A method for synthesizing a tetraazapentalene derivative optical limiting material

Abstract

The application discloses a synthesis method of a tetrazaporphyrin derivative optical limiting material. Different from a traditional modification strategy of isolated nitrogen atom doping, the application directly and accurately embeds a nitrogen atom pair (such as an azo group N=N or a hydrazine group N-N) at 3, 4, 10 and 11 positions (namely K positions) of a porphyrin skeleton, and excellent reverse saturation absorption performance is obtained by changing the hybridization state of the nitrogen atom to finely control the electronic structure of the molecule.

Description

Technical Field

[0001] This invention relates to the field of nonlinear optical materials technology, specifically to a method for synthesizing a tetraazine derivative optical limiting material. Background Technology

[0002] Nonlinear optics is an important branch of modern optics, mainly studying the interaction between strong light fields (such as lasers) and matter. Under strong light, the polarization intensity and electric field intensity of the medium exhibit a nonlinear relationship, and various nonlinear effects are generated by relying on high-order nonlinear polarizability. With the continuous development of laser technology, biological imaging, and quantum information, there is an urgent need to develop nonlinear optical materials that possess large nonlinear optical coefficients, ultrafast response, high laser damage threshold, low dielectric constant, easy modification, and excellent processability.

[0003] Nonlinear optical materials with π-extended conjugated systems are currently attracting significant attention in devices such as optical clipping, mode-locking, and optical switches. These include carbon-based materials like fullerenes and graphene, and organic π-conjugated molecules such as porphyrins and phthalocyanines. Carbon-based materials rely on scattering to generate nonlinear responses, while excited-state absorption is one of the sources of nonlinear optical effects in organic π-conjugated molecules. The photoelectric properties of these molecules can be flexibly controlled through framework structure modification. Therefore, directional functionalization of organic π-conjugated frameworks is an effective approach to developing high-performance nonlinear optical materials. Oleophane, as a typical large conjugated polycyclic aromatic hydrocarbon, possesses a highly delocalized rigid π-conjugated system and unique electronic orbital characteristics, making it suitable for controlling photoelectric properties through heteroatom doping and peripheral modification. However, existing synthetic methods can only introduce isolated nitrogen atoms at single sites. Precisely embedding continuous dinitrogen atom pairs such as azo or hydrazine groups at the edge of oleophane is extremely difficult. Furthermore, existing dopants are mostly pyridine-type nitrogens, which cause localization of molecular aromaticity, significantly limiting the controllability of photoelectric properties.

[0004] Existing technologies have developed various methods for modifying bis(anthracene) and ovalbenzene. One type is heteroatom doping modification, which involves nitrogen atom doping of the fully serrated periphery through a one-step reaction of a formyl precursor to obtain nitrogen-doped ovalbenzene. This can significantly reduce the highest occupied molecular orbital (HOMO) energy level of the molecule and endow it with acid-base response characteristics in the field of chemical sensors. Org. Lett. 2021, 21 (8640-8644), or by introducing a six-membered lactone ring at the bay position for oxygen doping to obtain lactone-embedded bis-anthracene, which can not only narrow the band gap and achieve near-infrared emission, but also promote the formation of a tight columnar packing of molecules, showing unique photothermal conversion potential ( Org. Lett. 2025, 44, 12331-12336); another type utilizes cyclic tetraamide precursors to construct a highly rigid framework containing four imide groups through intramolecular cyclization reactions, thereby obtaining ovalbenzene derivatives with extremely small Stokes shifts and strong visible light emission ( , 12331-12336); Org. Lett. 2025, 32 (9090-9094). However, the above modification schemes can only achieve the control of molecular frontier orbital energy levels, improve solid-state aggregation behavior, and enhance the rigidity of the framework plane, but it is difficult to finely control the molecular electronic structure and excited-state absorption characteristics. This not only limits the further development of its luminescent properties, but also becomes the fundamental bottleneck restricting these traditional polycyclic aromatic hydrocarbon derivatives from achieving excellent nonlinear optical performance, making it difficult to meet the stringent requirements of modern optoelectronic devices (including optical clipping, mode-locking, and optical switching) for cutting-edge nonlinear optical materials.

