Tetraaryl ethylene derivatives containing heteroaromatic ring structural units, and synthesis method and application thereof

Abstract

The application discloses a series of tetraaryl ethylene derivatives containing heteroaromatic ring structure units and a synthesis method and application thereof, and belongs to the technical field of organic optical material compounds. The tetraaryl ethylene derivatives containing heteroaromatic ring structure units are obtained by introducing oxazole, imidazole or thiazole heterocyclic aryl at a divinyl bridging site, the tetraaryl ethylene derivatives have various structures, and the obtained tetraaryl ethylene derivatives have obvious liquid and solid state light emitting characteristics and good aggregation induced emission performance.

Description

Technical Field

[0001] This invention relates to the field of organic optical material compound technology, specifically to tetraarylethylene derivatives containing heteroaryl ring structural units, their synthesis methods, and applications. Background Technology

[0002] Tetraphenylethylene (TPE) has long been a focus of research due to its unique aggregation-induced emission (AIE) properties, and its derivatives are widely used in chemical sensors, biosensors, bioimaging, explosive detection, organic light-emitting diodes, and other fields. However, the application potential of TPE molecules themselves is limited, and the device performance is poor, with a maximum luminescence of only 1800 cd / m². 2 The maximum current efficiency and maximum external quantum efficiency are only 0.45 cd / A and 0.4%, respectively. Tetraarylethylene (TAE) compounds containing heterocyclic structural units, where heterocyclic aromatic rings replace benzene rings, not only retain the AIE properties of the molecule but also exhibit the inherent characteristics of heterocyclic segments (such as reactivity, Lewis basicity, metal coordination ability, redox activity, and biological activity), giving these compounds a broader application prospect (Gabr, MT, Pigge, FCAIE Active Heteroarylethylenes [J]. Aggregation-Induced Emission: Materials and Applications Volume 1, 2016, Chapter 10, 175-191.). Furthermore, heteroatom substitution is an important way to regulate the properties of conjugated carbon-based materials at the molecular scale. Numerous experiments have demonstrated that heteroatom substitution doping in luminescent materials can significantly improve the hole or electron transport capability of the material, achieving high performance and multifunctionality of luminescent materials.

[0003] Patent application CN120774900A discloses a thiophene site-specific modified TAE material, the main structure of which is tetraarylethylene, wherein thiophene substitution exists on the tetraarylethylene, and an R group is introduced at the end of the thiophene, where R is -CHO or The preparation method of this material is as follows: under a protective atmosphere, 2-bromo-1,1,2-tristyrene, an aldehyde-containing thiophene boric acid compound, a palladium catalyst, a basic compound, and a first solvent are mixed and subjected to a Suzuki coupling reaction to prepare aldehyde intermediates with different substitution positions of the thiophene ring; then, the aldehyde intermediates are mixed with 2-aminobenzylthiophenol, sodium metabisulfite, and a second solvent to undergo a condensation reaction to obtain the final product. This invention forms a diarylethene functional unit with photoisomerization capability through the conjugated coupling of the thiophene ring and the ethylene-bridged benzene ring, thereby improving the aggregation-induced emission performance of the material while achieving photoresponsive activity. However, there are currently no reports on tetraarylethene derivatives containing heterocyclic aromatic ring structural units that have good aggregation-induced emission performance by introducing oxazole, imidazole, or thiazole heterocyclic aryl groups at the diethylene bridging site. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a series of tetraarylethylene derivatives containing heteroaryl ring structural units with good aggregation-induced emission properties, as well as their synthesis methods and applications.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] The tetraarylethylene derivatives containing heterocyclic structural units described in this invention are compounds having the structure shown in Formula 3 below, or pharmaceutically acceptable salts thereof:

[0007] ;

[0008] In this context, dashed lines represent either bonding or non-bonding;

[0009] X is O, S, or N-Me;

[0010] R is a hydrogen atom, a halogen atom, a phenyl group, or a carbon atom. 1~4 Alkyl groups.

[0011] Furthermore, R can be a hydrogen atom, a chlorine atom, a phenyl group, or a methyl group.

[0012] Preferably, the tetraarylethylene derivative containing a heterocyclic structural unit of the present invention is one of the following compounds 3a to 3g:

[0013] , , , , , , .

