CN116120259B - D-pi-A azobenzene piezochromic material and preparation method thereof - Google Patents
D-pi-A azobenzene piezochromic material and preparation method thereof Download PDFInfo
- Publication number
- CN116120259B CN116120259B CN202211578483.4A CN202211578483A CN116120259B CN 116120259 B CN116120259 B CN 116120259B CN 202211578483 A CN202211578483 A CN 202211578483A CN 116120259 B CN116120259 B CN 116120259B
- Authority
- CN
- China
- Prior art keywords
- azobenzene
- pressure
- nitrogen
- bromo
- piezochromic
- 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.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 47
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LTPLLZWVPBTAMH-UHFFFAOYSA-N bis(4-bromophenyl)diazene Chemical compound C1=CC(Br)=CC=C1N=NC1=CC=C(Br)C=C1 LTPLLZWVPBTAMH-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 13
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- -1 4-bromo-4 '-anthrylazobenzene Chemical compound 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 5
- 229950000688 phenothiazine Drugs 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 3
- VHHDLIWHHXBLBK-UHFFFAOYSA-N anthracen-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=C(C=CC=C3)C3=CC2=C1 VHHDLIWHHXBLBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 10
- 238000000862 absorption spectrum Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010979 ruby Substances 0.000 description 2
- 229910001750 ruby Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- JYMNQRQQBJIMCV-UHFFFAOYSA-N 4-(dimethylamino)benzonitrile Chemical compound CN(C)C1=CC=C(C#N)C=C1 JYMNQRQQBJIMCV-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- CGRJOQDFNTYSGH-UHFFFAOYSA-N tritylphosphane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(P)C1=CC=CC=C1 CGRJOQDFNTYSGH-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- 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
- C09K2211/1007—Non-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
- C09K2211/1003—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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Photometry And Measurement Of Optical Pulse Characteristics (AREA)
Abstract
The invention relates to a D-pi-A type azobenzene piezochromic material and a preparation method thereof, belonging to the technical field of piezochromic materials, wherein the molecular formula of the D-pi-A type azobenzene piezochromic material is C 38 H 25 N 3 S, the preparation method comprises the steps of preparation of 4,4 '-dibromoazobenzene, preparation of 4-bromo-4' -anthryl azobenzene, preparation of AN-Azo-PTZ and the like. The piezochromic material prepared by the invention realizes the large-scale movement of the absorption spectrum of the material at the pressure of about 8GPa and the significant change of the color from pale yellow to black brown. The band gap value and the pressure have good linear relation and good sensitivity.
Description
Technical Field
The invention belongs to the field of piezochromic material research, and particularly relates to AN organic piezochromic material 4-anthryl-4' -phenothiazinyl-azobenzene (AN-Azo-PTZ) and application thereof in pressure detection.
Background
As an independent thermodynamic parameter, pressure is different from other basic parameters affecting physical properties of materials such as temperature, components and the like, the method is an efficient and green technical means for regulating and controlling the structure of the materials and exploring the novel performance of the materials. By changing the molecular spacing, the pressure can effectively regulate and control the interaction between the material structure and the molecules, so as to change the material electronic structure, and play an important role in the fields of display imaging, pressure detection, aerospace, food safety and the like. With the improvement of the technical level, the need for accurate, sensitive and stable pressure calibration methods is also increasing. In the prior pressure calibration method, most of the pressure calibration methods are used for pressure calibration according to the relationship between the fluorescent peak position of the pressure calibration material and the pressure. However, due to the phenomenon of fluorescence quenching caused by pressure, the fluorescence of the material is difficult to be sustained to a very high pressure, and the standardization precision is further reduced due to the broadening of the fluorescence peak, so that the fluorescence method standard pressure is often faced with a plurality of limitations and challenges in practical application. However, unlike fluorescence properties, absorption spectra are more stable under pressure as one of the intrinsic signals of semiconductor materials, signals can be measured over a wider range of pressures, and their application potential is greater. In addition, the band gap change of the material often brings about the change of the color of the material, and no extra excitation light is needed, so that the method is more visual and simple. Therefore, developing the piezochromic material suitable for the high-pressure environment and establishing the pressure calibration method based on the absorption signal of the piezochromic material have important significance.
