CN111440193A - Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof - Google Patents
Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic photochromic materials, and particularly discloses an indene-condensed naphthospirooxazine photochromic compound which has a structure shown as a formula I, wherein R is1Is hydrogen, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, halogen or nitro; r2And R3Is straight chain or branched chain alkyl with 1-6 carbon atoms, and provides a synthesis method of the compound. The indene-thick naphthospirooxazine photochromic compound has the characteristics of quick photoresponse, quick fading, no ground color, good fatigue resistance and the like.
Description
Technical Field
The invention relates to the field of organic photochromic materials, in particular to an indene-condensed naphthospirooxazine photochromic compound and a preparation method thereof.
Background
Photochromic refers to that under the irradiation of light with a certain wavelength, the molecular structure of some compounds changes, which results in the obvious change of the absorption spectrum and the accompanying color change. And the original state is recovered under the irradiation of light with another wavelength or under the action of heat. The phenomenon of photochromism is a reversible chemical change process. In recent years, photochromic materials have been widely used in the fields of optical information storage, optical switches, optical modulation, optical devices, photochromic glasses, photochromic clothes, and the like.
The organic photochromic compound mainly comprises various types such as diarylethene, azobenzene, benzene/naphthopyran, spirooxazine and the like. Wherein, the color changing mechanism of the diarylethene photochromic compound is a pericyclic reaction, and is a P-type photochromic compound. The color-changing compound has the characteristics of bistable structure (open ring body and closed ring body), high photoresponse rate (open-loop and closed-loop reaction within picosecond range), excellent fatigue resistance and the like, and is widely applied to the fields of information storage, anti-counterfeiting printing and the like. The main drawback of diarylethene-based photochromic materials is represented by the low photoreaction conversion efficiency, generally not exceeding 50%. In addition, the synthesis conditions of the compounds are harsh, the cost is high, and the compounds are main factors for limiting the application of the compounds.
Azobenzene is a widely researched photochromic material, and the color change mechanism of azobenzene is cis-trans isomerization reaction based on azo double bonds, and the azobenzene is a T-type photochromic material. The azobenzene photochromic material has the main characteristics of simple structure and easy synthesis. The disadvantages are low conversion and slow conversion rates for cis-trans isomerisation, especially at room temperature. In addition, the fact that cis-trans isomers are all colored and the contrast is not significant also limits the practical application range.
The benzene/naphthopyran compounds also belong to T-type color-changing materials, and the color-changing mechanism is that C-O bond heterolysis under ultraviolet irradiation causes a ring-opening reaction, and the ring-closing reaction is stopped to return to an initial state after the ultraviolet irradiation. The compound has the outstanding advantages that the closed ring body is colorless, the open ring body presents color, the color can be regulated and controlled through structural modification, the fatigue resistance is better, and the compound has use value in the aspects of sunlight protective glasses, color-changing curtains and the like. The benzene/naphthopyran photochromic compounds have the disadvantages that the color change bodies contain TT-type isomers, the color fading speed is slow, and the complete color fading is generally required to be more than 8 minutes or even several hours.
The spirooxazine photochromic compound also belongs to a T-type photochromic material, a spiro C-O bond in a molecule is heterolytic under the excitation of ultraviolet light, so that a ring-opening reaction is caused to generate a color-changing body, and the color-changing body is subjected to a ring-closing reaction under the action of visible light or heat to return to an initial colorless state. Compared with naphthopyran photochromic compounds, spirooxazine photochromic compounds have outstanding photosensitivity and fatigue resistance, and have higher color ratio, so that the spirooxazine photochromic compounds have wider practical application range.
The development of photochromic compounds with fast photoresponse, fast fading and good fatigue resistance has become one of the research hotspots in the field of organic functional materials in recent years. Recently, we have disclosed a process for the preparation of indene fused ring naphthopyran based photochromic compounds (CN 110295037 a, CN 110343084A). The introduction of indene fused rings improves the rate of color and the rate of color fading of naphthopyran compounds, but the rate of color fading still needs to be further improved due to the presence of the color-changing TT-type isomer.