[0014] The method for synthesizing tetraarylethylene derivatives containing heterocyclic structural units according to the present invention includes: placing a compound (2-bromo-1,1,2-triphenylene) with the structure shown in Formula 1 and a compound with the structure shown in Formula 2 in an organic solvent, adding an organophosphorus ligand and a basic substance in the presence of a palladium catalyst and a copper catalyst, and then adding or not adding pentylene anhydride, and reacting under heating conditions to obtain a crude product of the target compound;

[0015] , ;

[0016] In this context, dashed lines represent either bonding or non-bonding;

[0017] X is O, S, or N-Me;

[0018] R is a hydrogen atom, a halogen atom, a phenyl group, or a carbon atom. 1~4 Alkyl groups.

[0019] Furthermore, higher yields can be obtained by confining the reaction to a protected atmosphere (such as nitrogen or argon).

[0020] In the synthesis method described in this invention, the organic solvent can specifically be one or a combination of two or more selected from toluene, dimethyl sulfoxide (DMSO), and 1,4-dioxane. The amount of organic solvent used can be determined as needed, preferably sufficient to fully dissolve the reactants.

[0021] In the synthesis method described in this invention, the selection and dosage of the palladium catalyst, copper catalyst, organophosphorus ligand, and basic substance are the same as in the prior art, and are preferably as follows:

[0022] The palladium catalyst is selected from one or more of tetra(triphenylphosphine)palladium (Pd(PPh3)4), palladium chloride (PdCl2), palladium acetate (Pd(OAc)2), bis(triphenylphosphine)palladium dichloride (PdCl2(PPh3)2), palladium trifluoroacetate (Pd(TFA)2), bis(acetylacetone)palladium (Pd(acac)2), and bis(dibenzylacetone)palladium (Pd(dba)2). Its preferred dosage is 2-10% of the molar amount of the compound with the structure shown in Formula 1.

[0023] The copper catalyst is selected from one or more of copper fluoride (CuF2), copper bromide (CuBr2), copper chloride (CuCl2), copper iodide (CuI2), copper acetate (Cu(OAc)2), copper trifluoromethanesulfonate (Cu(OTf)2), copper sulfate (CuSO4), cuprous iodide (CuI), cuprous bromide (CuBr), and cuprous chloride (CuCl). Its preferred dosage is 5-15% of the molar amount of the compound with the structure shown in Formula 1.

[0024] The organophosphine ligand is selected from one or more of triphenylphosphine (PPh3), tricyclohexylphosphine (PCy3), tris(4-trifluorotolyl)phosphine (P(4-CF3Ph)3), 4,5-bis(diphenylphosphine-9,9-dimethyloxanthracene (Xantphos), and 1,4-bis(diphenylphosphine)butane (dppb). Its preferred dosage is 5-15% of the molar amount of the compound with the structure shown in Formula 1.

[0025] The alkaline substance is selected from one or more of sodium acetate (CH3COONa), tripotassium phosphate (K3PO4), sodium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, cesium carbonate (Cs2CO3), potassium carbonate, sodium carbonate, potassium tert-butoxide (t-BuOK), sodium tert-butoxide, potassium fluoride, cesium fluoride, 4-dimethylaminopyridine (DMAP), and triethylamine (Et3N). Its preferred amount is 1.0 to 2.0 times the molar amount of the compound with the structure shown in Formula 1.

[0026] In the synthetic method described in this invention, pentovalinic anhydride (Piv2O) assists in the deprotonation of heterocyclic CH bonds, thus facilitating copper-catalyzed CH activation. The applicant's experiments show that the addition of pentovalinic anhydride can achieve higher yields.

[0027] In the synthesis method described in this invention, the reaction is preferably carried out at a temperature greater than or equal to 100°C, and more preferably at a temperature of 130–150°C. The reaction is monitored by TLC until completion. Based on the applicant's experience, when the reaction is carried out at 130–150°C, a reaction time of 3–8 hours is suitable.

[0028] The above method yields a crude product of the target compound, which can be purified using existing conventional purification methods to improve its purity. Specifically, the crude product can be purified by silica gel column chromatography to obtain the purified target compound. More preferably, the reactants are extracted first before silica gel column chromatography to reduce the load on the silica gel column. The eluent used for elution on the silica gel column is preferably a mixed solution of ethyl acetate and petroleum ether, with a volume ratio of ethyl acetate to petroleum ether of 1:30 to 1:50, more preferably 1:35 to 1:45. If extraction is involved, conventional extractants such as ethyl acetate or dichloromethane can be used.