[0005] Current research on nitrogen doping of polycyclic aromatic hydrocarbons focuses on isolated single nitrogen atoms. A few hydrazine-bonded structures simply embed nitrogen atoms within the framework, making it difficult to prepare polycyclic aromatic hydrocarbon molecules with multiple nitrogen atom pairs doped at the edges. Therefore, it is urgent to develop polycyclic aromatic hydrocarbon derivatives doped with multiple nitrogen atom pairs and their synthesis methods to expand the high-performance nonlinear optical material system. Summary of the Invention

[0006] The purpose of this invention is to solve the above-mentioned technical problems and provide a method for synthesizing a tetraazapyrobenzene derivative optical limiting material, which has nonlinear optical properties.

[0007] The above-mentioned objective of the present invention is achieved through the following technical solution: The first aspect of this invention provides a tetraazaphosphonium derivative, wherein the structural formula of the tetraazaphosphonium derivative is selected from one of the following structural formulas: , , .

[0008] A second aspect of the present invention provides a tetraazaphosphonium derivative. The synthesis method includes the following steps: (1) An oxidation reaction was carried out in the presence of elemental iodine and organic solvent I to obtain... ; (2) The reaction proceeds with hydrazine hydrate (N2H4·H2O) in organic solvent II via a condensation reaction to yield... ; (3) Under an inert atmosphere, The tetraazapyridine derivative was subjected to a cycloaddition reaction with 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione in organic solvent III to give the tetraazapyridine derivative. (Recorded as TAO2).

[0009] Further, in step (1), the organic solvent I is dimethyl sulfoxide (DMSO) and / or 1,4-dimethyl sulfoxide (DMSO) and / or 1,4-dimethyl sulfoxide (DMSO). Dioxane.

[0010] Furthermore, in step (1), the oxidation reaction is carried out at a temperature of 80-120 °C for 1-3 h.

[0011] Further, in step (1), the iodine element and The molar ratio is (3-5):1.

[0012] Furthermore, in step (2), the organic solvent II is ethanol.

[0013] Further, in step (2), the hydrazine hydrate and The molar ratio is (140-200):1.

[0014] Furthermore, in step (2), the temperature of the condensation reaction is 15-35 °C and the time is 0.5-2 h.

[0015] Furthermore, in steps (1) and (2), after the reaction is completed, a post-processing and purification step is also included. The post-processing includes quenching, extraction, washing, drying, and solvent removal. The purification is selected from at least one of silica gel column chromatography and recrystallization.

[0016] Furthermore, in step (3), the inert atmosphere is an argon atmosphere; and the organic solvent III is toluene.

[0017] Furthermore, in step (3), the cycloaddition reaction is carried out at a temperature of 100-120 °C for 1-3 h.

[0018] Further, in step (3), the 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione and The molar ratio is (8-12):1.

[0019] Furthermore, in step (3), the cycloaddition reaction further includes the steps of removing the solvent and then purifying by chromatography and recrystallization.

[0020] A third aspect of the present invention provides a tetraazaphosphonium derivative. The synthesis method includes the following steps: Will Dissolved in organic solvent IV, the tetraazaphosphonate derivative is hydrolyzed in the presence of alkali, water, and alcohol to yield the tetraazaphosphonate derivative. (Recorded as TAO1).

[0021] Furthermore, the organic solvent IV is tetrahydrofuran; the base is sodium hydroxide; and the alcohol is ethanol.

[0022] Furthermore, the alkali and The molar ratio is (280-320):1.

[0023] Furthermore, the hydrolysis reaction is carried out at a temperature of 60-80 °C for a time of 0.5-1.5 h.

[0024] Furthermore, the hydrolysis reaction further includes steps of quenching, extraction, drying to remove solvent, and then purification by chromatography and recrystallization.

[0025] Furthermore, the quenching reagent is a saturated ammonium chloride aqueous solution; the extraction solvent is ethyl acetate; and the drying reagent is anhydrous sodium sulfate.

[0026] Furthermore, the eluent used in the chromatography is a mixed solvent of petroleum ether and ethyl acetate, with a volume ratio of 1:(1-3); the solvent used in the recrystallization purification is methanol.

