CN116410174A - Aggregation-induced emission dye and synthesis method thereof - Google Patents
Aggregation-induced emission dye and synthesis method thereof Download PDFInfo
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- CN116410174A CN116410174A CN202310233186.4A CN202310233186A CN116410174A CN 116410174 A CN116410174 A CN 116410174A CN 202310233186 A CN202310233186 A CN 202310233186A CN 116410174 A CN116410174 A CN 116410174A
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- 230000002776 aggregation Effects 0.000 title claims abstract description 23
- 238000004220 aggregation Methods 0.000 title claims abstract description 23
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- -1 3-dicyanovinyl-1-indenone compound Chemical class 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 claims abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical group C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims abstract 2
- 230000005311 nuclear magnetism Effects 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 33
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007850 fluorescent dye Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 238000012984 biological imaging Methods 0.000 abstract description 3
- 238000006073 displacement reaction Methods 0.000 abstract description 3
- AHNMPNURDVZMND-UHFFFAOYSA-N 2-[(3-oxoinden-1-yl)methylidene]propanedinitrile Chemical class C(#N)C(=CC1=CC(C2=CC=CC=C12)=O)C#N AHNMPNURDVZMND-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002428 photodynamic therapy Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- QNVKZKOSAXYVFZ-UHFFFAOYSA-N 2-(3-oxoinden-1-ylidene)propanedinitrile Chemical compound C1=CC=C2C(=O)CC(=C(C#N)C#N)C2=C1 QNVKZKOSAXYVFZ-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WZUODJNEIXSNEU-UHFFFAOYSA-N 2-Hydroxy-4-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(O)=C1 WZUODJNEIXSNEU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NPOMSUOUAZCMBL-UHFFFAOYSA-N dichloromethane;ethoxyethane Chemical compound ClCCl.CCOCC NPOMSUOUAZCMBL-UHFFFAOYSA-N 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- 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
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention relates to an aggregation-induced emission dye and a synthesis method thereof, which are 3-dicyanovinyl-1-indenone compounds, wherein the compounds of formula II and formula III are dissolved in a compound of formula IV and stirred for reaction at 15-35 ℃; after the reaction is completed, the obtained solid is filtered and further purified to obtain the 3-dicyanovinyl-1-indenone compound of the formula I. The hydroxyl on the 2 # position of benzaldehyde and the carbonyl on the 1 # position of indenone form a molecular ketal, so that a benzene ring and indene form a stable approximate plane rigid structure, and the good luminous property of the molecule and high luminous efficiency are realized; the fluorescent dye provided by the invention has fluorescence in both a solid state and an aggregation state, can adjust the wavelength by changing substituents on salicylaldehyde, and has large Stocks displacement; the fluorescent dye provided by the invention has obvious color and fluorescence change under alkaline conditions, can be used as an acid-base indication probe, and can also be applied to the fields of luminescent materials, biological imaging, photodynamic therapy and the like.
Description
Technical Field
The invention relates to the technical field of luminescent dyes, in particular to an aggregation-induced luminescent dye and a synthesis method thereof.
Background
Organic fluorescent dyes have received extensive attention since the discovery of the aggregation-induced emission (AIE) phenomenon by team Tang Benzhong in 2001. The AIE phenomenon is mainly due to a special luminescence phenomenon of a limited motion in a molecule and a limited vibration mechanism in a molecule, and can emit stronger fluorescence in a high concentration or a solid state. As a new generation fluorescent material, the fluorescent material has the advantages of large Stocks displacement, low toxicity, high signal to noise ratio, light bleaching resistance and the like.
The active hydrogen at the No. 2 position of the 3-dicyanovinyl-1-indenone can form double bonds with benzaldehyde substances to construct a D-pi-A molecular system, and the molecular properties of the substituent groups on the benzaldehyde are regulated and controlled by changing, so that the method has more application in the fields of luminescent materials, data storage, photoelectric conversion, biological imaging and the like. However, since the benzene ring and the double bond are connected by a single bond, free rotation exists, so that the luminous efficiency is reduced, and the compound is difficult to break through in luminous behavior.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide an aggregation-induced emission dye which improves the emission efficiency by forming a stable approximately planar rigid structure between benzene rings and indenes, in view of the current state of the art.
The second technical problem to be solved by the invention is to provide a synthesis method of aggregation-induced emission dye aiming at the current state of the art.