[0029] The applicant discovered through experiments that the tetraarylethylene derivatives containing heterocyclic aromatic ring structural units described in this invention possess excellent aggregation-induced emission properties. Therefore, this invention also includes the application of the aforementioned tetraarylethylene derivatives containing heterocyclic aromatic ring structural units in color-changing materials (such as photochromic materials), information storage materials, anti-counterfeiting materials, or optical device materials (such as organic light-emitting diodes, organic thin-film transistors, organic photovoltaic devices, luminescent electrochemical cells, or chemical sensors). The application specifically refers to the color-changing and emission properties of the tetraarylethylene derivatives containing heterocyclic aromatic ring structural units described in this invention in solution, polymer film, solid powder, and single-crystal states.

[0030] More specifically, the tetraarylethylene derivative containing heteroaryl ring structural units described in this invention is used as a probe in Ce... 3+ Applications in ion detection.

[0031] The present invention also includes a color-changing material, information storage material, anti-counterfeiting material, or optical device material, which comprises the above-mentioned tetraarylethylene derivative containing heterocyclic aromatic structural units.

[0032] Compared with existing technologies, this invention introduces oxazole, imidazole, or thiazole heterocyclic aryl groups at the diethylene bridging site to obtain tetraarylethylene derivatives with diverse structures containing heterocyclic aryl ring structural units. These tetraarylethylene derivatives exhibit significant liquid and solid-state luminescence properties and good aggregation-induced emission performance. Compound 3g can be used as a highly selective "open-type" fluorescent probe in a water / ethanol mixture (concentration 10). -5 Detection of trivalent cerium ions (Ce) in (mol / L, water content 90%) 3+ The detection limit is 0.799 μM. Furthermore, the method described in this invention is simple to operate and has a high yield. Attached Figure Description

[0033] Figure 1 The luminescence properties of the target compounds of this invention in liquid and solid states are shown, wherein (a) is the luminescence properties of compounds 3a, 3b, 3c, 3d, 3e, 3f and 3g in ethanol solution (1×10⁻⁶). -5(a) Absorption spectrum of compounds 3a, 3b, 3c, 3d, 3e, 3f and 3g in mol / L; (b) Emission spectrum of thin films of compounds 3a, 3b, 3c, 3d, 3e, 3f and 3g under 365nm light irradiation.

[0034] Figure 2 The aggregation-induced emission properties of the target compound 3g of this invention are shown in (a) below. -5 Fluorescence emission spectra of compound 3g before and after the addition of different metal ions at a concentration of mol / L; (b) fluorescence emission spectra of compound 3g before and after the addition of different metal ions and Ce. 3+ Histograms of fluorescence intensity monitored at 360 nm in the ion coexistence system; (c) and (d) are the fluorescence intensity of 3 g of compound at different concentrations of Ce. 3+ Fluorescence spectra in the presence of ions; (e) shows the fluorescence spectrum of compound 3g with Ce. 3+ Linear relationship of ion concentration; (f) is the relationship between 3g of compound and Ce. 3+ Ion binding ratio curves. Inset: Fluorescence image of the solvent under ultraviolet light (365 nm) illumination. Detailed Implementation

[0035] To better explain the technical solution of the present invention, the present invention will be further described in detail below with reference to the embodiments, but the implementation of the present invention is not limited thereto.

[0036] In the following embodiments, compound 1 represents the compound with the structure shown in Formula 1, namely 2-bromo-1,1,2-triphenylene; and compound 2 represents the compound with the structure shown in Formula 2.

[0037] Example 1: General synthetic method for compounds 3a-3g

[0038]

[0039] 3a: X = O, the dashed line represents bonding, R = H, that is, the heterocyclic aryl group introduced at the diethylene bridging site is benzoxazole.

[0040] 3b: X = O, the dashed line represents bonding, R = 5-Me, that is, the heterocyclic aryl group introduced at the diethylene bridging site is 5-methylbenzoxazole.

[0041] 3c: X = O, the dashed line represents bonding, R = 5-Cl, that is, the heterocyclic aryl group introduced at the diethylene bridging site is 5-chlorobenzoxazole.

[0042] 3d: X = O, the dashed line indicates no bonding, R = 5-Me, that is, the heterocyclic aryl group introduced at the diethylene bridging site is 5-methyloxazole.