[0027] The fourth aspect of the present invention provides a tetraazaphosphonium derivative. The synthesis method includes the following steps: In an inert atmosphere, The tetraazapyridine derivative was cycloadditionally reacted with 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione in organic solvent V to give the tetraazapyridine derivative. (Recorded as TAO3).

[0028] Furthermore, the inert atmosphere is a nitrogen atmosphere.

[0029] Furthermore, the organic solvent V is toluene.

[0030] Further, the 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione and The molar ratio is (4-5):1.

[0031] Furthermore, the cycloaddition reaction is carried out at a temperature of 100-120 °C for a time of 1-3 h.

[0032] Furthermore, the cycloaddition reaction further includes steps of removing the solvent, followed by column chromatography and recrystallization purification.

[0033] Furthermore, the eluent used in the column chromatography is a mixed solvent of petroleum ether and dichloromethane, with a volume ratio of (0.8-1.2):1; the solvent used in the recrystallization is ethanol.

[0034] The above-described technical solution of the present invention has the following beneficial effects: This invention employs a nitrogen atom doping strategy to successfully synthesize three tetraazaphosphonium derivatives (TAO1, TAO2, and TAO3). By leveraging the hybridization effect introduced by nitrogen doping, the photophysical properties of the target molecules can be effectively controlled, and the resulting molecules can be applied in the field of organic optical limiting materials. With the structural evolution of the molecular skeleton, the π-conjugated system of TAO1 to TAO3 gradually expands, and the degree of π-electron delocalization continuously increases, causing its absorption behavior to reverse from saturated absorption to antisaturated absorption. Among them, TAO2 and TAO3 possess excellent antisaturated absorption characteristics and low-threshold optical limiting performance, showing great application potential in laser protection materials; while TAO1, due to its large ground-state absorption cross section, generates a strong ground-state bleaching (GSB) effect, reversing its optical behavior to saturated absorption, and has important application prospects in high-end optoelectronic devices such as ultrafast laser mode-locked devices. Furthermore, the synthesis reaction conditions in each step of this invention are mild, the raw materials are readily available, and the experimental operation is controllable, which is conducive to achieving large-scale production. Attached Figure Description

[0035] Figure 1 The image shows the 1H NMR spectrum of compound 2 from Example 1.

[0036] Figure 2 The image shows the carbon NMR spectrum of compound 2 in Example 1.

[0037] Figure 3 This is the mass spectrum of compound 2 in Example 1.

[0038] Figure 4 The image shows the 1H NMR spectrum of compound 3 in Example 1.

[0039] Figure 5 The image shows the carbon NMR spectrum of compound 3 in Example 1.

[0040] Figure 6 This is the mass spectrum of compound 3 in Example 1.

[0041] Figure 7 The image shows the 1H NMR spectrum of compound TAO2 synthesized in Example 1.

[0042] Figure 8 The image shows the carbon NMR spectrum of compound TAO2 synthesized in Example 1.

[0043] Figure 9 This is the mass spectrum of compound TAO2 synthesized in Example 1.

[0044] Figure 10 The image shows the 1H NMR spectrum of compound TAO1 synthesized in Example 2.

[0045] Figure 11 The image shows the carbon NMR spectrum of compound TAO1 synthesized in Example 2.

[0046] Figure 12 This is the mass spectrum of compound TAO1 synthesized in Example 2.

[0047] Figure 13 The image shows the 1H NMR spectrum of the compound TAO3 synthesized in Example 3.

[0048] Figure 14 The image shows the carbon NMR spectrum of compound TAO3 synthesized in Example 3.

[0049] Figure 15 This is the mass spectrum of compound TAO3 synthesized in Example 3.

[0050] Figure 16 The images show the UV-Vis absorption and fluorescence emission spectra of compounds TAO1, TAO2, and TAO3 synthesized in Examples 1-3 in toluene solution; the insets are photographs of the solutions under sunlight irradiation (left) and 254 nm UV irradiation (right).