Therefore, the same intermediate for synthesizing the indene fused ring naphthopyran compound is adopted to prepare the novel indene fused ring naphthospirooxazine photochromic compound through two-step reaction, and the compound has the advantages of outstanding photoresponse, rapid fading, good fatigue resistance and the like, and has practical application value in the fields of solar protective glasses, glass windows, decorative articles, clothes, paint ink, anti-counterfeiting materials and the like.
Disclosure of Invention
The invention aims to provide an indene thick naphtho spirooxazine photochromic compound which has the advantages of quick photoresponse, quick fading, no bottom color and good fatigue resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an indene thick naphtho spirooxazine photochromic compound has a structure shown in a formula I:
in formula I: r1Hydrogen, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, halogen, nitro and the like; r2And R3Each independently is a linear or branched hydrocarbon group having 1 to 6 carbon atoms.
Preferably, R1Is hydrogen, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, halogen; r2And R3Each independently is a straight-chain or branched-chain hydrocarbon group having 1 to 6 carbon atoms.
Further preferably, R1Hydrogen, straight chain alkyl, straight chain alkoxy, halogen; r2And R3Is a straight chain hydrocarbon group with 1-6 carbon atoms.
Most preferably, R1Hydrogen, methyl, methoxy, chlorine; r2And R3Is methyl.
In another aspect, the present invention provides a method for preparing the compound as described above, comprising the steps of:
(1) synthesis of 7, 7-dimethyl-5-nitroso-7H-benzo [ c ] fluoren-6-ol
Reacting 7, 7-dimethyl-7H-benzo [ c]Adding fluorene-6-alcohol, a proper amount of organic solvent and water with the same volume into a round-bottom flask, and cooling in an ice bath. Adding NaOH dilute solution, continuously stirring for 30 minutes, and slowly adding a small amount of NaNO2The reaction was carried out in an ice bath for 1 hour. And (3) dropwise adding a dilute sulfuric acid solution into the reaction system, reacting for 1 hour at low temperature after dropwise adding is finished, and concentrating the reaction solution under reduced pressure to remove the solvent after the reaction is finished. The residue was subjected to silica gel column chromatography to obtain an orange solid product.
(2) Synthesis of Compounds of formula I
The 7, 7-dimethyl-5-nitroso-7H-benzo [ c ] obtained in the previous step]Adding the fluorene-6-alcohol into a reaction bottle, and adding ethanol for dissolving. N is a radical of2Protecting, stirring and heating to 90 ℃. And slowly dripping an ethanol solution of the 2-methylene indoline derivative, and carrying out reflux reaction for 12-24 hours. The reaction mixture was cooled to room temperature, and the solvent was removed by concentrating the reaction mixture under reduced pressure. The residue was separated by silica gel column chromatography to give brown solid I.
In the preparation method as described above, preferably, the organic solvent in the first step reaction is a water-miscible solvent, and may be acetone, acetonitrile, tetrahydrofuran, dioxane; in the reaction, the mole number of the sodium nitrite is 1 to 1.2 times that of the 7, 7-dialkyl-7H-benzo [ c ] fluorene-6-alcohol; the eluent for silica gel column chromatography adopts a mixed solution with the volume ratio of petroleum ether to ethyl acetate being 20: 1.
Preferably, the mole number of the 2-methylene indoline derivative in the second step reaction is 1.1-1.5 times that of 7, 7-dimethyl-5-nitroso-7H-benzo [ c ] fluorene-6-alcohol, and the eluent for silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 200: 1.
The invention provides application of a compound shown as a formula I as a photochromic material in the fields of sun protection glasses, glass windows, decorative articles, clothes, paint ink, anti-counterfeiting materials and the like.
The compound solution of the formula I can be changed into blue or green from colorless under the irradiation of ultraviolet rays. The light can fade from a colored state to colorless after stopping illumination, and the fading rate is high, and the light can fade to the colorless state within 3 seconds. The compound has the advantages of quick photoresponse, quick fading, no ground color, good fatigue resistance and the like, and has practical application prospects in the fields of sun protection glasses, glass windows, decorative articles, clothes, paint ink, anti-counterfeiting materials and the like.
