CN114634546A - High-luminous-power photochromic material from red to near infrared and preparation method thereof - Google Patents
High-luminous-power photochromic material from red to near infrared and preparation method thereof Download PDFInfo
- Publication number
- CN114634546A CN114634546A CN202210280685.4A CN202210280685A CN114634546A CN 114634546 A CN114634546 A CN 114634546A CN 202210280685 A CN202210280685 A CN 202210280685A CN 114634546 A CN114634546 A CN 114634546A
- Authority
- CN
- China
- Prior art keywords
- red
- reaction
- sodium carbonate
- ethanol
- thiadiazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000003333 near-infrared imaging Methods 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 50
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 formamidobenzyl cyanide Chemical compound 0.000 claims abstract description 32
- 235000012000 cholesterol Nutrition 0.000 claims abstract description 29
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 22
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- PAMBVPQLDDXPCQ-UHFFFAOYSA-N boric acid;n,n-diphenylaniline Chemical compound OB(O)O.C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 PAMBVPQLDDXPCQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000013067 intermediate product Substances 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 238000004440 column chromatography Methods 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000005964 Acibenzolar-S-methyl Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 6
- VPDPNJVAWKCZEH-UHFFFAOYSA-N 4-bromo-2,1,3-benzothiadiazole-7-carbaldehyde Chemical compound BrC1=CC=C(C=O)C2=NSN=C12 VPDPNJVAWKCZEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- IWHQXSQPWFXQEZ-UHFFFAOYSA-N OBO.C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound OBO.C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 IWHQXSQPWFXQEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims 2
- 230000008859 change Effects 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000000523 sample Substances 0.000 abstract 1
- 230000003068 static effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 238000004020 luminiscence type Methods 0.000 description 6
- 239000007850 fluorescent dye Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical class F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000008423 fluorobenzenes Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J43/00—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J43/003—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton not condensed
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
Abstract
The invention belongs to the field of high luminous power photochromic materials, and provides a high luminous power photochromic material from red to near infrared and a preparation method thereof, wherein the preparation method comprises the following steps of 1, weighing 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, triphenylamine boric acid, tetratriphenyl phosphorus palladium and sodium carbonate, preparing the sodium carbonate into a sodium carbonate aqueous solution, and dissolving the raw materials in chromatographic toluene and tetrahydrofuran; then extracting, filtering, separating by column chromatography and rotary evaporating to obtain red powder to obtain 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole; step 2, dissolving the intermediate product, the cholesterol formamidobenzyl cyanide and sodium methoxide in ethanol; and leaching the filter cake with ethanol for 3 times, and drying to obtain red powder, namely the target product. The invention has larger force-induced ratio color change, can be used as a fluorescent pressure sensing probe, and has the following characteristics: the fluorescence efficiency is high (44.3%), the synthesis is simple, the relationship between pressure and emission wavelength can be quantitatively determined, the color change range is large, and the material has great application potential in a pressure sensing system.
Description
Technical Field
The invention belongs to the field of high-luminous-power photochromic materials, and particularly relates to a preparation method of a high-luminous-power photochromic material from red to near infrared.
Background
In recent years, organic near-infrared (680nm-900nm) fluorescent dyes have wide application prospects in the fields of biological imaging, pressure sensing, infrared camouflage, anti-counterfeiting detection, fluorescence identification and the like due to the advantages of strong penetrability, strong anti-interference capability, good sensitivity and the like.
Several kinds of near-infrared fluorescent probes have been reported so far, and such materials can be classified into: stilbene nitriles, difluoroboron compounds, tetrastyrenes, arylcyanines, thiazines, BODIPY compounds, and the like. For example, (chem. eur. j.,2014,21,2474-2479) reported a diphenylvinylnitrile-based electron donating-electron withdrawing structure compound pCN-TPA, which exhibits 508nm luminescence at an initial normal pressure, gradually red-shifted to 618nm under the action of static pressure, red-shifted to 110nm, and restored to the initial state after the static pressure is released. (chem. Commun.,2016,52,3836-3839) a cyano-substituted stilbene derivative structure CzCNDSB was synthesized, the initial luminescence was 529nm, red-shifted by 155nm to 684nm under the action of external static pressure, a change from green to deep red was achieved, and the luminescence returned to the initial state after the removal of the static pressure. (Angew. chem. int. Ed.,2020,59,15267-15267) by using a eutectic strategy, the anthracene derivative and the fluorobenzene derivative are fumigated by a solvent to obtain the eutectic, the eutectic can realize 554nm luminescence in an initial state, and can be red-shifted to 92nm to 646nm (green-red conversion) under the action of static pressure.