[0051] Figure 17 The compounds TAO1, TAO2, and TAO3 synthesized in Examples 1-3, and C 60 The nonlinear optical properties are plotted as follows: a) is the Z-scan curve of the aperture at a laser wavelength of 532 nm and an incident laser energy of 50 nJ; b) is the Z-scan curve of the aperture at a laser wavelength of 532 nm and an incident laser energy of 103 nJ; c) is the Z-scan curve of the aperture at a laser wavelength of 532 nm and an incident laser energy of 211 nJ; d) is the Z-scan curve of the aperture at a laser wavelength of 532 nm and an incident laser energy of 850 nJ; e) is the relationship between transmittance and input energy density; and f) is the relationship between output energy density and input energy density. Detailed Implementation

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0053] The structural formulas of nitrogen-doped ovobenzene, lactone-embedded bis(anthracene), and ovobenzene derivatives with four peripheral amide linkage groups in the prior art are as follows: ; Among them, (a) is an isolated nitrogen-doped ovalbenzene, (b) is a lactone-embedded bis(anthracene), and (c) is an ovalbenzene derivative with four peripheral amide linkage groups.

[0054] Current research on nitrogen-doped polycyclic aromatic hydrocarbons mainly focuses on isolated nitrogen atoms or hydrazine bond structures embedded in the framework. There are few reports on molecules doped with multiple nitrogen atoms (such as azo and hydrazine groups), especially the synthesis and application of azo and hydrazine groups located at the edge of polycyclic aromatic hydrocarbons.

[0055] This invention provides a tetraazaphosphonium derivative, wherein the structural formula of the tetraazaphosphonium derivative is selected from one of the following structural formulas: , , .

[0056] In one embodiment of the present invention, an I2 / DMSO system is used for... Direct oxidation is performed, and this method can efficiently and regioselectively convert it into... Subsequently, It undergoes a direct condensation with hydrazine hydrate in ethanol to give Subsequently, It undergoes a Diels-Alder cycloaddition reaction with an excess of dienophile (4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione) to transform into the target compound. .

[0057] In one embodiment of the present invention, Hydrolysis occurs under the action of excess NaOH to generate the target compound. .

[0058] In one embodiment of the present invention, The target compound can be directly generated by the Diels-Alder reaction with the dienophile (4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione). .

[0059] Unlike traditional modification strategies that involve doping with a single nitrogen atom, this invention precisely inserts nitrogen atom pairs (such as azo N=N or hydrazine NN) directly into the 3, 4, 10, 11-positions (i.e., K-positions) of the ovobenzide skeleton, and finely controls the hybridization state of these nitrogen atoms. By adjusting the electronic structure of the molecule, superior results compared to standard C can be obtained. 60 Its anti-saturation absorption properties.

[0060] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0061] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials and reagents used are commercially available.

[0062] Example 1 A tetrazonylbenzene derivative The synthesis method includes the following steps:

[0063] (1) Compound 1 (7,14-bis(2,4,6-trimethylphenyl)bisanthracene, 103 mg, 0.175 mmol) and I2 (170 mg, 0.671 mmol) were dissolved in a mixed solvent of DMSO (2.00 mL) and 1,4-dioxane (7.00 mL), and the mixture was heated to 100 °C for 2 hours. After the reaction was complete, the mixture was cooled to 25 °C, the reaction was quenched with saturated sodium thiosulfate solution, and the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with water, dried over anhydrous Na2SO4, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 5 / 1, v / v ), yielding a brownish-red solid compound 2 (7,14-bis(2,4,6-trimethylphenyl)bisanthracite-3,4-quinone, C 46 H 32 O2, 75.8 mg, yield 70%), NMR data are as follows: 1 H NMR (400 MHz, CDCl3, 298 K) δ 9.33 – 9.24 (m, 2H), 8.09 (t, J = 7.9 Hz, 2H), 7.93 (dd, J = 7.9, 0.9 Hz, 2H), 7.54 (d, J = 10.1 Hz, 2H), 7.16 (s, 4H), 6.95 (d, J = 10.0 Hz, 2H), 2.50 (s, 6H), 1.94 (s, 12H), the proton NMR spectrum is as follows: Figure 1 As shown; 13 C NMR (100 MHz, CDCl3, 298 K) δ186.9, 144.6, 138.5, 137.4, 137.2, 133.0, 131.3, 130.8, 130.6, 128.7, 128.6, 128.2, 126.5, 125.7, 124.7, 124.6, 124.6, 21.4, 20.3, the carbon NMR spectra are as follows: Figure 2 As shown. Mass spectrometry data are: HR MS (ASAP): Theoretical value C 46 H 33 O2[M+H] + , m / z = 617.2481, experimental value 617.2480, error = 0.1620 ppm, mass spectrum as shown Figure 3 As shown.