[0043] 3e: X = O, the dashed line indicates no bonding, R = 5-Ph, that is, the heterocyclic aryl group introduced at the diethylene bridging site is 5-phenyloxazole.

[0044] 3f: X = S, the dashed line represents bonding, R = H, that is, the heterocyclic aryl group introduced at the diethylene bridging site is benzothiazole.

[0045] 3g: X = N-Me, the dashed line represents bonding, R = H, that is, the heterocyclic aryl group introduced at the diethylene bridging site is 1-methylbenzimidazole.

[0046] In a reaction tube sealed at one end, 0.3 mmol of compound 1, 0.2 mmol of compound 2, 5% palladium acetate (equivalent to 5% of the molar amount of compound 1), 10 mol% copper fluoride, 10 mol% triphenylphosphine, 1.5 equivalents of potassium carbonate, and 1.5 equivalents of pentanoic anhydride were added, followed by 1 mL of 1,4-dioxane as solvent. The reaction tube was sealed and reacted at 140 °C for 5 h under nitrogen protection, with the reaction progress monitored by TLC. After the reaction was completed, the system was cooled to room temperature, the reaction was quenched with 30 mL of water, and extracted with ethyl acetate (3 × 30 mL). The organic phases were combined, washed successively with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was purified by rapid silica gel column chromatography (ethyl acetate / petroleum ether = 1:40, v / v) to obtain target compound 3. The structural characterization data of different target products are as follows:

[0047] 3a: 2-(1,2,2-triphenylvinyl)benzo[d]oxazole

[0048]

[0049] Yellow solid, yield: 71%. 1 H NMR (500 MHz, CDCl3) δ 7.64-7.60 (m, 1H), 7.29-7.24 (m, 3H), 7.23-7.14 (m, 13H), 7.08 (d, J = 6.6 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 165.16, 150.24, 150.08, 142.68, 141.57, 141.43, 139.00, 131.18,130.79, 129.76, 128.15, 128.05, 127.93, 127.82, 127.75, 127.58, 127.55,125.00, 124.13, 120.20, 110.41. HRMS (ESI) m / z: calcd for C 27 H 20 NO [M + H] + 374.1539; found 374.1547.

[0050] 3b: 5-Methyl-2-(1,2,2-triphenylvinyl)benzo[d]oxazole

[0051]

[0052] Yellow solid, yield: 63%. 1 H NMR (400 MHz, CDCl3) δ 7.40 (s, 1H), 7.24-7.11(m, 14H), 7.10-7.03 (m, 3H), 2.40 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ 165.22,149.96, 148.31, 142.72, 141.75, 141.45, 139.03, 133.94, 131.18, 130.77,129.76, 128.12, 128.02, 127.88, 127.81, 127.70, 127.50, 126.15, 120.04,109.79, 21.40. HRMS (ESI) m / z: calcd for C 28 H 22 NO [M + H] + 388.1696; found388.1703.

[0053] 3c: 5-Chloro-2-(1,2,2-triphenylvinyl)benzo[d]oxazole

[0054]

[0055] Yellow solid, yield: 68%. 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 2.1 Hz, 1H), 7.24-7.10 (m, 15H), 7.07 (dd, J = 8.1, 1.7 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ166.61, 150.97, 148.66, 142.66, 142.55, 141.19, 138.73, 131.17, 130.75,129.71, 129.67, 128.25, 128.13, 127.94, 127.88, 127.71, 127.16, 125.35,120.09, 111.15. HRMS (ESI) m / z: calcd for C 27 H 20 NO [M + H] + 408.1149; found 408.1150.

[0056] 3d: 4-Methyl-2-(1,2,2-triphenylvinyl)oxazole

[0057]

[0058] Yellow solid, yield: 59%. 1 H NMR (400 MHz, CDCl3) δ 7.16-7.11 (m, 3H) ,7.07-6.93 (m, 13H) , 1.98 (s, 3H) . 13 C NMR (101 MHz, CDCl3) δ 163.06, 147.78,142.97, 141.64, 139.23, 137.12, 133.59, 131.11, 130.69, 129.74, 127.94,127.83, 127.78, 127.73, 127.45, 127.36, 127.27, 11.56. HRMS (ESI) m / z: calcdfor C 24 H 20 NO [M + H] + 338.1539; found 338.1549.