However, the hydrostatic photochromic materials having high fluorescence quantum efficiency and in the near infrared region are still relatively few. The key to constructing high-contrast color change from near-infrared deep red to near-infrared is to inhibit the intermolecular pi-pi interaction under pressure.
Disclosure of Invention
The invention aims to solve the problems recorded in the background technology and provides a preparation method of a high-luminous-power photochromic material from red to near infrared.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a high-luminous-power photochromic material from red to near infrared comprises the following steps:
weighing 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, triphenylamine boric acid, tetratriphenylphosphine palladium and sodium carbonate, preparing sodium carbonate into a sodium carbonate solution, and dissolving the raw materials in chromatographic toluene and tetrahydrofuran; under the protection of nitrogen atmosphere, carrying out reflux stirring reaction, confirming the reaction process by a point plate when a large amount of red solid particles are separated out, and stopping the reaction if the reaction is complete; then extracting, filtering, separating by column chromatography and rotary evaporating to obtain red powder, namely the 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole;
dissolving the intermediate product, cholesterol formamido benzyl cyanide and sodium methoxide in ethanol; stirring and reacting at 60 ℃ under the protection of nitrogen atmosphere, and stopping the reaction when a large amount of solid particles are separated out; and then, putting the ethanol solution of the product into a refrigerator for cooling and separating out, filtering after the solid is completely separated out, leaching a filter cake obtained by filtering for 3 times by using ethanol, and drying to obtain red powder, namely the target product.
The target product is a near-infrared light region color-changing dye benzothiadiazole cholesterol formamido benzyl cyanide derivative, and the chemical formula is as follows: c61H67N5O2S。
In a preferred embodiment of the invention, the molar ratio of 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole to triphenylamine boronic acid is 1:1 to 1: 1.5; 7-bromo-4-formylbenzo [ c ] [1,2,5] thiadiazole: sodium carbonate: toluene: the dosage ratio of the tetrahydrofuran is as follows: 0.8-1.2mmol of 10-60 ml of 50-40 ml of sodium carbonate solution, wherein the concentration of the sodium carbonate solution is 3 mol/L.
In a preferred embodiment of the present invention, in step 1, the reaction time is 12-24h under reflux and the reaction temperature is 80-100 ℃.
In a preferred embodiment of the invention, the extraction liquid is dichloromethane and the eluent for the column chromatography is petroleum ether and dichloromethane.
In a preferred embodiment of the present invention, in step 2, the molar ratio of the cholesterol formamidophenylacetonitrile to the intermediate product is 1:1 to 1: 1.3; cholesterol formamidophenylacetonitrile: sodium methoxide: chromatographic ethanol is 3mmol, 0.3-0.6mmol, 30-50 ml.
In a preferred embodiment of the present invention, in step 2, the reaction time is stirred for 10 to 12 hours.
In a preferred embodiment of the present invention, in step 2, the temperature in the refrigerator is-10 to 0 ℃, and the time for putting into the refrigerator is 2 to 3 hours.
In a preferred embodiment of the invention, in step 2, the volume molar ratio of ethanol to cholesterol formamidophenylacetonitrile used for each leaching is 2:1, and the leaching times are 3-6 times.
In a preferred embodiment of the present invention, a high luminous power color-changing material from red to near infrared, prepared by the method of any one of claims 1 to 8, is applied to a pressure detecting material.
The principle and the beneficial effects of the invention are as follows: the static pressure ratio color-changing material provided by the invention has the characteristics of obvious color change (red is changed into near infrared) and good sensitivity to external stimulation, and the material can be used for pressure sensing elements and optical recording by applying static pressure to change the color ratio of the material.
Molecules form unique dimer accumulation during aggregation, and non-conjugated cholesterol can inhibit strong pi-pi action among molecules in the process of close accumulation.
Compared with the prior art, most near-infrared fluorescent molecules have low fluorescent efficiency and complex synthesis, the near-infrared fluorescent molecules have high fluorescent efficiency (44.3 percent), generate 157nm spectrum red shift and are simple to synthesize, and the application potential of the material in the field of pressure detection is greatly enhanced.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a fluorescence spectrum of static pressure ratio discoloration of near infrared benzothiadiazole cholesterol formamido benzyl cyanide fluorescent dyes under pressure of 0atm-2.0 GPa;
FIG. 2 is a fluorescence spectrum of static pressure ratio discoloration of near infrared benzothiadiazole cholesterol formamido phenylacetonitrile fluorescent dye under the pressure of 2.6-7 GPa;
FIG. 3 is a graph showing the relationship between the static pressure and the spectrum of the near-infrared benzothiadiazole cholesterol formamido phenylacetonitrile fluorescent dye.