[0064] (2) Compound 2 (7,14-bis(2,4,6-trimethylphenyl)bisanthraquinone-3,4-quinone, 71.2 mg, 0.115 mmol) was dissolved in ethanol (10 mL), and then N2H4·H2O (1 mL) was added. The mixture was stirred at 25 °C for 1 hour. After the reaction was completed, the reaction was quenched with saturated ammonium chloride solution, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, washed with water, dried over anhydrous Na2SO4, and the solvent was removed by vacuum distillation. The crude product was purified by column chromatography (petroleum ether / ethyl acetate = 2 / 1, v / v ), yielding the red target compound 3 (7,14-bis(2,4,6-trimethylphenyl)-1,2-diazabenzo[ghi]bisanthracene, C 46 H 32 N2 (68.8 mg, yield 98%), NMR data are as follows: 1 H NMR (400 MHz, CDCl3, 298 K) δ 9.32 (dd, J =6.6, 2.1 Hz, 2H), 8.54 (d, J = 9.6 Hz, 2H), 8.19 – 8.11 (m, 4H), 7.99 (d, J = 9.6 Hz, 2H), 7.24 (s, 4H), 2.55 (s, 6H), 1.91 (s, 12H), the 1H NMR spectrum is as follows: Figure 4 As shown; 13 CNMR (100 MHz, CDCl3, 298 K) δ148.6, 138.3, 138.2, 137.8, 133.6, 132.0, 131.8, 131.0, 128.9, 128.3, 128.2, 128.0, 126.7, 125.0, 125.0, 122.5, 119.4, 116.5, 21.5, 20.4, the carbon NMR spectra are as follows: Figure 5 As shown. Mass spectrometry data are: HR MS (ASAP): Theoretical value C 46 H 33 N2[M+H] + , m / z = 613.2644, experimental value 613.2643, error = 0.1631 ppm, mass spectrum as shown Figure 6 As shown.

[0065] (3) Under argon protection, compound 3 (51.2 mg, 83.6 μmol) and 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione (146 mg, 0.836 mmol) were dissolved in ultra-dry toluene (15 mL) and heated to reflux at 110 °C for 2 hours. After the reaction was complete, the reaction solution was cooled to 25 °C, and then the solvent was removed by vacuum distillation. The crude product was purified by silica gel column chromatography (dichloromethane / ethyl acetate = 5 / 1, v / v Then, recrystallization with acetone yielded the target compound (10,11-(diazepine)-3,4-[4-phenyl-3,5-dioxo-1,2,4-triazolidine-1,2-diyl]-7,14-dimetromethylbenzanthracene, C) – a purplish-black solid. 54 H 35 N5O2 (47.9 mg, yield 73%), denoted as TAO2, NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.94(d, J = 9.2 Hz, 2H), 8.40 (d, J = 9.6 Hz, 2H), 7.91 (d, J = 9.2 Hz, 2H), 7.82 (d, J =9.6 Hz, 2H), 7.64 (d, J = 7.9 Hz, 2H), 7.57 (t, J = 7.8 Hz, 2H), 7.48 (t, J= 7.4Hz, 1H), 7.21 (s, 4H), 2.52 (s, 6H), 1.92 (s, 12H), the 1H NMR spectrum is as follows: Figure 7 As shown; 13 CNMR (100 MHz, CDCl3, 298 K) δ 148.9, 144.0, 138.6, 138.6, 137.5, 132.3, 132.0, 131.0, 130.6, 129.7, 129.2, 129.0, 128.9, 128.6, 128.5, 128.4, 126.4, 125.0, 123.7, 120.5, 117.0, 115.9, 115.4, 21.5, 20.3, NMR carbon spectra are shown below. Figure 8 As shown. Mass spectrometry data are: HR MS (ASAP): Theoretical value C 54 H 36 N5O2[M+H] + , m / z = 786.2869, experimental value 786.2861, error = 1.0174 ppm, mass spectrum as shown Figure 9 As shown.