[0059] 3e: 5-Phenylacetyl-2-(1,2,2-triphenylvinyl)oxazole

[0060]

[0061] Yellow solid, yield: 65%. 1 H NMR (400 MHz, CDCl3) δ 7.30-7.16 (m, 14H), 7.14-7.08 (m, 5H), 7.07-7.02 (m, 2H). 13 C NMR (101 MHz, CDCl3) δ 163.00, 150.26,147.91, 143.56, 141.77, 139.09, 131.16, 131.10, 129.65, 128.60, 128.16,128.08, 127.99, 127.73, 127.70, 127.56, 127.42, 127.40, 124.06, 122.97. HRMS(ESI) m / z: calcd for C 29 H 22 NO [M + H] + 400.1696; found 400.1704.

[0062] 3f: 2-(1,2,2-triphenylvinyl)benzo[d]thiazole

[0063]

[0064] Yellow solid, yield: 67%. 1 H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.2 Hz,1H), 7.70 (d, J = 7.9 Hz, 1H), 7.37 (t, J = 7.6 Hz, 1H), 7.29 (t, J = 7.6 Hz,1H), 7.24-7.10 (m, 13H), 7.09-7.02 (m, 2H). 13 C NMR (101 MHz, CDCl3) δ 170.57,152.95, 147.40, 142.33, 141.95, 141.07, 136.29, 133.84, 131.09, 130.99,130.78, 128.12, 128.00, 127.83, 127.76, 127.39, 127.34, 125.70, 124.96,123.41, 121.23. HRMS (ESI) m / z: calcd for C 27 H 20NS [M + H] + 390.1311; found 390.1321.

[0065] 3g: 1-Methyl-2-(1,2,2-triphenylvinyl)-1H-benzo[d]imidazole

[0066]

[0067] Yellow solid, yield: 69%. 1 H NMR (400 MHz, CDCl3) δ 7.73-7.66 (m, 1H), 7.24-7.13 (m, 8H), 7.12-6.96 (m, 10H), 3.39 (s, 3H). 13 C NMR (101 MHz, CDCl3) δ154.68, 147.78, 143.02, 142.17, 141.64, 140.10, 134.85, 131.19, 130.25,129.82, 129.19, 128.04, 127.98, 127.94, 127.69, 127.53, 127.14, 122.31,121.96, 119.91, 109.26, 30.34. HRMS (ESI) m / z: calcd for C 28 H 23 N2 [M + H] + 387.1856; found 387.1861.

[0068] Example 2: Synthesis of compound 3a

[0069]

[0070] Following the synthetic route described above and referring to the method of Example 1, compound 3a was synthesized under the synthetic conditions listed in Table 1 below. The synthesized products were characterized, and compound 3a was obtained in all cases except when DMF (N,N-dimethylformamide) was used as the solvent. The results are shown in Table 1.

[0071] Table 1. Optimization of Reaction Conditions a,b

[0072]

[0073] aReaction conditions: Compound 1 (0.3 mmol), Compound 2a (0.2 mmol), palladium catalyst (5 mol%), copper catalyst (10 mol%), ligand (10 mol%), additive (1.5 equivalent), pentovalinic anhydride (Piv2O, 1.5 equivalent), 1,4-dioxane (1 mL), reaction at 140 °C for 5 h, sealed in a nitrogen atmosphere. b Based on compound 1, the yield of the pure product is determined. c The reaction temperature is 130 ℃. d The reaction temperature was 150 °C. ND = No product detected. Trace indicates that the target product was detected but difficult to separate.

[0074] Example 3: Synthesis of compound 3a

[0075] Compound 3a was synthesized according to the method in Example 1, except that pentovalinic anhydride was not added. A yellow solid was obtained in 32% yield. The yellow solid was identified as compound 3a by 1H NMR, 1C NMR, high-resolution mass spectrometry combined with electrospray ionization analysis.