The invention solves at least one of the technical problems by adopting the following technical proposal:
an aggregation-induced emission dye is a 3-dicyanovinyl-1-indenone compound, and has a structural formula as follows:
wherein R is 1 Is one or two of hydrogen, halogen, alkyl oxygen, alkyl amino, alkyl sulfide, aryl and heteroaryl; r is R 2 Is a straight or branched alkyl group.
Preferably, said R 2 Is methyl, ethyl, propyl, n-butyl, isobutyl or tert-butyl.
In the present invention, the 3-dicyanovinyl-1-indenone compound is obtained by forming an intramolecular ketal with a hydroxyl group in the 2-position of benzaldehyde and a carbonyl group in the 1-position of indenone. The benzene ring and indene in the 3-dicyanovinyl-1-indenone compound form a planar rigid structure, so that the aggregation-induced emission dye has a stable structure and improves the emission efficiency.
Preferably, the 3-dicyanovinyl-1-indenone compound is:
nuclear magnetism 1 The H hydrogen spectrogram data are: 1 H NMR(CDCl 3 ，500MHz，ppm):8.58(d,J＝8Hz,1H),8.08(s,1H),7.87(d,J＝7.5Hz,1H),7.73(td,J 1 ＝8Hz,J 2 ＝1Hz,2H),7.64(td,J 1 ＝8Hz,J 2 ＝1Hz,1H),7.50(dd,J 1 ＝7.5Hz,J 2 ＝1.5Hz,1H),7.44(td,J 1 ＝8Hz,J 2 ＝1.5Hz,2H),7.18(t,J＝8.5Hz,1H),7.15(dd,J 1 ＝7.5Hz,J 2 ＝1Hz),3.82(m,1H),3.55(m,1H),1.02(t,J＝7Hz,3H)；
nuclear magnetism 13 The C carbon spectrum data are: 13 C NMR(CDCl 3 ，500MHz，ppr)δ159.7，153.4，143.43，135.7，134.3，132.8，131.8，131.1，130.4，129.2，126.3，124.3，123.2，121.1，117.4，113.7，110.4，72.4，59.0，15.0。
preferably, the 3-dicyanovinyl-1-indenone compound is:
nuclear magnetism 1 The H hydrogen spectrogram data are: 1 H NMR(500MHz,Chloroform-d)δ8.56(dt,J＝8.1,0.9Hz,1H),8.08–8.05(m,1H),7.83(dd,J＝7.6,1.2Hz,1H),7.70(td,J＝7.6,1.0Hz,1H),7.62(td,J＝7.8,1.1Hz,1H),7.41(dt,J＝9.2,1.1Hz,1H),6.74–6.68(m,2H),3.91(s,3H),3.77(dq,J＝8.7,7.1Hz,1H),3.54(dq,J＝8.8,7.0Hz,1H),1.40–1.18(m,3H),1.03(t,J＝7.0Hz,3H)。
preferably, the 3-dicyanovinyl-1-indenone compound is:
nuclear magnetism 1 The H hydrogen spectrogram data are: 1 H NMR(500MHz,Chloroform-d)δ8.61(d,J＝7.8Hz,1H),8.34(s,1H),7.85(d,J＝6.8Hz,1H),7.71(td,J＝7.5,1.3Hz,1H),7.66(t,J＝7.3Hz,1H),7.53(d,J＝9.3Hz,1H),7.36–7.29(m,1H),3.53(q,J＝7.2Hz,4H),3.48(t,J＝6.9Hz,1H),1.31(t,J＝7.1Hz,8H),1.27(t,J＝6.9Hz,4H)。
a method for synthesizing aggregation-induced emission dye, comprising the steps of:
dissolving the compound of the formula II and the formula III in the compound of the formula IV, stirring the mixture at the temperature of 15-35 ℃ for reaction, and tracking the reaction by TLC;
after the reaction is completed, filtering, further purifying the obtained solid to obtain the 3-dicyanovinyl-1-indenone compound of the formula I,
preferably, the molar ratio of the compounds of formula II and formula III is 1.2:1 to 1:1.2.
Preferably, the purification process is recrystallisation or washing with an inert solvent or column chromatography.
Preferably, the purification method is column chromatography, the adopted mobile phase is petroleum ether-dichloromethane mixed solvent, and the stationary phase is 200-300 mesh silica gel.