[0066] Example 2 A tetrazonylbenzene derivative The synthesis method includes the following steps:

[0067] The compound TAO2 (29.8 mg, 37.9 μmol) synthesized in Example 1 was dissolved in THF (20 mL), and then a mixed solution of water (2 mL) and ethanol (2 mL) containing NaOH (455 mg, 11.4 mmol) was added. The mixture was heated to 70 °C and reacted for 1 hour. During the reaction, the solution color gradually changed from purplish-black to orange-yellow. After the reaction was completed, saturated ammonium chloride solution was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 1 / 2). v / v Then, recrystallization with methanol yielded the target compound (7,14-dimetatrimethyl-3,4:10,11-bis(diazepine-bridged)bisanthracene, C...) in an orange-yellow solid. 46 H 30 N4 (22.6 mg, yield 93%), denoted as TAO1, NMR data are as follows: 1 H NMR (400 MHz, CDCl3, 298 K) δ 9.72 (d, J =9.4 Hz, 4H), 9.16 (d, J = 9.5 Hz, 4H), 7.42 (s, 4H), 2.67 (s, 6H), 1.90 (s, 12H), the proton NMR spectrum is as follows: Figure 10 As shown; 13 C NMR (100 MHz, CDCl3, 298K) δ 145.9, 139.1, 138.7, 138.1, 133.0, 130.4, 130.0, 129.4, 129.2, 121.9, 117.8, 114.1, 77.5, 77.4, 77.2, 76.8, 21.6, 20.9, NMR carbon spectra are shown below. Figure 11 As shown. Mass spectrometry data are: HR MS (ASAP): Theoretical value C 46 H 31 N4[M+H] + , m / z = 639.2549, experimental value 639.2548, error = 0.1564ppm, mass spectrum as follows Figure 12 As shown.

[0068] Example 3 A tetrazonylbenzene derivative The synthesis method includes the following steps:

[0069] Compound 1 (20.8 mg, 35.5 μmol) and 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione (26.7 mg, 0.152 mmol) were dissolved in ultra-dry toluene (3.80 mL) under nitrogen protection and heated to reflux at 110 °C for 2 hours. After the reaction was complete, the mixture was cooled to 25 °C and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (petroleum ether / dichloromethane = 1 / 1). v / v Then, recrystallization with ethanol yielded the target compound (3,4:10,11-bis[4-phenyl-3,5-dioxo-1,2,4-triazolidine-1,2-diyl]-7,14-dimetromethylbis(anthracene), C10- ... 62 H 40 N6O4 (12.3 mg, yield 37%), denoted as TAO3, NMR data are as follows: 1 H NMR (400 MHz, CDCl3, 298 K) δ 8.24 (d,J = 9.5 Hz, 4H), 7.59 – 7.49 (m, 8H), 7.48 – 7.41 (m, 2H), 7.08 (s, 4H), 6.98 (d, J = 9.6 Hz, 4H), 2.42 (s, 6H), 1.90 (s, 12H), the proton NMR spectrum is as follows: Figure 13 As shown; 13 C NMR (100MHz, CDCl3, 298 K) δ 143.3, 138.0, 137.2, 136.4, 132.1, 130.5, 130.3, 129.4, 129.0, 129.0, 128.8, 127.7, 126.3, 126.0, 125.2, 116.1, 115.8, 21.2, 19.9, NMR carbon spectra are shown below. Figure 14 As shown. Mass spectrometry data are: HR MS (ASAP): Theoretical value C 62 H 41 N6O4[M+H] + , m / z =933.3189, experimental value 933.3202, error = 1.3929 ppm, mass spectrum as shown Figure 15 As shown.

[0070] Test Example 1 The UV-Vis absorption (Abs) and fluorescence emission (PL) spectra of compounds TAO1, TAO2, and TAO3 synthesized in Examples 1-3 were tested in toluene solution to investigate the effect of skeletal edge modification on the molecular photophysical properties. The testing method involved dissolving compounds TAO1, TAO2, and TAO3 in toluene to prepare a solution with a concentration of approximately 10... -5 A mol / L solution was prepared and placed in a quartz cuvette with a 1 cm optical path. The UV-Vis absorption and fluorescence emission spectra were measured at room temperature. The excitation wavelengths for the fluorescence emission spectra of TAO1 and TAO2 were 500 nm and 636 nm, respectively. The appearance and luminescence of each solution were also observed under sunlight and 254 nm UV light irradiation.