Drawings
FIG. 1 shows the discoloration phenomena of the compound Ia of example 1 before and after light irradiation in a toluene solution, from left to right, before light irradiation, after light irradiation was stopped, respectively.
FIG. 2 shows the discoloration phenomena before and after light irradiation of the compound Ib of example 2 in a toluene solution, from left to right, before light irradiation, after light irradiation is stopped.
FIG. 3 is a graph showing the change of absorbance with the number of cycles in a toluene solution of Compound Id of example 4
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, the drugs and reagents used are commercially available or known in the art.
Example 1 preparation of photochromic Compound Ia
The first step is as follows: synthesis of 7, 7-dimethyl-5-nitroso-7H-benzo [ c ] fluoren-6-ol
Adding 7, 7-dialkyl-7H-benzo [ c ] fluorene-6-alcohol (0.41g,1.6mmol), 20M L acetonitrile, 20M L water and 3M L sodium hydroxide (2%) solution into a round-bottom flask, carrying out ice bath, stirring, adding a small amount of sodium nitrite (0.11g, 1.65mmol) solid, stirring and reacting at 0-5 ℃ for 1 hour, adding 0.38M L dilute sulfuric acid solution (5.6M) into the reaction solution, continuing to react for 1 hour, carrying out suction filtration, washing the filter cake for 2 times with a small amount of water, drying, purifying the crude product by silica gel column chromatography with a mixed solution of petroleum ether and ethyl acetate (30: 1) as an eluent to obtain an orange solid product of 0.36g and 78% yield.
7, 7-dihydrocarbyl-7H-benzo [ c]The nuclear magnetic resonance hydrogen spectrum characterization data of the fluorene-6-alcohol is as follows:1H NMR(400MHz,CDCl3)8.36(d,J＝7.7Hz,1H),8.26(d,J＝7.8Hz,1H),8.20(d,J＝7.2Hz,1H),7.74(t,J＝7.2Hz,1H),7.59–7.52(m,3H),7.52–7.47(m,1H),1.56(s,6H).
7, 7-dihydrocarbyl-7H-benzo [ c]The nuclear magnetic resonance carbon spectrum characterization data of the fluorene-6-alcohol are as follows:13C NMR(101MHz,CDCl3):181.33,177.15,158.62,149.44,146.97,136.91,135.06,133.46,131.84,130.85,130.54,130.20,127.75,126.38,125.35,122.81,48.59,24.54.
the second step is that: preparation of photochromic Compound Ia, the reaction scheme is as follows:
reacting 7, 7-dimethyl-5-nitroso-7H-benzo [ c]Adding 0.35g (1.20mmol) of fluorene-6-alcohol and 30m L ethanol into a reaction bottle, stirring for dissolving, heating to 90 ℃, and heating to N2Protecting, slowly adding a 5m L ethanol solution containing 0.27g (1.50mmol) of 1,3,3, 5-tetramethyl-2-methyleneindoline dropwise, refluxing for 24 hours, cooling to room temperature, concentrating the reaction solution under reduced pressure to remove the solvent, and purifying the crude product by silica gel column chromatography with a mixed solution of petroleum ether and ethyl acetate at a volume ratio of 200:1 as an eluent to obtain 90mg of a brown oily product with the yield of 17%.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ia are:1H NMR(400MHz,CDCl3)8.73(d,J＝8.0Hz,1H),8.70(d,J＝8.0Hz,1H),8.32(d,J＝8.0Hz,1H),7.83(s,1H),7.63–7.60(m,1H),7.56–7.53(m,1H),7.42–7.40(m,2H),7.36–7.32(m,1H),7.00(d,J＝8.0Hz),6.94(s,1H),6.43(d,J＝8.0Hz,1H),2.63(s,3H),2.36(s,3H),1.46(s,3H),1.44(s,6H),1.34(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ia are as follows:13C NMR(101MHz,CDCl3):155.82,148.77,145.24,141.78,139.76,139.55,136.44,136.27,131.34,129.21,128.13,127.14,126.89,126.15,125.39,124.69,123.78,123.38,123.06,122.72,122.18,122.12,106.87,98.00,51.27,47.49,29.81,25.90,24.72,24.21,21.11,20.75.