The organic micromolecule piezochromic material is used as an emerging intelligent material, is very sensitive to the external environment, especially the mechanical actions such as pressure, has wide color changing range and short response time, can be effectively regulated and controlled by the pressure, and is considered to have great application potential in the fields such as pressure sensing, environment monitoring, information safety and the like. The piezochromic property is derived from the change of the absorption property of the material. How to carry out wide-band large-range accurate regulation and control on the band gap of the material, thereby realizing more obvious piezochromic performance of the material and improving the pressure sensitivity of the material, and being a key problem for developing an organic piezochromic material. The sensitivity of the organic piezochromic material reported at present is higher, but the band gap movement range under pressure is limited. Most of organic molecular materials under pressure have band gap reduction which is realized by enhancing the formation of excimer by means of pi-pi interaction of reduced intermolecular distance after molecular planarization, but the band gap is limited along with the pressure change amplitude after excimer formation, so that the red shift range of the molecular absorption spectrum is difficult to break through 200nm, and the improvement of the contrast of color change is quite challenging. For example, the band gap of triphenylamine derivative material TPA-AN is reduced by less than 80nm under the pressure change from normal pressure to 4.75 GPa; typical charge transfer molecules DMABN have a band gap red shift of only around 100nm at a pressure range of 0.73GPa to 15.22 GPa. Therefore, increasing the range of band gap variation under pressure, achieving more pronounced color change is critical to organic piezochromic materials.
Azobenzene molecules have been attracting attention in the past decades due to their unique photoinduced cis-trans isomerism properties, and are widely used in research fields such as stimulus response and intelligent materials. Through planarization of molecular conformation under high pressure, the D-pi-A azo phenyl molecule not only can realize generation of intramolecular charge transfer state, but also can realize formation of excimer by enhancement of intermolecular pi-pi interaction, both are beneficial to reduction of molecular band gap, realize wide-range regulation of material band gap, and obtain better piezochromic performance. However, the research on azobenzene-based organic materials is limited to the structure and physical property research of the optical stimulus response under normal pressure, and the research on azobenzene molecules under high pressure is still very little, and the research on azobenzene charge transfer materials under high pressure is very rare; in addition, a method for realizing external pressure detection by utilizing the piezochromic property of the D-pi-A type azo phenyl material is not reported yet.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a D-pi-A azobenzene-based piezochromic material which has good optical stability and excellent color contrast and sensitivity, and is applied to pressure detection.
The technical scheme of the invention is as follows:
a D-pi-A azobenzene piezochromic material with a molecular formula of C 38 H 25 N 3 S, the structural formula is as follows:
a preparation method of a D-pi-A azobenzene piezochromic material comprises the following steps:
1) Preparing 4,4 '-dibromoazobenzene, dissolving p-bromoaniline and manganese dioxide in benzene according to a molar ratio of 1:2, reacting for 24 hours at 100 ℃ in a nitrogen environment, dissolving an organic phase with methylene dichloride, collecting filtrate by a suction filtration mode, adding the organic phase into silica gel, concentrating and spin-drying, and separating by column chromatography to obtain yellow solid 4,4' -dibromoazobenzene;