FIG. 4 is a unique dimer stack formed by the molecules.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "longitudinal", "lateral", "vertical", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description of the present invention, unless otherwise specified and limited, it is to be noted that the terms "mounted," "connected," and "connected" are to be interpreted broadly, and may be, for example, a mechanical connection or an electrical connection, a communication between two elements, a direct connection, or an indirect connection via an intermediate medium, and specific meanings of the terms may be understood by those skilled in the art according to specific situations.
The application provides a preparation method of a high-luminous-power photochromic material from red to near infrared, which comprises the following steps:
the synthetic route is as follows:
the specific operation is as follows: weighing 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, triphenylamine boric acid, tetratriphenylphosphine palladium and sodium carbonate, preparing sodium carbonate into a sodium carbonate aqueous solution, and dissolving the raw materials in chromatographic toluene and tetrahydrofuran, wherein the molar ratio of the 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole (III) to the triphenylamine boric acid (IV) is 1:1-1: 1.5; 7-bromo-4-formylbenzo [ c ] [1,2,5] thiadiazole: sodium carbonate: chromatographic toluene: chromatographic tetrahydrofuran 10mmol, 0.8-1.2mmol, 50-60ml, 30-40 ml; under the protection of nitrogen atmosphere, refluxing and stirring for 12-24h, confirming the reaction process by a point plate when a large amount of red solid particles are separated out, and stopping the reaction when the reaction is basically finished; then the reaction solution is extracted, filtered and separated by silica gel column chromatography, and petroleum ether: dichloromethane ═ 2:1, leaching, decompressing and rotary steaming to obtain red powder, namely a product intermediate (II);
the synthetic route is as follows:
the specific operation is as follows: weighing an intermediate (II), cholesterol formamido phenylacetonitrile (V) and sodium methoxide, and dissolving in chromatographic ethanol, wherein the molar ratio of the cholesterol formamido phenylacetonitrile (V) to the intermediate (II) is 1:1-1: 1.3; cholesterol formamidophenylacetonitrile (v): sodium methoxide: chromatographic ethanol is 3mmol, 0.3-0.6mmol, 30-50 ml. Stirring and reacting for 8-12h at 60 ℃ under the protection of nitrogen atmosphere, and stopping the reaction when a large amount of solid particles are separated out; and then placing the reaction system in a refrigerator at the temperature of-20-0 ℃ for 8-10h, filtering to obtain a filter cake, leaching the filter cake for 3-6 times by using ethanol, wherein the volume molar ratio (L/mol) of the ethanol to the cholesterol formamido phenylacetonitrile used for leaching each time is 2:1, and drying to obtain red powder, namely the target product benzothiadiazole cholesterol formamido phenylacetonitrile derivative (I). Wherein (I) the molecular weight is 933.5 g/mol; (II) the molecular weight is 407 g/mol; (V) a molecular weight of 544 g/mol;
the feeding ratio of the substances (II) and (V) is controlled to be 1:1 or (II) is slightly excessive but not more than 1: 1.3; the amount of the catalyst sodium methoxide is controlled within the following range: cholesterol formamidophenylacetonitrile (v): sodium methoxide 1mmol:0.1-0.2 mmol. The target molecule in the invention has higher fluorescence quantum efficiency and simple synthesis, thus greatly increasing the huge application potential as a pressure sensing system.