example 2 preparation of photochromic Compound Ib, the reaction scheme is as follows:
reacting 7, 7-dimethyl-5-nitroso-7H-benzo [ c]Adding 0.29g (1.00mmol) of fluorene-6-alcohol and 30m L ethanol into a reaction bottle, stirring for dissolving, heating to 90 ℃, and heating to N2Protecting, slowly adding dropwise 0.25g (1.20mmol) of 5-chloro-1, 3, 3-trimethyl-2-methyleneindoline) The reaction solution is refluxed for 24 hours, cooled to room temperature, and the reaction solution is concentrated under reduced pressure to remove the solvent, and the residue is eluted with a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 200:1, and the crude product is purified by silica gel column chromatography to obtain 80mg of a brown oily product with a yield of 17%.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ib are as follows:1H NMR(400MHz,CDCl3)8.71(d,J＝8.0Hz,2H),8.32(d,J＝8.0Hz,1H),7.82(s,1H),7.64–7.60(m,1H),7.57–7.53(m,1H),7.42–7.38(m,2H),7.37–7.33(m,1H),7.16(d,J＝8.0Hz),7.09(s,1H),6.44(d,J＝8.0Hz,1H),2.64(s,3H),1.44(s,3H),1.42(s,6H),1.33(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ib are as follows:13C NMR(101MHz,CDCl3):155.74,147.81,146.06,141.45,139.54,139.43,138.11,136.76,131.30,127.76,127.19,127.04,126.27,125.49,124.85,124.66,123.80,123.42,122.98,122.72,122.23,121.86,108.02,97.75,51.27,47.47,29.78,25.69,24.76,24.24,20.47
example 3 preparation of photochromic Compound Ic the reaction scheme is as follows:
the 7, 7-dimethyl-5-nitroso-7H-benzo [ c ] obtained in the previous step]Adding 0.15g (0.52mmol) of fluorene-6-alcohol and 20m L ethanol into a reaction flask, stirring for dissolving, heating to 90 ℃, and heating to N2Protecting, slowly adding a 5m L ethanol solution containing 111mg (0.62mmol) of 1,3, 3-trimethyl-2-methyleneindoline dropwise, refluxing for 24 hours, cooling to room temperature, concentrating the reaction solution under reduced pressure to remove the solvent, and purifying the crude product by silica gel column chromatography with a mixed solution of petroleum ether and ethyl acetate at a volume ratio of 200:1 as an eluent to obtain 70mg of a brown oily product with the yield of 30%.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ic are:1H NMR(400MHz,CDCl3)8.74(d,J＝8.0Hz,1H),8.70(d,J＝8.0Hz,1H),8.31(d,J＝8.0Hz,1H),7.84(s,1H),7.63–7.59(m,1H),7.56–7.52(m,1H),7.43–7.39(m,2H),7.35–7.31(m,1H),7.22–7.19(m,1H),7.13(d,J＝8.0Hz,1H),6.92(t,J＝8.0Hz,1H),6.53(d,J＝8.0Hz,1H),2.67(s,3H),1.45(s,3H),1.44(s,3H),1.43(s,3H),1.32(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ic are:13C NMR(101MHz,CDCl3):155.81,148.64,147.41,141.71,139.72,139.54,136.55,136.17,131.35,128.00,127.18,126.95,126.21,125.44,124.76,123.81,123.41,123.01,122.75,122.22,121.25,120.01,107.13,97.83,51.27,47.48,29.72,25.81,24.68,24.18,20.71.
example 4 preparation of photochromic compound Id, the reaction scheme is as follows:
reacting 7, 7-dimethyl-5-nitroso-7H-benzo [ c]Adding 0.30g (1.04mmol) of fluorene-6-alcohol and 30m L ethanol into a reaction bottle, stirring for dissolving, heating to 90 ℃, and heating to N2Protecting, slowly adding 5m L ethanol solution containing 0.25g (1.25mmol) of 5-methoxy-1, 3, 3-trimethyl-2-methylene indoline dropwise, refluxing for 24 hours, cooling to room temperature, concentrating the reaction solution under reduced pressure to remove the solvent, and purifying the crude product by silica gel column chromatography with a mixed solution of petroleum ether and ethyl acetate 200:1 as an eluent to obtain 100mg of brown oily product with the yield of 20%.