Compared with the prior art, the invention has the advantages that: the synthesis method of the fluorescent dye is simple, the condition is mild, and the hydroxy on the 2 # position of benzaldehyde and the carbonyl on the 1 # position of indenone form intramolecular ketal, so that a stable approximate plane rigid structure is formed by the benzene ring and indene, and the good luminous property of the molecule is realized, and the luminous efficiency is high; the fluorescent dye provided by the invention has fluorescence in both a solid state and an aggregation state, can adjust the wavelength by changing substituents on salicylaldehyde, and has large Stocks displacement; the fluorescent dye provided by the invention has obvious color and fluorescence change under alkaline conditions, can be used as an acid-base indication probe, and can also be applied to the fields of luminescent materials, biological imaging, photodynamic therapy and the like.
Drawings
FIG. 1 shows the nuclear magnetism of dye molecules prepared in example 1 of the present invention 1 H hydrogen spectrum (solvent: CDCl) 3 )；
FIG. 2 shows the nuclear magnetism of dye molecules prepared in example 1 of the present invention 13 C carbon spectrogram (solvent: CDCl) 3 )；
FIG. 3 is a crystal structure diagram of the dye molecule prepared in example 1 of the present invention;
FIG. 4 is another angular view of FIG. 3;
FIG. 5 is an ultraviolet-visible light absorption spectrum of the dye molecule prepared in example 1 of the present invention;
FIG. 6 is a photograph showing dye molecules prepared in example 1 of the present invention under white light (left) and 365nm ultraviolet light (right);
FIG. 7 shows AIE effect of dye molecules prepared in example 1 of the present invention;
FIG. 8 shows the change in ultraviolet absorption spectrum of dye molecules prepared in example 1 of the present invention after alkali addition;
FIG. 9 shows the change in fluorescence spectrum of dye molecules prepared in example 1 of the present invention after alkali addition;
FIG. 10 is an ultraviolet-visible light absorption spectrum of the dye molecule prepared in example 2 of the present invention;
FIG. 11 is an ultraviolet-visible light absorption spectrum of a dye molecule prepared in example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Example 1:
the aggregation-induced emission dye of the embodiment is a 3-dicyanovinyl-1-indenone compound, which is an organic fluorescent dye, and the 3-dicyanovinyl-1-indenone compound is as follows:
the synthetic method of the 3-dicyanovinyl-1-indenone compound comprises the following steps:
2- (2, 3-dihydro-3-oxo-1H-indene-1-ylidene) malononitrile (0.40 g,2.06 mmoL), salicylaldehyde (0.21 mL,2.1 mmoL) and 10mL of ethanol were added to a 50mL flask, stirred at room temperature for 30min, after the reaction was completed, the solution was yellow, filtered, and the obtained solid was washed with ethanol, washed and dried to give a bright yellow solid of 0.46g, yield 70%.
As shown in fig. 1, 2 and 3, the detection data of the obtained dye molecular material are as follows:
nuclear magnetism 1 The H hydrogen spectrogram data are: 1 H NMR(CDCl 3 ，500MHz，ppm):8.58(d,J＝8Hz,1H),8.08(s,1H),7.87(d,J＝7.5Hz,1H),7.73(td,J 1 ＝8Hz,J 2 ＝1Hz,2H),7.64(td,J 1 ＝8Hz,J 2 ＝1Hz,1H),7.50(dd,J 1 ＝7.5Hz,J 2 ＝1.5Hz,1H),7.44(td,J 1 ＝8Hz,J 2 ＝1.5Hz,2H),7.18(t,J＝8.5Hz,1H),7.15(dd,J 1 ＝7.5Hz,J 2 ＝1Hz),3.82(m,1H),3.55(m,1H),1.02(t,J＝7Hz,3H)。
nuclear magnetism 13 The C carbon spectrum data are: 13 C NMR(CDCl 3 ，500MHz，ppr)δ159.7，153.4，143.43，135.7，134.3，132.8，131.8，131.1，130.4，129.2，126.3，124.3，123.2，121.1，117.4，113.7，110.4，72.4，59.0，15.0。
the crystal structure data are:
as can be seen from fig. 4, the product obtained in this example has a stable approximately planar rigid structure with good stability.
FIG. 5 is a graph of the UV-visible absorption spectrum of the dye molecules prepared, the maximum absorption peak occurring at 408nm, as measured in acetonitrile.
