphosphine palladium was added and the mixture was refluxed at 75 °C. After the reaction was completed by TLC monitoring, the reaction solution was concentrated and separated by silica gel column chromatography to obtain the final product as a red powder.

4. The method for preparing a dynamic photo-switching molecule containing endogenous and exogenous chirality according to claim 3, characterized in that: In step (1), the reaction vessel that has been dried at high temperature is selected from the vessel that has been dried by flame; The halogenated derivatives of 1,4-dibutane are selected from 1,4-diiodobutane, 1,4-dibromobutane, or 1,4-dichlorobutane; The carbonate is selected from any one of potassium carbonate, sodium carbonate, and magnesium carbonate; The aprotic polar organic solvent is selected from any one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran; The inert gas is selected from nitrogen or argon. In step (2), the anhydrous aprotic polar organic solvent is selected from any one of anhydrous N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran; The amount of n-butyllithium is 2-4 times that of the product from step 1; The stirring time should be 40-60 minutes. 1,2-Dihalogen-substituted tetrachloroethane is selected from 1,2-dibromotetrachloroethane, 1,2-dichlorotetrachloroethane, or 1,2-diiodotetrachloroethane; The low-temperature reaction temperature was -75℃, and the reaction time was 1 h.

5. The method for preparing a dynamic photo-switching molecule containing endogenous and exogenous chirality according to claim 3, characterized in that: In step (3), the molar ratio of the product from step (2), potassium acetate, X-Phos, Xphos Pd G2, and methanol is 1:3:0.01:0.005:

50. In step (4), the BBTE-2 halogenated derivative is selected from BBTE-2Cl or BBTE-2Br; The aprotic polar organic solvent is selected from any one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran; The carbonate is selected from any one of potassium carbonate, sodium carbonate, and magnesium carbonate, and the concentration is 2 mol / L; The reflux reaction time at 75℃ is 8 hours.

6. The method for preparing a dynamic optical switch molecule containing endogenous and exogenous chirality according to claim 3, Its features are, It also includes a chiral separation step, using a CHIRALPAK IC chiral separation column, with a mobile phase of Hexane / DCM / DEA=60 / 40 / 0.1, a flow rate of 1.0 ml / min, and a detection light source wavelength of 254 nm. After separation, a pair of diastereomers are formed.

7. The application of the dynamic light-switching molecule containing endogenous and exogenous chirality as described in claim 1 or 2 in the preparation of liquid crystal materials.

8. A liquid crystal material, characterized in that, The molecule contains the dynamic optical switch molecule with endogenous and exogenous chirality as described in claim 1 or 2.

9. The method for preparing the liquid crystal material according to claim 8, characterized in that, Dynamic light-switching molecules containing intrinsic and extrinsic chirality are chiralized and then mixed with nematic commercial liquid crystal TEB 300 in a ratio of 1~2 wt%: 98~99 wt% to form the liquid crystal material.

10. A liquid crystal device, characterized in that, It contains the liquid crystal material as described in claim 8.

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