The NMR hydrogen spectrum characterization data of Id is:1H NMR(400MHz,CDCl3)8.71(d,J＝8.4Hz,1H),8.68(d,J＝8.4Hz,1H),8.30(d,J＝8.4Hz,1H),7.82(s,1H),7.62–7.58(m,1H),7.55–7.52(m,1H),7.41–7.39(m,2H),7.35–7.31(m,1H),6.76–6.71(m,2H),6.42(d,J＝8.4Hz,1H),3.83(s,3H),2.61(s,3H),1.44(s,3H),1.43(s,3H),1.42(s,3H),1.32(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Id is as follows:13C NMR(101MHz,CDCl3):155.80,154.28,148.51,141.77,141.58,139.73,139.52,137.81,136.46,131.32,127.13,126.90,126.16,125.38,124.68,123.77,123.37,122.69,126.19,111.51,109.15,107.31,98.19,55.92,51.38,47.48,30.04,25.75,24.70,24.19,20.55.
example 5 photochromic Properties testing of Compound Ia
Weighing and combiningObject Ia, arrangement 8 × 10-5The toluene solution of mol/L is colorless before illumination, and is rapidly changed from colorless to blue-green by illumination with xenon lamp light source (electric power of 180W; light power of 50W; ultraviolet power of 2.6W; visible light power of 19.6W).
FIG. 1 shows the discoloration of a toluene solution of compound Ia after 30 seconds of light exposure. The compound is colorless before color change and is blue-green after illumination according to the color change phenomenon. The light was stopped and the solution changed from blue-green to colorless and transparent within 3 seconds.
EXAMPLE 6 testing of photochromic Properties of Compound Ib
Weighing compound Ib, and preparing into 8 × 10-5The toluene solution of mol/L is colorless before illumination, and is rapidly changed from colorless to blue by illumination with xenon lamp light source (electric power of 180W; optical power of 50W; ultraviolet power of 2.6W; visible light power of 19.6W).
FIG. 2 shows the discoloration of a toluene solution of compound Ib after 30 seconds of light irradiation. The compound is colorless before color change and blue after illumination according to the color change phenomenon. The light was stopped and the solution changed from blue to colorless and transparent within 3 seconds.
As can be seen from the color-changing property test, the indene thick naphthospirooxazine photochromic compound has the outstanding advantages of colorless solution before illumination, quick illumination color change, high decolorization rate (complete color-changing time is 3 seconds) and no ground color. The decolorization rate is significantly better than that of the currently commercialized indene thick naphthopyran compounds (the complete decolorization time is 8 minutes, DyesPigments2019,169, 118-124.).
In practical tests, after the illumination is stopped, the solution is instantly changed from blue or blue-green to colorless and transparent, even is lower than the lowest detection limit of an instrument and can only be observed by naked eyes.
Fatigue resistance test of Compound Id of example 7
Weighing compound Id, configuration 8 × 10-5The method comprises the steps of measuring a photochromic/fading cycle curve of a toluene solution of mol/L by using an ultraviolet spectrophotometer, irradiating the solution for 30s under an Xe-150 xenon lamp in an experiment to saturate absorbance, then placing the solution in the dark for 30min, and respectively measuringMaximum absorption wavelength (lambda) at saturation of photochromism and at bleaching to a colorless statemax560 nm). The cycle was repeated 10 times and the collected data was plotted as a cycle graph as shown in fig. 3.
The above description is made in detail for the preferred embodiments of the present invention, but the above description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (8)
1. An indene thick naphtho spirooxazine photochromic compound has a structural formula shown as the following formula I:
in the formula: r1Is hydrogen, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, halogen or nitro; r2And R3Each independently is a linear or branched hydrocarbon group having 1 to 6 carbon atoms.