The prepared dye molecule solid powder is respectively placed under natural light and 365nm ultraviolet lamp irradiation, as shown in fig. 6, the dye solid is observed to be yellow under natural light, and the dye solid emits yellow green fluorescence under 365nm ultraviolet lamp, which indicates that the dye molecule of the invention has solid fluorescence.
The prepared dye molecule is prepared into 10 -4 The fluorescence spectra of the mol/L solution and the solvent are respectively acetonitrile, acetonitrile and water mixed solution (volume ratio is 2:1 and 1:2), the optical property data are shown in figure 7, dye molecules basically do not have fluorescence in pure organic solvent, and the fluorescence is obviously enhanced after water is added, so that the dye molecules have AIE effect.
As can be seen from FIGS. 5 and 7, the Stocks shift of the dye molecule prepared was 132nm.
The prepared dye molecule is prepared into 10 -4 The solution is changed from yellow to blue by adding 2 equivalents of sodium hydroxide water-acetonitrile (1:5) solution into the mol/L acetonitrile solution, the ultraviolet-visible absorption spectrum is shown in figure 7, the prepared dye molecule shows a new absorption peak at 560nm, and strong blue fluorescence is emitted, and the fluorescence spectrum is shown in figure 9. And hydrochloric acid is used for neutralizing sodium hydroxide, the color of the solution turns yellow, and the fluorescence disappears, which indicates that the prepared dye molecule has good fluorescence characteristics.
Example 2:
the 3-dicyanovinyl-1-indenone compound in this example is:
the preparation method comprises the following steps:
2- (2, 3-dihydro-3-oxo-1H-indene-1-ylidene) malononitrile (0.20 g,1.02 mmol), 2-hydroxy-4-methoxybenzaldehyde (0.17 g,1.09 mmol) and 10ml ethanol were added to a 50ml flask, stirred at room temperature until the reaction was completed, the reaction solution was dark red, filtered, washed with ethanol, dried to give an orange solid, and column chromatography was performed to give 0.35g of an orange solid.
Nuclear magnetism of the obtained product 1 The H hydrogen spectrogram data are: 1 H NMR(500MHz,Chloroform-d)δ8.56(dt,J＝8.1,0.9Hz,1H),8.08–8.05(m,1H),7.83(dd,J＝7.6,1.2Hz,1H),7.70(td,J＝7.6,1.0Hz,1H),7.62(td,J＝7.8,1.1Hz,1H),7.41(dt,J＝9.2,1.1Hz,1H),6.74–6.68(m,2H),3.91(s,3H),3.77(dq,J＝8.7,7.1Hz,1H),3.54(dq,J＝8.8,7.0Hz,1H),1.40–1.18(m,3H),1.03(t,J＝7.0Hz,3H)。
the ultraviolet-visible light absorption spectrum of the obtained product is shown in FIG. 10, and the maximum absorption peak appears at 447nm.
Example 3:
the 3-dicyanovinyl-1-indenone compound in this example is:
the preparation method comprises the following steps:
2- (2, 3-dihydro-3-oxo-1H-indene-1-ylidene) malononitrile (0.22 g,1.13 mmol), 4- (N, N-diethyl) aminosalicylaldehyde (0.20 g,1.05 mmol) and 10ml ethanol were added to a 50ml flask, stirred at room temperature, stirred overnight to complete the reaction, filtered, washed with ethanol and dried to give a dark green solid, 0.39g.
Nuclear magnetism of the obtained product 1 The H hydrogen spectrogram data are: 1 H NMR(500MHz,Chloroform-d)δ8.61(d,J＝7.8Hz,1H),8.34(s,1H),7.85(d,J＝6.8Hz,1H),7.71(td,J＝7.5,1.3Hz,1H),7.66(t,J＝7.3Hz,1H),7.53(d,J＝9.3Hz,1H),7.36–7.29(m,1H),3.53(q,J＝7.2Hz,4H),3.48(t,J＝6.9Hz,1H),1.31(t,J＝7.1Hz,8H),1.27(t,J＝6.9Hz,4H)。
the ultraviolet-visible light absorption spectrum of the obtained product is shown in FIG. 11, and the maximum absorption peak appears at 550nm.
Comparing the preparation parameters of examples 1, 2,3 of the present invention, and FIGS. 5, 10, 11, it is known that the wavelength of the product can be tuned by changing the substituents on the salicylaldehyde.