The experimental mode is as follows:
The characterization data are as follows:1H NMR(400MHz,CDCl3)δ8.72(d,J＝7.6Hz,1H),8.49(s,1H),7.94(d,J＝8.8Hz,2H),7.84(d,J＝7.6Hz,1H),7.79(d,J＝8.8Hz,2H),7.54(d,J＝8.8Hz,2H),7.34(t,J＝8.4Hz,4H),7.23(m,6H),7.11(t,J＝7.6Hz,2H),6.77(s,1H),5.44(d,J＝4.8Hz,1H),4.67(m,1H),2.41(m,2H),1.61(m,12H),1.36(m,3H),1.16(m,8H),1.07(m,6H),0.94(d,J＝6.4Hz,3H),0.89(dd,J＝2.0Hz,J＝1.6Hz,6H),0.71(s,3H)；[M]+934.4986。
The target product benzothiadiazole cholesterol formamido benzyl cyanide derivative (i) obtained by the above experimental modes 1 to 4 is shown in fig. 4, molecules form unique dimer accumulation, red flaky crystals are obtained in a mixed solution of n-hexane/tetrahydrofuran by a solvent volatilization method, emission spectra under different pressures are explored, and the relationship between the fluorescence emission spectrum intensity and wavelength and the static pressure is roughly determined, as shown in fig. 1 and 2: the crystal can emit red to near infrared fluorescence, and the fluorescence intensity is continuously reduced and the color of the fluorescence is gradually changed from red to near infrared along with the increase of pressure. This phenomenon presupposes that the material can be used in the field of pressure sensors or in the field of information storage. In addition, the spectrogram is processed to obtain the position of the emission peak, and a relation graph of the static pressure and the position of the emission peak of the fluorescence emission spectrum is obtained by linear fitting, as shown in fig. 3: in the process of gradually increasing static pressure, the luminescence of the red crystal is gradually red-shifted, the luminescence position and the static pressure show a certain linear relation, the relation between pressure and spectrum is 22.1nm/GPa, the wavelength is changed by 157nm, and the material can be used for a pressure sensing element.
In summary, the static pressure-induced proportional color-changing material provided by the invention has the characteristics of obvious color change (as shown in fig. 3, in the range of 1atm to 7Gpa, the wavelength is red-shifted from 650nm to 806nm along with the increase of pressure, the red shift reaches 156nm, the red is changed into near infrared, so the color change is obvious), and good sensitivity to external stimuli (as can be seen from the spectrograms of fig. 1 and 2, the fluorescence intensity is obviously reduced along with the increase of pressure), and the material can change the color ratio by applying static pressure to the material, and can be used for pressure sensing elements and optical recording.
Most of near-infrared fluorescent molecules have low fluorescence efficiency and relatively complex synthesis, and the near-infrared fluorescent molecules have high fluorescence efficiency (44.3 percent) and simple synthesis, thereby greatly increasing the huge application potential as a pressure sensing system
In the description herein, reference to the description of the terms "preferred embodiment," "one embodiment," "some embodiments," "an example," "a specific example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A preparation method of a high-luminous-power photochromic material from red to near infrared is characterized by comprising the following steps:
step 1, synthesizing an intermediate product 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole:
weighing 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, triphenylamine boric acid, tetratriphenylphosphine palladium and sodium carbonate, preparing sodium carbonate into a sodium carbonate solution, and dissolving the raw materials in chromatographic toluene and tetrahydrofuran; under the protection of nitrogen atmosphere, carrying out reflux stirring reaction, confirming the reaction process by a point plate when a large amount of red solid particles are separated out, and stopping the reaction if the reaction is complete; then extracting, filtering, separating by column chromatography and rotary evaporating to obtain red powder, namely the 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole;
step 2, synthesis of a target product:
dissolving the intermediate product, cholesterol formamido benzyl cyanide and sodium methoxide in ethanol; stirring and reacting at 60 ℃ under the protection of nitrogen atmosphere, and stopping the reaction when a large amount of solid particles are separated out; and then, cooling and separating out the ethanol solution of the product in a refrigerator, filtering after the solid is completely separated out, leaching the filter cake obtained by filtering for 3 times by using ethanol, and drying to obtain red powder, namely a target product, wherein the target product is the near-infrared region color-changing dye benzothiadiazole cholesterol formamido benzyl cyanide derivative.
2. The method of claim 1, wherein the molar ratio of 7-bromo-4-formylbenzo [ c ] [1,2,5] thiadiazole to triphenylamine boronic acid is 1:1 to 1: 1.5; 7-bromo-4-formylbenzo [ c ] [1,2,5] thiadiazole: sodium carbonate: toluene: the dosage ratio of the tetrahydrofuran is as follows: 0.8-1.2mmol of 10-60 ml of 50-60ml of 30-40ml of 10mmol, wherein the concentration of the sodium carbonate solution is 3 mol/L.
3. The method for preparing a high luminous power of red to near infrared photochromic material of claim 2 wherein in step 1, the reaction time is 12-24 hours under reflux and stirring, and the reaction temperature is 80-100 ℃.