2. The process for preparing the indene-fused naphthospirooxazine photochromic compound of claim 1, wherein: r1Is hydrogen, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, halogen; r2And R3Each independently is a straight-chain or branched-chain hydrocarbon group having 1 to 6 carbon atoms.
3. The process for preparing the indene-fused naphthospirooxazine photochromic compound of claim 1, wherein: r1Hydrogen, straight chain alkyl, straight chain alkoxy, halogen; r2And R3Is a straight chain hydrocarbon group with 1-6 carbon atoms.
4. The process for preparing the indene-fused naphthospirooxazine photochromic compound of claim 1, wherein: r1Is hydrogen, methyl or methylOxy, chloro; r2And R3Is methyl.
5. The process for preparing the indene-fused naphthospirooxazine photochromic compound of any one of claims 1 to 4, wherein the process comprises the steps of:
(1) synthesis of 7, 7-dimethyl-5-nitroso-7H-benzo [ c ] fluoren-6-ol
Reacting 7, 7-dimethyl-7H-benzo [ c]Adding fluorene-6-alcohol, a proper amount of organic solvent and water with the same volume into a round-bottom flask, and cooling in an ice bath; adding NaOH dilute solution, continuously stirring for 30 minutes, and slowly adding a small amount of NaNO2Reacting for 1 hour in ice bath; dropwise adding a dilute sulfuric acid solution into the reaction system, and reacting for 1 hour at low temperature after dropwise adding; after the reaction is finished, decompressing and concentrating the reaction solution to remove the solvent; separating the residue by a silica gel column chromatography to obtain an orange solid product;
(2) synthesis of Compounds of formula I
The 7, 7-dimethyl-5-nitroso-7H-benzo [ c ] obtained in the previous step]Adding fluorene-6-ol and ethanol into a reaction flask, N2Protecting, stirring and heating to 90 ℃; slowly dripping an ethanol solution of the 2-methylene indoline derivative, and carrying out reflux reaction for 12-24 hours; cooling to room temperature, and concentrating the reaction solution under reduced pressure to remove the solvent; the residue was separated by silica gel column chromatography to give brown solid I.
6. The process for producing the indene-fused naphthospirooxazine-based photochromic compound according to any one of claims 1 to 4, characterized in that: the organic solvent in the first step of reaction is a water-miscible solvent selected from acetone, acetonitrile, tetrahydrofuran and dioxane; the mole number of the sodium nitrite in the reaction is 1 to 1.2 times that of the 7, 7-dialkyl-7H-benzo [ c ] fluorene-6-alcohol; the eluent for silica gel column chromatography adopts a mixed solution with the volume ratio of petroleum ether to ethyl acetate being 20: 1.
7. The process for producing the indene-fused naphthospirooxazine-based photochromic compound according to any one of claims 1 to 4, characterized in that: in the second step of reaction, the mole number of the 2-methylene indoline derivative is 1.1-1.5 times that of 7, 7-dimethyl-5-nitroso-7H-benzo [ c ] fluorene-6-alcohol, and the eluent of the silica gel column chromatography adopts a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 200: 1.
8. Use of a compound according to any one of claims 1 to 4 in the field of sun protection glasses, glazings, decorative articles, clothing, paint inks, security materials.
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|---|---|---|---|---|
| CN113501827A (en) * | 2021-07-12 | 2021-10-15 | 南开大学 | Chiral binaphthopyran photochromic compound and preparation method and application thereof |
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| CN113896736A (en) * | 2021-11-18 | 2022-01-07 | 南开大学 | Aryl-substituted spirooxazine photochromic compound and preparation method and application thereof |
| CN114014886A (en) * | 2021-11-18 | 2022-02-08 | 南开大学 | Silicon-fused-ring naphthopyran photochromic compound and preparation method and application thereof |
| CN114014886B (en) * | 2021-11-18 | 2022-12-27 | 南开大学 | Silicon fused ring naphthopyran photochromic compound and preparation method and application thereof |
| CN113896736B (en) * | 2021-11-18 | 2023-03-03 | 南开大学 | Aryl-substituted spirooxazine photochromic compound and preparation method and application thereof |
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