[0076] Experimental Example 1: Photochromic Experiment of Compound 3a~3g

[0077] To further investigate its optical properties, the applicant used an aqueous solution of ethanol (1×10⁻⁶) -5 Compounds 3a to 3g were characterized by UV-Vis absorption spectroscopy and photoluminescence (PL) spectroscopy in both mol / L and thin film states. The results are shown in Table 2 and [Table data missing]. Figure 1 As shown, all compounds exhibit three similar sets of absorption peaks in ethanol solution (Figure 1a): a strong absorption peak at 201–205 nm, a moderate intensity absorption peak at 230–244 nm, and a long-wavelength absorption peak at 284–338 nm. These absorption peaks can be attributed to the conjugated framework. Transitions and intramolecular charge transfer (ICT) processes. The molar absorptivity (ε) of compounds 3a to 3g are 37120, 62542, 58019, 57563, 52804, 47800, and 52238, respectively. As shown in Figure 1b, the maximum emission wavelengths of compounds 3a-3g in the thin film state are between 431 and 486 nm. Compared with compound 3b (431 nm), the maximum emission wavelength of compound 3f (486 nm) shows a significant redshift (Δλ = 55 nm), which may be attributed to the enhanced intermolecular interactions in the solid state. These results indicate that substituents with different electronic properties lead to different intramolecular charge transfer (ICT) effects. The fluorescence quantum yields (Φ) of compounds 3a-3g in the thin film are shown in Figure 1b.F.film The percentages were 79.56%, 86.43%, 43.74%, 19.55%, 81.40%, 79.55%, and 47.53%, respectively; in a dilute ethanol solution (1×10⁻⁶), the percentages were 47.53%. -5 The corresponding quantum yield (Φ) in mol / L) F.soln The aggregation-induced emission (AIE) factors were 9.82%, 7.43%, 7.82%, 6.78%, 7.16%, 9.84%, and 9.54%, respectively. Based on this, the aggregation-induced emission (AIE) factor (α) was calculated. AIE =Φ F,film / Φ F,soln The fluorescence lifetimes were 8.1, 11.6, 5.6, 2.9, 11.3, 8.1, and 5.0, respectively. These results clearly demonstrate that compounds 3a–3g all exhibit aggregation-induced emission behavior. Furthermore, the applicant also investigated their fluorescence lifetimes in the thin film state (…). The lifetimes of 3a to 3g are 1.32, 2.57, 2.04, 2.64, 1.94, 2.23 and 2.13 ns, respectively.

[0078] Table 2. Photophysical properties of compounds 3a, 3b, 3c, 3d, 3e, 3f and 3g

[0079]

[0080] Experimental Example 2: Test of Aggregation-Induced Emission Properties of 3g of Compound

[0081] Given the good aggregation-induced emission properties and potential metal ion binding sites of the synthesized compound, the applicant, in a water / ethanol mixture (water volume fraction f...), w =90%), the effects of adding 1 equivalent of different metal ions on the compound 3g (1×10) were investigated. -5 The change in fluorescence emission intensity (mol / L), the metal ions investigated include Ce 3+ Mn 2+ Fe 3+ Ag + Cd 2+ Cu + Bi 3+ Co 2+ Cu 2+ Al 3+ and Zn 2+ Compound 3g exhibited a significant fluorescence response to Ce³⁺ ions. (From...) Figure 2 As can be seen, the addition of Ce³⁺ significantly enhances the emission intensity, while other metal ions (Mn)... 2+ Fe 3+ Ag +Cd 2+ Cu + Bi 3+ Co 2+ Cu 2+ Al 3+ Zn 2+ This only causes a slight increase or decrease in fluorescence intensity. Therefore, compound 3g can be used as a selective fluorescence-activated probe for Ce. 3+ Ion detection.

[0082] In Ce 3+ (1 equivalent) and other competing metal ions (Mn equivalents) 2+ Fe 3+ Ag + Cd 2+ Cu + Bi 3+ Co 2+ Cu 2+ Al 3+ Zn 2+ In the presence of ), 3g of compound solution (1×10) -5 The fluorescence emission intensity changes of (mol / L, water / ethanol volume ratio 9:1) are as follows: Figure 2 As shown in b. The results indicate that Ce is present. 3+ A 3g solution of the compound exhibited strong fluorescence; although the addition of other competing metal ions slightly reduced the fluorescence emission, Fe... 3+ As a notable exception, it can quench fluorescence intensity by approximately 50%. Experimental results show that, except for Fe... 3+ In addition, the presence of other competing metal ions affects the detection of Ce by the 3g fluorescence-on-demand method using the probe compound. 3 + Ions do not cause significant interference.