[0071] Test results are as follows Figure 16As shown, with the evolution of molecular structure and electronic effects, the three compounds exhibit distinctly different yet regularly changing optical characteristics. Compound TAO3 displays a very broad absorption band, with its absorption edge extending into the near-infrared region (NIR), and exhibits strong characteristic absorption peaks at 815 nm and 910 nm. This is due to the "donor-π-donor (D-π-D)" structure formed by its two electron-donating amide groups, resulting in an extremely narrow optical band gap. TAO3 has strong absorption bands in the ultraviolet and near-infrared regions, but almost no absorption in the visible light range.

[0072] When the electron-donating amide group on one side of the molecule is replaced with an electron-withdrawing azo group, forming the compound TAO2 with an asymmetric "donor-π-acceptor (D-π-A)" structure, the frontier orbital energy levels of the system are significantly modulated, and its absorption spectrum exhibits a marked blue shift. The main absorption band of TAO2 is concentrated in the visible light region of 500-750 nm, with the maximum absorption peak located at approximately 660 nm. Furthermore, the formation of this asymmetric push-pull electron structure allows the radiative transition pathway to be restored, and TAO2 exhibits distinct fluorescence emission characteristics, with its emission peak located near 685 nm and a relatively small Stokes shift. Figure 16 As shown in the illustration, its solution emits a bright red fluorescence under ultraviolet light.

[0073] When both sides of the molecule are converted into a strongly electron-withdrawing azo structure, resulting in the highly symmetric "acceptor-π-acceptor (A-π-A)" compound TAO1, the spectrum of the system undergoes a more significant blue shift. The main absorption band of TAO1 is concentrated in the 400-510 nm region (with the maximum absorption peak at approximately 500 nm). Correspondingly, its fluorescence emission peak also undergoes a significant blue shift to around 500 nm, exhibiting a bright yellow-green fluorescence under ultraviolet light irradiation.

[0074] In summary, the structural evolution from TAO3 to TAO1 (D-π-D to D-π-A to A-π-A) clearly demonstrates that the transformation of the hybridization effect of the doped atoms significantly modulates the band structure of the molecule, not only shifting the absorption wavelength from the near-infrared region to the visible region, but also effectively activating and precisely regulating the fluorescence emission color of the system (from no fluorescence in the visible region to red fluorescence and then to yellow-green fluorescence).

[0075] Test Example 2 Picosecond aperture Z-scan experiments and optical limiting performance tests were conducted on compounds TAO1, TAO2, and TAO3 synthesized in Examples 1-3 to evaluate their nonlinear optical response and compare them with typical nonlinear optical materials C 60A comparison was made. The test method was as follows: compounds TAO1, TAO2, and TAO3 were dissolved in toluene to prepare solutions with a transmittance of 75% at a wavelength of 532 nm. These solutions were then placed in a quartz cuvette with a 2 mm optical path and subjected to different incident laser energies (E). in Under these conditions, Z-scan tests were performed on the aperture. For optical limiting performance testing, compounds TAO1, TAO2, and TAO3 were dissolved in toluene to prepare solutions with a transmittance of 64% at 532 nm. The prepared solutions were then placed in a quartz cuvette with a 2 mm optical path length, and optical limiting performance was characterized using a 532 nm picosecond pulsed laser at different incident laser energies.

[0076] Test results are as follows Figure 17 As shown, from Figure 17 As can be seen in (a)-d), with E in As the laser energy increases from 50 nJ to 850 nJ, both TAO2 and TAO3 exhibit significant reverse saturation absorption (RSA) characteristics, as evidenced by their valley-shaped Z-scan curves. However, TAO1 exhibits significant saturation absorption (SA) at low incident laser energies of 50–211 nJ, and its optical behavior gradually shifts to RSA at high incident laser energies of 850 nJ.