2) Preparation of 4-bromo-4 '-anthrylazobenzene 4,4' -dibromoazobenzene and 9-anthraceneboronic acid were usedDissolving toluene, adding K after complete dissolution 2 CO 3 And H 2 O was purged with nitrogen for one cycle and Pd (pph was added 3 ) 4 Vacuumizing again, introducing nitrogen for three cycles, reacting for 48 hours under the protection of nitrogen at 90 ℃, extracting with dichloromethane and deionized water after the reaction is finished, standing for layering, taking a lower organic phase, adding silica gel for spin drying, and separating by column chromatography to obtain yellow solid 4-bromo-4' -anthryl azobenzene; 4,4' -dibromoazobenzene 9-anthracene boric acid K according to the molar ratio 2 CO 3 :Pd(pph 3 ) 4 ＝11:10:100:1；
3) Preparing AN-Azo-PTZ, namely dissolving 4-bromo-4' -anthryl azobenzene and phenothiazine with 10mL of toluene, adding tri-tert-butyl phosphine, adding sodium tert-butoxide, and vacuumizing and introducing nitrogen for one cycle; weighing Pd 2 (dba) 3 Adding the mixture into a round bottom flask, vacuumizing again, introducing nitrogen for three cycles, and reacting for 36 hours in an oil bath at 110 ℃ under the protection of nitrogen; after the reaction is finished, the organic phase is added with silica gel to be dried into a surface, and column chromatography is carried out for separation; spin-drying the obtained product solution to obtain yellow solid AN-Azo-PTZ, namely the D-pi-A azobenzene piezochromic material; according to the mole ratio, 4-bromo-4' -anthryl azobenzene, phenothiazine, sodium tert-butoxide and Pd 2 (dba) 3 2mL of trityl phosphine per mmol of 4-bromo-4' -anthracenyl azobenzene is used =10:12:50:1.
According to the invention, a charge donor group phenothiazinyl group and a charge acceptor group anthryl group are connected with AN azobenzene molecule to construct a D-pi-A type charge transfer molecule with larger steric hindrance, so that a loose arrangement mode with weaker interaction is formed between molecules, a piezoinduced conformation planarization and charge transfer state are utilized to form, and the obtained material AN-Azo-PTZ has excellent piezochromic performance, and the reaction path is shown as follows:
compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, a D-pi-A type charge transfer molecule is constructed by connecting a charge donor group and a receptor group with an azobenzene molecule, and is applied to the field of piezochromic materials, a target molecule is obtained through the design and synthesis of a molecular reaction path, the piezochromic performance under high pressure is characterized, and the excellent piezochromic material with high color contrast is realized.
(2) The pressure response range is 0.82 GPa-7.92 GPa, the intermolecular pi-pi interaction is enhanced to form ICT state and excimer through pressure induced molecule planarization, and the large-range movement of the absorption spectrum of the material at 232nm under the pressure of about 8GPa is realized, and the color is changed from pale yellow to dark brown remarkably. The band gap value and the pressure have better linear relation, and have good sensitivity of-0.0943 (eV.GPa -1 ) Has great application potential and good application prospect in pressure sensing detection.
Drawings
FIG. 1 is AN in situ ultraviolet-visible absorption spectrum of 0.82GPa to 7.92GPa of AN AN-Azo-PTZ crystal in example 1.
FIG. 2 is AN in situ optical photograph of 0.82GPa to 7.92GPa of AN-Azo-PTZ crystal in example 1.
FIG. 3 shows AN AN-Azo-PTZ crystal of 0.82GPa to 7.92GPa (. Alpha.hv) in example 1 2 -hv curve.
FIG. 4 is a linear plot of AN-Azo-PTZ crystal band gap versus corresponding pressure for example 1.
Detailed Description
The present invention will be described in further detail with reference to example 1.