4. The method of claim 3, wherein the extraction liquid is dichloromethane and the eluent for column chromatography is petroleum ether and dichloromethane.
5. The method for preparing a high luminous power chromic material from red to near infrared as claimed in claim 4 wherein, in the step 2, the molar ratio of the cholesterylaminobenzylcyanide to the intermediate product is 1:1 to 1: 1.3; cholesterol formamidophenylacetonitrile: sodium methoxide: chromatographic ethanol is 3mmol, 0.3-0.6mmol, 30-50 ml.
6. The method for preparing a high luminous power chromic material from red to near infrared as claimed in claim 5 wherein, in the step 2, the stirring reaction time is 10-12 h.
7. The method for preparing a high luminous power chromic material from red to near infrared as claimed in claim 6 wherein, in the step 2, the temperature in the refrigerator is-10-0 ℃ and the time of putting into the refrigerator is 2-3 h.
8. The method for preparing a red to near-infrared high luminous force electrochromic material according to claim 7, wherein in the step 2, the volume molar ratio of ethanol to cholesterol formamidophenylacetonitrile used for each elution is 2:1, and the elution times are 3 to 6.
9. C prepared by the method of any one of claims 1 to 861H67N5O2S。
10. A high luminous power chromic material from red to near infrared prepared by the method of any one of claims 1 to 8 applied to a pressure detecting material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210280685.4A CN114634546B (en) | 2022-03-22 | 2022-03-22 | High-luminous-power electrochromic material from red to near infrared and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210280685.4A CN114634546B (en) | 2022-03-22 | 2022-03-22 | High-luminous-power electrochromic material from red to near infrared and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114634546A true CN114634546A (en) | 2022-06-17 |
| CN114634546B CN114634546B (en) | 2023-07-28 |
Family
ID=81948923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210280685.4A Active CN114634546B (en) | 2022-03-22 | 2022-03-22 | High-luminous-power electrochromic material from red to near infrared and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114634546B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957095A (en) * | 2022-06-30 | 2022-08-30 | 江西科技师范大学 | Carbazole derivative and preparation method and application thereof |
| CN115109054A (en) * | 2022-07-11 | 2022-09-27 | 湖州学院 | Preparation method and application of color-changing material with multiple stimulus responses |
| CN115947701A (en) * | 2022-12-05 | 2023-04-11 | 浙江工业大学 | Deep red to near-infrared high-luminous-power photochromic material and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3578680A (en) * | 1967-06-09 | 1971-05-11 | Fuji Photo Film Co Ltd | Photochromic compound |
| EP0389813A1 (en) * | 1989-03-30 | 1990-10-03 | Matsushita Electric Industrial Co., Ltd. | A method for preparing a photochromic material |
| CN102875398A (en) * | 2012-06-08 | 2013-01-16 | 浙江工业大学 | Application of triphenylamine derivative as reversible force stimulus fluorescent switch material |
| CN103102286A (en) * | 2012-12-08 | 2013-05-15 | 浙江工业大学 | Triphenylamine derivatives as well as preparation method and application thereof |
| CN109651293A (en) * | 2019-02-21 | 2019-04-19 | 湖州师范学院 | A kind of diazosulfide phenylacetonitrile derivative and its preparation method and application |
| CN111574578A (en) * | 2020-06-24 | 2020-08-25 | 湖州师范学院 | Circular polarization luminescent material with intelligent response multicolor conversion and preparation method and application thereof |
| CN112159452A (en) * | 2020-09-30 | 2021-01-01 | 深圳大学 | Multiple stimulus response color-changing material and preparation method and application thereof |
| CN113637028A (en) * | 2021-08-03 | 2021-11-12 | 湖州师范学院 | Hydrostatic pressure fluorescent sensing material based on carborane, and preparation method and application thereof |
-
2022
- 2022-03-22 CN CN202210280685.4A patent/CN114634546B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3578680A (en) * | 1967-06-09 | 1971-05-11 | Fuji Photo Film Co Ltd | Photochromic compound |
| EP0389813A1 (en) * | 1989-03-30 | 1990-10-03 | Matsushita Electric Industrial Co., Ltd. | A method for preparing a photochromic material |
| CN102875398A (en) * | 2012-06-08 | 2013-01-16 | 浙江工业大学 | Application of triphenylamine derivative as reversible force stimulus fluorescent switch material |
| CN103102286A (en) * | 2012-12-08 | 2013-05-15 | 浙江工业大学 | Triphenylamine derivatives as well as preparation method and application thereof |