Claims (10)
1. An aggregation-induced emission dye, characterized in that: is 3-dicyanovinyl-1-indenone compound with a structural formula of
Wherein R is 1 Is one or two of hydrogen, halogen, alkyl oxygen (), alkyl amino, alkyl sulfide, aryl and heteroaryl; r is R 2 Is a straight or branched alkyl group.
2. The aggregation-induced emission dye according to claim 1, wherein: the R is 2 Is methyl, ethyl, propyl, n-butyl, isobutyl or tert-butyl.
3. The aggregation-induced emission dye according to claim 1 or 2, characterized in that: the 3-dicyanovinyl-1-indenone compound is obtained by forming a molecular ketal from a hydroxyl group in the 2-position of benzaldehyde and a carbonyl group in the 1-position of indenone.
4. The aggregation-induced emission dye according to claim 3, wherein: the benzene ring in the 3-dicyanovinyl-1-indenone compound and indene form a plane rigid structure.
5. The aggregation-induced emission dye according to claim 1 or 2, characterized in that: the 3-dicyanovinyl-1-indenone compound is
Nuclear magnetism 1 The H hydrogen spectrogram data are: 1 H NMR(CDCl 3 ，500MHz，ppm):8.58(d,J＝8Hz,1H),8.08(s,1H),7.87(d,J＝7.5Hz,1H),7.73(td,J 1 ＝8Hz,J 2 ＝1Hz,2H),7.64(td,J 1 ＝8Hz,J 2 ＝1Hz,1H),7.50(dd,J 1 ＝7.5Hz,J 2 ＝1.5Hz,1H),7.44(td,J 1 ＝8Hz,J 2 ＝1.5Hz,2H),7.18(t,J＝8.5Hz,1H),7.15(dd,J 1 ＝7.5Hz,J 2 ＝1Hz),3.82(m,1H),3.55(m,1H),1.02(t,J＝7Hz,3H)；
nuclear magnetism 13 The C carbon spectrum data are: 13 C NMR(CDCl 3 ，500MHz，ppr)δ159.7，153.4，143.43，135.7，134.3，132.8，131.8，131.1，130.4，129.2，126.3，124.3，123.2，121.1，117.4，113.7，110.4，72.4，59.0，15.0。
6. the aggregation-induced emission dye according to claim 1 or 2, characterized in that: the 3-dicyanovinyl-1-indenone compound is
Nuclear magnetism 1 The H hydrogen spectrogram data are: 1 H NMR(500MHz,Chloroform-d)δ8.56(dt,J＝8.1,0.9Hz,1H),8.08–8.05(m,1H),7.83(dd,J＝7.6,1.2Hz,1H),7.70(td,J＝7.6,1.0Hz,1H),7.62(td,J＝7.8,1.1Hz,1H),7.41(dt,J＝9.2,1.1Hz,1H),6.74–6.68(m,2H),3.91(s,3H),3.77(dq,J＝8.7,7.1Hz,1H),3.54(dq,J＝8.8,7.0Hz,1H),1.40–1.18(m,3H),1.03(t,J＝7.0Hz,3H)。
7. the aggregation-induced emission dye according to claim 1 or 2, characterized in that: the 3-dicyanovinyl-1-indenone compound is
Nuclear magnetism 1 The H hydrogen spectrogram data are: 1 H NMR(500MHz,Chloroform-d)δ8.61(d,J＝7.8Hz,1H),8.34(s,1H),7.85(d,J＝6.8Hz,1H),7.71(td,J＝7.5,1.3Hz,1H),7.66(t,J＝7.3Hz,1H),7.53(d,J＝9.3Hz,1H),7.36–7.29(m,1H),3.53(q,J＝7.2Hz,4H),3.48(t,J＝6.9Hz,1H),1.31(t,J＝7.1Hz,8H),1.27(t,J＝6.9Hz,4H)。
8. the synthesis method of the aggregation-induced emission dye is characterized by comprising the following steps of:
dissolving a compound of the formula II and a compound of the formula III in a compound of the formula IV, and stirring and reacting at the temperature of 15-35 ℃;
after the reaction is completed, filtering, further purifying the obtained solid to obtain the 3-dicyanovinyl-1-indenone compound of the formula I,
9. the method for synthesizing an aggregation-induced emission dye according to claim 8, wherein: the molar ratio of the compounds of the formula II to the formula III is 1.2:1-1:1.2.
10. The method for synthesizing an aggregation-induced emission dye according to claim 8, wherein: the purification method is recrystallization or inert solvent washing or column chromatography.
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