Example 1:
a method for preparing AN-Azo-PTZ molecule comprising the steps of:
para-bromoaniline (29.24 g,0.17 mmol), manganese dioxide (29.58 g,0.34 mmol) and 30mL benzene were placed in a 100mL round bottom flask. After 24h of reaction at 100 ℃ under nitrogen, the organic phase is dissolved by methylene chloride, and the filtrate is collected by suction filtration. The organic phase was concentrated on silica gel and dried by spin-drying with petroleum ether: column chromatography with dichloromethane=10:1 as eluent gave 10.11g of 4,4' -dibromoazobenzene as a yellow solid. 4,4' -dibromoazobenzene (0.374 g,1.1 mmol) and 9-anthraceneboronic acid (0.222 g,1 mmol) were charged to a 50mL round bottom flaskIn the process, 10mL of toluene is used for dissolution, and K is added after complete dissolution 2 CO 3 (1.38 g,10 mmol) and 5mL H 2 O vacuumizes and lets in nitrogen for one cycle. Pd (pph) was added 3 ) 4 (0.116 g,0.1 mmol) was again evacuated and purged with nitrogen three cycles and reacted at 90℃under nitrogen for 48h. After the reaction is finished, dichloromethane and deionized water are used for extraction for multiple times, standing and layering are carried out, and a lower organic phase is taken out. The organic phase was dried over silica gel, petroleum ether: column chromatography with methylene chloride=7:1 as developing solvent gives 0.431g of 4-bromo-4' -anthrylazobenzene as a yellow solid. 4-bromo-4' -anthrylazobenzene (0.435 g,1 mmol) and phenothiazine (0.240 g,1.2 mmol) were taken in a 50mL round-bottom flask; 10mL of toluene was added to dissolve the mixture, 2mL of tributylphosphine was added, sodium tert-butoxide (0.284 g,5 mmol) was added, and the mixture was evacuated and purged with nitrogen for one cycle; weighing Pd 2 (dba) 3 (0.04 g,0.1 mmol) was added to the round bottom flask, again evacuated and purged with nitrogen for three cycles, reacted in an oil bath at 110℃under nitrogen protection for 36h; after the reaction is finished, the organic phase silica gel is spin-dried to form a surface, petroleum ether: column chromatography separation is carried out by using methylene dichloride=3:1 as developing agent; the resulting product solution was spin-dried to give 0.420g of yellow solid AN-Azo-PTZ in a yield of about 76%. 1 H NMR(500MHz,CDCl 3 ):δ8.54(s,1H),δ8.16(d,2H),δ8.07(d,1H),δ7.72(d,1H),δ7.61(d,1H),δ7.47(d,2H),δ7.43-7.34(m,1H),δ7.22(d,1H),δ7.08(t,1H),δ6.99(d,3H),δ6.75(d,1H)。
The preparation method of the AN-Azo-PTZ crystal comprises the following steps:
weighing a certain mass of the product in a beaker, adding dichloromethane at 30 ℃ to fully dissolve the product, and mixing the product with dichloromethane according to the following steps: absolute ethyl alcohol=1:3 (volume ratio), and placing the absolute ethyl alcohol into a water bath kettle for preheating, dropwise adding the preheated absolute ethyl alcohol into a beaker along the wall of the beaker, and placing the beaker at a dark place for crystal precipitation.
Example 2: piezochromic performance and pressure calibration display
The diamond anvil cell with the anvil surface diameter of 300 mu m is selected as a pressurizing device, firstly, a T301 steel sheet is pre-pressed, the thickness of the pre-pressed steel sheet is 50 mu m, and a small hole with the diameter of 100 mu m is drilled at the center of an indentation by laser and is used as a sample cavity. Firstly, ruby microspheres are added as pressure calibration objects, and AN-Azo-PTZ crystals with the sizes of about 50 mu m multiplied by 20 mu m multiplied by 15 mu m are put in the pressure calibration objects, and the pressure is applied after the cover of the press is sealed. The ruby has an initial fluorescence peak position of 694.7nm and a corresponding pressure of 1atm. In situ UV-visible absorption spectra were measured at various pressures as shown in FIG. 1. As the pressure increases, the absorption edge of AN-Azo-PTZ gradually red shifts to 232nm, and the color of AN-Azo-PTZ crystal gradually changes from pale yellow to red and finally to black brown as shown in fig. 2 (fig. 2 is only shown in black-and-white format because the patent document does not support color).