[0083] To further investigate the relationship between fluorescence intensity and Ce 3+ The relationship between concentrations, the applicant's reaction to a 3g solution of the compound (1×10⁻⁶) -5 Ce was added in successive additions at a concentration of mol / L. 3+ Titration experiment of ions. With Ce 3+ As the concentration increases, the maximum fluorescence emission intensity at 360 nm gradually increases; when Ce 3+ When the concentration is in the range of 17~20 μM, the fluorescence intensity at 360 nm tends to stabilize. Figure 2 c, 2d). For example... Figure 2 As shown in equation e, the linear fitting equation in the low concentration range is y = 2.389x + 1.089, and the correlation coefficient R0 is [value missing]. 2 =0.996, calculated to yield Ce 3+The limit of detection (LOD) is 0.799 μM.

[0084] To elucidate the possible coordination mode between compound 3g and Ce³⁺ ions, the formed complex was subjected to spectroscopic titration using the Job continuous transformation method. The relationship between compound 3g and Ce³⁺ ions was maintained. 3+ The total concentration is 2×10 -5 mol / L, changing the molar ratio of the two components. For example... Figure 2 As shown in f, the maximum photoluminescence intensity occurs at a mole fraction of 0.46, indicating that compound 3g reacts with Ce. 3+ Ions combine in a stoichiometric ratio of 1:1.

Claims

1. A tetraarylethylene derivative containing a heterocyclic structural unit, or a pharmaceutically acceptable salt thereof, of the structure shown in Formula 3 below: ； in, Dashed lines indicate whether bonds are formed or not; X is O, S, or N-Me; R is a hydrogen atom, a halogen atom, a phenyl group, or a C atom. 1~4 Alkyl groups.

2. The tetraarylethylene derivative containing a heterocyclic structural unit according to claim 1, characterized in that, R can be a hydrogen atom, a chlorine atom, a phenyl group, or a methyl group.

3. The tetraarylethylene derivative containing a heterocyclic structural unit according to claim 1, characterized in that it is... One of the following compounds 3a to 3g: 、 、 、 、 、 、 。 4. The method for synthesizing the tetraarylethylene derivative containing a heterocyclic structural unit as described in claim 1, characterized in that, Take the compounds with the structure shown in Formula 1 and the compounds with the structure shown in Formula 2 and place them in an organic solvent. In the presence of a palladium catalyst and a copper catalyst, add an organophosphorus ligand and a basic substance, and then add or not add pentanoic anhydride. React under heating conditions to obtain the crude product of the target compound. 、 ； In this context, dashed lines represent either bonding or non-bonding; X is O, S, or N-Me; R is a hydrogen atom, a halogen atom, a phenyl group, or a C atom. 1~4 Alkyl groups.

5. The synthesis method according to claim 4, characterized in that, The reaction was carried out under a protective atmosphere.

6. The synthesis method according to claim 4, characterized in that, It also includes a step of purifying the crude target compound obtained.

7. The synthesis method according to any one of claims 4 to 6, characterized in that, The organic solvent is selected from one or more of toluene, dimethyl sulfoxide and 1,4-dioxane; The palladium catalyst is selected from one or more of tetra(triphenylphosphine)palladium, palladium chloride, palladium acetate, bis(triphenylphosphine)dichloride palladium, palladium trifluoroacetate, bis(acetylacetone)palladium and bis(dibenzylideneacetone)palladium; The copper catalyst is selected from one or more of copper fluoride, copper bromide, copper chloride, copper iodide, copper acetate, copper trifluoromethanesulfonate, copper sulfate, cuprous iodide, cuprous bromide and cuprous chloride; The organophosphine ligand is selected from one or more of triphenylphosphine, tricyclohexylphosphine, tris(4-trifluorotolyl)phosphine, 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene and 1,4-bis(diphenylphosphine)butane; The alkaline substance is selected from one or more of sodium acetate, tripotassium phosphate, sodium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, cesium carbonate, potassium carbonate, sodium carbonate, potassium tert-butoxide, sodium tert-butoxide, potassium fluoride, cesium fluoride, 4-dimethylaminopyridine, and triethylamine.

8. The synthesis method according to any one of claims 4 to 6, characterized in that, The reaction is carried out at a temperature of 100°C or higher.

9. The application of the tetraarylethylene derivative containing heterocyclic structural units as described in claim 1 in color-changing materials, information storage materials, anti-counterfeiting materials, or optical device materials.

10. A color-changing material, information storage material, anti-counterfeiting material, or optical device material, comprising the tetraarylethylene derivative containing heterocyclic aromatic structural units as described in claim 1.

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