| CN109651293A (en) * | 2019-02-21 | 2019-04-19 | 湖州师范学院 | A kind of diazosulfide phenylacetonitrile derivative and its preparation method and application |
| CN111574578A (en) * | 2020-06-24 | 2020-08-25 | 湖州师范学院 | Circular polarization luminescent material with intelligent response multicolor conversion and preparation method and application thereof |
| CN112159452A (en) * | 2020-09-30 | 2021-01-01 | 深圳大学 | Multiple stimulus response color-changing material and preparation method and application thereof |
| CN113637028A (en) * | 2021-08-03 | 2021-11-12 | 湖州师范学院 | Hydrostatic pressure fluorescent sensing material based on carborane, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| LI WEN ET AL.: "Rich-colour mechanochromism of a cyanostilbene derivative with chiral self-assembly", 《NEW J. CHEM.》, vol. 45, pages 11530 * |
| 毛文纲;陈康;欧阳密;孙玮;周永兵;宋庆宝;张诚;: "基于苯乙烯腈结构的可逆力致变色化合物的合成及性能", 化学学报, no. 04, pages 613 - 618 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957095A (en) * | 2022-06-30 | 2022-08-30 | 江西科技师范大学 | Carbazole derivative and preparation method and application thereof |
| CN115109054A (en) * | 2022-07-11 | 2022-09-27 | 湖州学院 | Preparation method and application of color-changing material with multiple stimulus responses |
| CN115109054B (en) * | 2022-07-11 | 2023-05-05 | 湖州学院 | Preparation method and application of color-changing material with multiple stimulus responses |
| CN115947701A (en) * | 2022-12-05 | 2023-04-11 | 浙江工业大学 | Deep red to near-infrared high-luminous-power photochromic material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114634546B (en) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114634546A (en) | High-luminous-power photochromic material from red to near infrared and preparation method thereof | |
| CN109651293B (en) | Benzothiadiazole benzyl cyanide derivative and preparation method and application thereof | |
| CN111995580B (en) | Fluorescent dye with tetraphenyl ethylene imidazole ring structure and application thereof | |
| CN111875811B (en) | Supermolecule polymer and preparation method and application thereof | |
| Gao et al. | Facile synthesis of highly fluorescent BF 2 complexes bearing isoindolin-1-one ligand | |
| CN111825634B (en) | Novel compounds, process for their preparation and their use | |
| Yang et al. | Synthesis and properties of aggregation-induced emission enhancement compounds derived from triarylcyclopentadiene | |
| CN110655524B (en) | Naphthoquinone pyranoindole derivatives, and preparation method and application thereof | |
| CN113929659B (en) | Preparation and application of pressure-induced color-changing material with AIE (aluminum-doped aluminum-oxide) property | |
| CN105733504B (en) | A kind of near-infrared absorbing material with liquid crystal property | |
| CN111574578B (en) | Circular polarization luminescent material with intelligent response multicolor conversion and preparation method and application thereof | |
| CN111253338B (en) | Efficient organic near-infrared fluorescent material and preparation and application thereof | |
| CN113387905A (en) | Organic room temperature phosphorescent material, preparation method and application | |
| CN115109054B (en) | Preparation method and application of color-changing material with multiple stimulus responses | |
| CN113292607B (en) | Ionic luminescent platinum complex based on benzimidazole phosphine ligand and preparation method thereof | |
| CN110041226B (en) | Compound with AIE characteristics and preparation method and application thereof | |
| CN113493445B (en) | Imidazolyl spiro derivative with aggregation-induced emission property and application thereof | |
| CN114874145A (en) | Water-soluble trityl free-based material and preparation method and application thereof | |
| CN112812088A (en) | Near-infrared luminescent triphenylamine derivative fluorescent molecule and preparation method and application thereof | |
| CN110950861B (en) | Mononuclear dysprosium complex with 1, 10-phenanthroline-2, 9-dicarboxylic acid as ligand and preparation method and application thereof | |
| CN112110887A (en) | Synthetic method and application of 3-position formyl substituted 2H-chromene derivative | |
| CN102887915A (en) | Heteronuclear bimetallic complex light-emitting material and preparation method and application thereof | |
| CN108250224B (en) | Method for regulating and controlling service life of Cu (I) complex and application thereof | |
| CN116120259B (en) | D-pi-A azobenzene piezochromic material and preparation method thereof | |
| CN111499573A (en) | Pressure-induced color-changing fluorescent molecule and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |