An aggregation-induced emission dye and its synthesis method

Abstract

The present invention relates to aggregation-induced emission dyes of 3-dicyanovinyl-1-indanone compounds and their synthesis methods. The compounds of formula II and formula III are dissolved in the compound of formula IV, and stirred and reacted at a temperature of 15-35 °C; after the reaction is completed, filtration is carried out, and the obtained solid is further purified to obtain the 3-dicyanovinyl-1-indanone compound of formula I. By forming an intramolecular ketal between the hydroxyl group at the 2-position of benzaldehyde and the carbonyl group at the 1-position of indanone, a stable approximate planar rigid structure is formed between the benzene ring and indan, realizing good luminescence properties of the molecule and high luminescence efficiency; the fluorescent dyes of the present invention have fluorescence in both solid state and aggregated state, and have obvious color and fluorescence changes under alkaline conditions and can be used as acid-base indicator probes, and can also be applied to fields such as luminescent materials, bioimaging, and photodynamic therapy.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent dyes, and specifically refers to an aggregation-induced emission dye and a synthesis method thereof. Background Art

[0002] Since the aggregation-induced emission (AIE) phenomenon was discovered by the team of Tang Benzhong in 2001, organic fluorescent dyes have received extensive attention. The AIE phenomenon is mainly attributed to the special luminescence phenomenon of the restricted intramolecular motion and restricted intramolecular vibration mechanisms, and can emit strong fluorescence at high concentrations or in the solid state. As a new generation of fluorescent materials, it has advantages such as large Stokes shift, low toxicity, high signal-to-noise ratio, and anti-photobleaching ability.

[0003] The active hydrogen at the 2nd position of 3-dicyanovinyl-1-indanone can form a double bond with benzaldehyde substances to construct a D-π-A molecular system, and the molecular properties can be regulated by changing the substituents on benzaldehyde, which has many applications in the fields of luminescent materials, data storage, optoelectronic conversion, biological imaging, etc. However, since the benzene ring and the double bond are connected by a single bond, its free rotation reduces the luminescence efficiency, resulting in it being difficult for this type of compound to make a breakthrough in luminescence behavior. Summary of the Invention

[0004] The first technical problem to be solved by the present invention is, in view of the current situation of the prior art, to provide an aggregation-induced emission dye that improves the luminescence efficiency by making the benzene ring and indene form a stable approximate planar rigid structure.

[0005] The second technical problem to be solved by the present invention is, in view of the current situation of the prior art, to provide a synthesis method of an aggregation-induced emission dye.

[0006] The technical solution adopted by the present invention to solve at least one of the above technical problems is as follows:

[0007] An aggregation-induced emission dye, which is a 3-dicyanovinyl-1-indanone compound, and the structural formula is:

[0008]

[0009] Wherein, R1 is one or two of hydrogen, halogen, alkyl, alkoxy, alkylamino, alkylthio, aryl, heteroaryl; R2 is a straight-chain or branched-chain alkyl.

[0010] Preferably, the R2 is methyl, ethyl, propyl, n-butyl, isobutyl or tert-butyl.

[0011] In the present invention, the 3-dicyanovinyl-1-indanone compound is obtained by forming an intramolecular ketal between the hydroxyl group at the 2-position of benzaldehyde and the carbonyl group at the 1-position of indanone. The benzene ring and indene in the 3-dicyanovinyl-1-indanone compound form a planar rigid structure, thereby stabilizing the structure of the aggregation-induced emission dye and improving the luminescence efficiency.

[0012] Preferably, the 3-dicyanovinyl-1-indanone compound is:

[0013]

[0014] Nuclear magnetic 1 The data of the 1H nuclear magnetic resonance spectrum are as follows: 1 1H NMR (CDCl3, 500 MHz, ppm): 8.58 (d, J = 8 Hz, 1H), 8.08 (s, 1H), 7.87 (d, J = 7.5 Hz, 1H), 7.73 (td, J1 = 8 Hz, J2 = 1 Hz, 2H), 7.64 (td, J1 = 8 Hz, J2 = 1 Hz, 1H), 7.50 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 7.44 (td, J1 = 8 Hz, J2 = 1.5 Hz, 2H), 7.18 (t, J = 8.5 Hz, 1H), 7.15 (dd, J1 = 7.5 Hz, J2 = 1 Hz), 3.82 (m, 1H), 3.55 (m, 1H), 1.02 (t, J = 7 Hz, 3H);

[0015] Nuclear magnetic 13 The data of the 13C nuclear magnetic resonance spectrum are as follows: 13 13C NMR (CDCl3, 500 MHz, ppr) δ 159.7, 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.

[0016] Preferably, the 3-dicyanovinyl-1-indanone compound is:

[0017]

[0018] Nuclear magnetic 1 The data of the 1H nuclear magnetic resonance spectrum are as follows: 11H NMR (500 MHz, Chloroform-d) δ 8.56 (dt, J = 8.1, 0.9 Hz, 1H), 8.08–8.05 (m, 1H), 7.83 (dd, J = 7.6, 1.2 Hz, 1H), 7.70 (td, J = 7.6, 1.0 Hz, 1H), 7.62 (td, J = 7.8, 1.1 Hz, 1H), 7.41 (dt, J = 9.2, 1.1 Hz, 1H), 6.74–6.68 (m, 2H), 3.91 (s, 3H), 3.77 (dq, J = 8.7, 7.1 Hz, 1H), 3.54 (dq, J = 8.8, 7.0 Hz, 1H), 1.40–1.18 (m, 3H), 1.03 (t, J = 7.0 Hz, 3H).

[0019] Preferably, the 3-dicyanovinyl-1-indanone compound is:

[0020]

[0021] Nuclear magnetic 1 The data of the 1H hydrogen spectrum is: 1 1H NMR (500 MHz, Chloroform-d) δ 8.61 (d, J = 7.8 Hz, 1H), 8.34 (s, 1H), 7.85 (d, J = 6.8 Hz, 1H), 7.71 (td, J = 7.5, 1.3 Hz, 1H), 7.66 (t, J = 7.3 Hz, 1H), 7.53 (d, J = 9.3 Hz, 1H), 7.36–7.29 (m, 1H), 3.53 (q, J = 7.2 Hz, 4H), 3.48 (t, J = 6.9 Hz, 1H), 1.31 (t, J = 7.1 Hz, 8H), 1.27 (t, J = 6.9 Hz, 4H).

[0022] A method for synthesizing an aggregation-induced emission dye, comprising the following steps:

[0023] Dissolve the compounds of formula II and formula III in the compound of formula IV, stir and react at a temperature of 15–35 °C, and monitor the reaction by TLC;

[0024] After the reaction is completed, filter, and further purify the obtained solid to obtain the 3-dicyanovinyl-1-indanone compound of formula I,

[0025]

[0026] Preferably, the molar ratio of the compounds of formula II and formula III is 1.2:1 to 1:1.2.

[0027] Preferably, the purification method is recrystallization, washing with an inert solvent, or column chromatography.

[0028] Preferably, the purification method is column chromatography, the mobile phase used is a mixed solvent of petroleum ether and dichloromethane, and the stationary phase is silica gel with a mesh size of 200 - 300.

[0029] Compared with the prior art, the advantages of the present invention are as follows: The synthesis method of the fluorescent dye of the present invention is simple and the conditions are mild. An intramolecular ketal is formed by the hydroxyl group at the 2-position of benzaldehyde and the carbonyl group at the 1-position of indanone, thereby forming a stable approximate planar rigid structure between the benzene ring and indan, and then realizing good luminescence properties of the molecule with high luminescence efficiency; The fluorescent dye of the present invention has fluorescence in both solid state and aggregated state, and the wavelength can be adjusted by changing the substituents on salicylaldehyde, having a large Stokes shift; The fluorescent dye of the present invention has obvious color and fluorescence changes under alkaline conditions and can be used as an acid-base indicator probe, and can also be applied to fields such as luminescent materials, bioimaging, and photodynamic therapy. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 1H NMR spectrum of the dye molecule prepared in Example 1 of the present invention (solvent: CDCl3); 1 H hydrogen spectrum (solvent: CDCl3);

[0031] Figure 2 13C NMR spectrum of the dye molecule prepared in Example 1 of the present invention (solvent: CDCl3); 13 C carbon spectrum (solvent: CDCl3);

[0032] Figure 3 Crystal structure diagram of the dye molecule prepared in Example 1 of the present invention;

[0033] Figure 4 For Figure 3 Another perspective view;

[0034] Figure 5 UV-visible absorption spectrum of the dye molecule prepared in Example 1 of the present invention;

[0035] Figure 6 Photographs of the dye molecule prepared in Example 1 of the present invention under white light (left) and 365 nm ultraviolet light (right);

[0036] Figure 7 AIE effect of the dye molecule prepared in Example 1 of the present invention;

[0037] Figure 8 Change in ultraviolet absorption spectrum of the dye molecule prepared in Example 1 of the present invention after adding alkali;

[0038] Figure 9 Change in fluorescence spectrum of the dye molecule prepared in Example 1 of the present invention after adding alkali;

[0039] Figure 10 The UV-Vis absorption spectrum of the dye molecule prepared in Example 2 of the present invention;

[0040] Figure 11 The UV-Vis absorption spectrum of the dye molecule prepared in Example 3 of the present invention. Detailed implementation manners

[0041] The present invention will be further described in detail below in conjunction with the embodiments and the drawings.

[0042] Example 1:

[0043] The aggregation-induced emission dye in this example is a 3-dicyanovinyl-1-indanone compound, which is an organic fluorescent dye. The 3-dicyanovinyl-1-indanone compound is:

[0044]

[0045] The synthesis method of the above 3-dicyanovinyl-1-indanone compound is as follows:

[0046] Add 2-(2,3-dihydro-3-oxo-1H-inden-1-ylidene) malononitrile (0.40 g, 2.06 mmol), salicylaldehyde (0.21 ml, 2.1 mmol) and 10 mL of ethanol into a 50 mL flask, stir at room temperature for 30 min. After the reaction is completed, the solution is yellow. Filter, wash the obtained solid with ethanol, and dry after washing to obtain 0.46 g of bright yellow solid, with a yield of 70%.

[0047] Such as Figure 1 、 2 3, are the detection data of the obtained dye molecular material:

[0048] Nuclear magnetic 1 The 1H NMR spectrum data is as follows: 1 1H NMR (CDCl3, 500 MHz, ppm): 8.58 (d, J = 8 Hz, 1H), 8.08 (s, 1H), 7.87 (d, J = 7.5 Hz, 1H), 7.73 (td, J1 = 8 Hz, J2 = 1 Hz, 2H), 7.64 (td, J1 = 8 Hz, J2 = 1 Hz, 1H), 7.50 (dd, J1 = 7.5 Hz, J2 = 1.5 Hz, 1H), 7.44 (td, J1 = 8 Hz, J2 = 1.5 Hz, 2H), 7.18 (t, J = 8.5 Hz, 1H), 7.15 (dd, J1 = 7.5 Hz, J2 = 1 Hz), 3.82 (m, 1H), 3.55 (m, 1H), 1.02 (t, J = 7 Hz, 3H).

[0049] Nuclear magnetic 13 The 13C NMR spectrum data is as follows: 1313C NMR (CDCl3, 500 MHz, ppm) δ 159.7, 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.

[0050] The crystal structure data are as follows:

[0051]

[0052]

[0053] As Figure 4 , it can be seen that the product obtained in this example has a stable approximate planar rigid structure and good stability.

[0054] Figure 5 is the UV-Vis absorption spectrum of the prepared dye molecule, measured in acetonitrile, and the maximum absorption peak appears at 408 nm.

[0055] The prepared solid powder of the dye molecule was placed separately under natural light and irradiated with a 365 nm UV lamp. As Figure 6 shown, it was observed that the dye solid showed yellow under natural light and emitted yellow-green fluorescence under the 365 nm UV lamp, indicating that the dye molecule of the present invention has solid fluorescence.

[0056] The prepared dye molecule was made into a 10 -4 mol / L solution, and the solvents were acetonitrile and a mixed solution of acetonitrile and water (volume ratio 2:1 and 1:2) respectively. Its fluorescence spectrum was measured, and the optical property data are as Figure 7 shown. In pure organic solvents, the dye molecule basically has no fluorescence, while the fluorescence is significantly enhanced after adding water, indicating that the dye molecule has an AIE effect.