Band gap values were further read by Tauc equation:
(αhv) 2 =c (hv-Eg) (C is a constant)
Coordinate transformation is performed on the absorption data to obtain (alpha hv) 2 -hv curve and making the x-axis intercept of the absorption edge tangent, eg, as shown in figure 3. Further, the pressure value P is taken as an abscissa, and the band gap value Eg is taken as an ordinate to obtain a band gap value variation curve with pressure, as shown in fig. 4. The linear correlation equation for Eg-P obtained by linear fitting is as follows:
Eg(eV)＝-0.0943×P(GPa)+2.304
wherein the slope k is the sensitivity of the pressure detection method to the pressure-induced color change, and the value is k= -0.0943 (eV. GPa -1 )。
The above embodiments are provided for further explanation and illustration of the present invention, not for limiting the scope of the present invention, and any modification and variation based on the above-mentioned idea should be included in the scope of the appended claims, which are within the spirit and principle of the present invention.
Claims (2)
1. A D-pi-A azobenzene piezochromic material with a molecular formula of C 38 H 25 N 3 S, the structural formula is as follows:
。
2. a process for preparing a D-pi-a type azobenzene piezochromic material according to claim 1, comprising the steps of:
1) Preparing 4,4 '-dibromoazobenzene, dissolving p-bromoaniline and manganese dioxide in benzene according to a molar ratio of 1:2, reacting at 100 ℃ under a nitrogen environment for 24h, dissolving an organic phase with methylene dichloride, collecting filtrate by a suction filtration mode, adding the organic phase into silica gel, concentrating and spin-drying, and separating by column chromatography to obtain yellow solid 4,4' -dibromoazobenzene;
2) Preparation of 4-bromo-4 '-anthrylazobenzene, dissolving 4,4' -dibromoazobenzene and 9-anthraceneboronic acid in toluene, and adding K after complete dissolution 2 CO 3 And H 2 O was purged with nitrogen for one cycle and Pd (pph was added 3 ) 4 Vacuumizing again, introducing nitrogen for three cycles, reacting 48 and h under the protection of nitrogen at 90 ℃, extracting with dichloromethane and deionized water after the reaction is finished, standing for layering, taking a lower organic phase, adding silica gel for spin drying, and separating by column chromatography to obtain yellow solid 4-bromo-4' -anthryl azobenzene; 4,4' -dibromoazobenzene 9-anthracene boric acid K according to the molar ratio 2 CO 3 : Pd(pph 3 ) 4 =11:10:100:1；
3) Preparing AN-Azo-PTZ, dissolving 4-bromo-4' -anthryl azobenzene and phenothiazine with 10mL toluene, adding tri-tert-butyl phosphine, adding sodium tert-butoxide, vacuumizing, and introducing nitrogen for one cycle; weighing Pd 2 (dba) 3 Adding the mixture into a round bottom flask, vacuumizing again, introducing nitrogen for three cycles, and reacting in an oil bath at 110 ℃ under the protection of nitrogen for 36h; after the reaction is finished, the organic phase is added with silica gel to be dried into a surface, and column chromatography is carried out for separation; spin-drying the obtained product solution to obtain yellow solid AN-Azo-PTZ, namely the D-pi-A azobenzene piezochromic material according to claim 1; according to the mole ratio, 4-bromo-4' -anthryl azobenzene, phenothiazine, sodium tert-butoxide and Pd 2 (dba) 3 2mL tributylphosphine per mmol of 4-bromo-4' -anthracenyl azobenzene is used =10:12:50:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211578483.4A CN116120259B (en) | 2022-12-09 | 2022-12-09 | D-pi-A azobenzene piezochromic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211578483.4A CN116120259B (en) | 2022-12-09 | 2022-12-09 | D-pi-A azobenzene piezochromic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116120259A CN116120259A (en) | 2023-05-16 |
| CN116120259B true CN116120259B (en) | 2024-03-12 |
Family
ID=86298308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211578483.4A Active CN116120259B (en) | 2022-12-09 | 2022-12-09 | D-pi-A azobenzene piezochromic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116120259B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001664A (en) * | 2015-07-10 | 2015-10-28 | 岭南师范学院 | D-pi-A-type aminoazobenzene dye and preparation method therefor |
| CN105694853A (en) * | 2016-03-14 | 2016-06-22 | 上海电力学院 | Organic luminescent material and preparation method and application thereof |