[0077] Compared to TAO2, it is doped with four sps. 3 TAO3 with nitrogen atoms exhibits better performance than C. 60 The superior RSA performance is likely attributed to its more delocalized π system. Specifically, although in E in At 50 nJ, TAO2 (0.993) and C 60 The minimum normalized transmittance (T) of (0.989) min The values ​​are close to each other, but T3 is observed to have a lower T value. min The value is even smaller, at 0.93. In the Z-scan experiment, the smaller T... min The value typically reflects a material's better nonlinear optical (NLO) response. However, when E... in When the concentration is increased from 50 nJ to 850 nJ, TAO2 and C 60 T min The values ​​all decreased slightly, indicating that when E in Above 50 nJ, their excited-state absorption reaches saturation. In contrast, when E in When the value of TAO3 increases from 50 nJ to 850 nJ, the T min The value decreased significantly from 0.93 to 0.62, indicating that at higher E... in The RSA effect was significantly enhanced. Furthermore, the nonlinear extinction coefficient of TAO3 was much higher than that of TAO2 and C.60 .

[0078] Combination Figure 17 As shown in e) and f), the transmittance of TAO2 and TAO3 decreases significantly with increasing input energy density, while the increase in output energy density gradually slows down, exhibiting typical optical limiting response characteristics, consistent with the NLO response results measured in the Z-scan experiment. Further quantitative analysis of the optical limiting threshold (E) is needed. th E is defined as the input energy density corresponding to the decrease of the material's nonlinear transmittance to half of its initial linear transmittance. th Only 0.086 J·cm -2 TAO2, C 60 E th They are 0.209 J·cm -2 and 0.197 J·cm -2 TAO1's E th Up to 0.288 J·cm -2 The optical limiting ability is weak. The above results indicate that introducing consecutive dinitrogen atom pairs such as azo and hydrazine groups at the edge of the polycyclic aromatic hydrocarbon skeleton can effectively control the nonlinear optical and optical limiting properties of the molecule. This molecular modification strategy has good application prospects for the development of novel nonlinear optical functional materials.

[0079] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art should understand that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A tetraazaphosphonium derivative, characterized in that, The structural formula of the tetrazazobenzene derivative is selected from one of the following structural formulas: 、 、 。 2. A tetrazolomide derivative The synthesis method is characterized by, Includes the following steps: (1) An oxidation reaction was carried out in the presence of elemental iodine and organic solvent I to obtain... ; (2) It undergoes a condensation reaction with hydrazine hydrate in organic solvent II to obtain ; (3) Under an inert atmosphere, The tetraazapyridine derivative was subjected to a cycloaddition reaction with 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione in organic solvent III to give the tetraazapyridine derivative. .

3. The synthesis method according to claim 2, characterized in that, In step (1), the organic solvent I is dimethyl sulfoxide and / or 1,4-dimethyl sulfoxide. Dioxane; the oxidation reaction is carried out at a temperature of 80-120 ℃ for 1-3 h; the iodine and The molar ratio is (3-5):

1.

4. The synthesis method according to claim 2, characterized in that, In step (2), the organic solvent II is ethanol; the condensation reaction temperature is 15-35 °C and the time is 0.5-2 h; in step (3), the organic solvent III is toluene; the cycloaddition reaction temperature is 100-120 °C and the time is 1-3 h; the 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione and The molar ratio is (8-12):

1.

5. A tetrazolomide derivative The synthesis method is characterized by, Includes the following steps: Will Dissolved in organic solvent IV, the tetraazaphosphonate derivative is hydrolyzed in the presence of alkali, water, and alcohol to yield the tetraazaphosphonate derivative. .

6. The synthesis method according to claim 5, characterized in that, The organic solvent IV is tetrahydrofuran; the base is sodium hydroxide; the alcohol is ethanol; the base and... The molar ratio is (280-320):

1.

7. The synthesis method according to claim 5, characterized in that, The hydrolysis reaction is carried out at a temperature of 60-80 °C for a time of 0.5-1.5 h.

8. A tetrazolebenzene derivative The synthesis method is characterized by, Includes the following steps: In an inert atmosphere, The tetraazapyridine derivative was cycloadditionally reacted with 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione in organic solvent V to give the tetraazapyridine derivative. .

9. The synthesis method according to claim 8, characterized in that, The organic solvent V is toluene; the 4-phenyl-3H-1,2,4-triazol-3,5(4H)-dione and The molar ratio is (4-5):

1.

10. The synthesis method according to claim 8, characterized in that, The cycloaddition reaction is carried out at a temperature of 100-120℃ for 1-3 hours.

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