[0057] According to Figure 5 and Figure 7 , it can be known that the Stokes shift of the prepared dye molecule is 132 nm.

[0058] The prepared dye molecule was made into a 10 -4 mol / L acetonitrile solution, and 2 equivalents of sodium hydroxide water-acetonitrile (1:5) solution was added. It was observed that the solution changed from yellow to blue, and the UV-Vis absorption spectrum was measured as Figure 7 shown. A new absorption peak appeared at 560 nm for the prepared dye molecule, and strong blue fluorescence was emitted. The fluorescence spectrum is as Figure 9As shown, neutralize sodium hydroxide with hydrochloric acid, and the solution color turns back to yellow and the fluorescence disappears, indicating that the prepared dye molecule has good fluorescence properties.

[0059] Example 2:

[0060] The 3-dicyanovinyl-1-indanone compound in this example is:

[0061]

[0062] The preparation method is:

[0063] Add 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 10 ml of ethanol into a 50 ml flask, stir at room temperature, stir overnight until the reaction is complete. The reaction solution is dark red. Filter, wash with ethanol, dry to obtain an orange-red solid, and perform column chromatography to obtain 0.35 g of orange-red solid.

[0064] The nuclear magnetic 1 H nuclear magnetic resonance spectrum 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).

[0065] The ultraviolet-visible absorption spectrum of the obtained product is shown in Figure 10 , and the maximum absorption peak appears at 447 nm.

[0066] Example 3:

[0067] The 3-dicyanovinyl-1-indanone compound in this example is:

[0068]

[0069] The preparation method is:

[0070] 2-(2,3-Dihydro-3-oxo-1H-inden-1-ylidene)malononitrile (0.22 g, 1.13 mmol), 4-(N,N-diethyl)aminosalicylaldehyde (0.20 g, 1.05 mmol) and 10 ml of ethanol were added to a 50 ml flask. Stir at room temperature overnight until the reaction was complete. Filter, wash with ethanol and dry to obtain 0.39 g of dark green solid.

[0071] The nuclear magnetic resonance of the obtained product 1 The data of the 1H NMR spectrum is as follows: 1 H NMR (500 MHz, Chloroform-d) δ 8.61 (d, J = 7.8 Hz, 1H), 8.34 (s, 1H), 7.85 (d, J = 6.8 Hz, 1H), 7.71 (td, J = 7.5, 1.3 Hz, 1H), 7.66 (t, J = 7.3 Hz, 1H), 7.53 (d, J = 9.3 Hz, 1H), 7.36–7.29 (m, 1H), 3.53 (q, J = 7.2 Hz, 4H), 3.48 (t, J = 6.9 Hz, 1H), 1.31 (t, J = 7.1 Hz, 8H), 1.27 (t, J = 6.9 Hz, 4H).

[0072] The ultraviolet-visible absorption spectrum of the obtained product is shown in Figure 11 and the maximum absorption peak appears at 550 nm.

[0073] Comparing the preparation parameters of Examples 1, 2, and 3 of the present invention, as well as Figure 5 and 10 11, it can be seen that the wavelength of the product can be adjusted by changing the substituents on salicylaldehyde.

Claims

1. An aggregation-induced emission dye, characterized in that: It is a 3-dicyanovinyl-1-indanone compound, and its structural formula is Selected from:

2. The aggregation-induced emission dye according to claim 1, wherein: The benzene ring and indene in the 3-dicyanovinyl-1-indanone compound form a planar rigid structure.

3. A method for synthesizing the aggregation-induced emission dye according to claim 1, characterized in that: It includes the following steps Dissolve the compounds of formula II and formula III in the compound of formula IV, and stir and react at a temperature of 15-35 °C; After the reaction is completed, filter, and the obtained solid is further purified to obtain the 3-dicyanovinyl-1-indanone compound of formula I.

4. The synthesis method of the aggregation-induced emission dye according to claim 3, characterized in that: The molar ratio of the compounds of formula II and formula III is 1.2:1 to 1:1.

2.

5. The synthesis method of the aggregation-induced emission dye according to claim 3, wherein: The purification method is recrystallization or washing with an inert solvent or column chromatography.

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