| CN108947933A (en) * | 2018-08-17 | 2018-12-07 | 天津师范大学 | The diethyl terephthalate class compound and preparation method and purposes of power mutagens color |
-
2022
- 2022-12-09 CN CN202211578483.4A patent/CN116120259B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001664A (en) * | 2015-07-10 | 2015-10-28 | 岭南师范学院 | D-pi-A-type aminoazobenzene dye and preparation method therefor |
| CN105694853A (en) * | 2016-03-14 | 2016-06-22 | 上海电力学院 | Organic luminescent material and preparation method and application thereof |
| CN108947933A (en) * | 2018-08-17 | 2018-12-07 | 天津师范大学 | The diethyl terephthalate class compound and preparation method and purposes of power mutagens color |
Non-Patent Citations (1)
| Title |
|---|
| Azobenzene Photoisomerization under High External Pressures: Testing the Strength of a Light-Activated Molecular Muscle;Singleton Thomas A.等;《The Journal of Physical Chemistry B》;第116卷;第9860-9865页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116120259A (en) | 2023-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109651293B (en) | Benzothiadiazole benzyl cyanide derivative and preparation method and application thereof | |
| CN114634546B (en) | High-luminous-power electrochromic material from red to near infrared and preparation method thereof | |
| CN111205271B (en) | Ligand compound, functionalized metal-organic framework compound prepared from ligand compound, and preparation method and application of functionalized metal-organic framework compound | |
| CN112679518A (en) | Pure organic room temperature phosphorescent material based on thiochromanone derivative and preparation method and application thereof | |
| Gao et al. | Piezochromic luminescence of cyano substituted E/Z isomeric derivatives: different responses to external stimuli | |
| CN113929659B (en) | Preparation and application of pressure-induced color-changing material with AIE (aluminum-doped aluminum-oxide) property | |
| CN116120259B (en) | D-pi-A azobenzene piezochromic material and preparation method thereof | |
| CN111574578B (en) | Circular polarization luminescent material with intelligent response multicolor conversion and preparation method and application thereof | |
| CN110117235B (en) | Compound with aggregation-induced light emission and mechanochromism characteristics and preparation method and application thereof | |
| CN115819281B (en) | Cyano-substituted p-phenylene ethylene derivative, preparation method and application | |
| CN111039930A (en) | bis-N-phenyl-3-carbazole substituted phenanthroimidazole compound, preparation method thereof and application thereof as electroluminescent device | |
| CN115109054B (en) | Preparation method and application of color-changing material with multiple stimulus responses | |
| CN110041226B (en) | Compound with AIE characteristics and preparation method and application thereof | |
| CN110028427B (en) | Pressure-induced fluorescence color-changing material containing 9, 10-bis (diphenylmethylene) anthracene structure and application thereof in pressure detection | |
| CN112010854B (en) | Trnano-ger's alkali derivative, preparation method thereof and test method for mechanical-induced fluorescence enhancement characteristics | |
| CN111499573B (en) | Pressure-induced color-changing fluorescent molecule and preparation method thereof | |
| CN113637028A (en) | Hydrostatic pressure fluorescent sensing material based on carborane, and preparation method and application thereof | |
| CN111471455B (en) | Preparation method and application of acetophenone and derivative-substituted thiazolyl viologen high-fluorescence photochromic material | |
| CN109749732B (en) | Preparation method and application of photochromic/tribochromic luminescent material | |
| CN108250224B (en) | Method for regulating and controlling service life of Cu (I) complex and application thereof | |
| CN108558595B (en) | P-phenylene ethylene bridged trimer indene derivative and preparation method thereof | |
| CN109265394B (en) | Zinc terpyridyl (II) complex and preparation method and application thereof | |
| CN109575242B (en) | Cross-conjugated polymer, and preparation method and application thereof | |
| CN113292607A (en) | Ionic luminescent platinum complex based on benzimidazole phosphine ligand and preparation method thereof | |
| CN109180506B (en) | Two-display static pressure ratio 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 |