Semiconductor hole fluorescence probe and application thereof

Abstract

The invention relates to a semiconductor hole fluorescent probe and application thereof, and belongs to the technical field of fluorescent probes. The semiconductor hole fluorescent probe has a diarylmethane skeleton structure, and can be efficiently oxidized by holes by utilizing the high electron cloud density of carbon atoms in the center of the diarylmethane skeleton, so that intramolecular cyclization reaction is carried out, a fluorescent dye with a rigid plane structure is generated, and fluorescent lightening is realized; the carbon positive ion active site in the center of the oxidation product can be rapidly and irreversibly quenched by water molecules in the environment to realize signal reset, so that the semiconductor hole specificity response can be realized, and the single particle level lossless imaging of hole behaviors in P-type, N-type and PN junctions can be realized.

Description

Technical Field

[0001] This invention belongs to the field of fluorescent probe technology, and particularly relates to a class of semiconductor hole fluorescent probes and their applications. Background Technology

[0002] Semiconductor materials and devices are the cornerstone of modern information technology society, and their core performance lies in the generation, separation, transport, and recombination behavior of charges (electrons and holes). Among these, the behavior of holes (P-type charge carriers) profoundly affects the efficiency and performance of many key fields such as photocatalysis, photovoltaic cells, light-emitting diodes (LEDs), and semiconductor chips. For example, in photocatalysis, the oxidation capacity of holes is crucial for degrading pollutants or splitting water; in chip manufacturing, the mobility and recombination rate of holes directly determine the performance and reliability of P-type transistors. Therefore, achieving in-situ, real-time, and high spatial resolution dynamic tracing of hole behavior in semiconductors is a core frontier for revealing its working mechanism, optimizing material performance, and diagnosing device defects, possessing significant fundamental research significance and engineering application value. However, achieving this goal faces enormous technical challenges. Holes themselves do not possess signal emission properties, and their short lifetime and rapid migration make it difficult for traditional electrical measurement methods to achieve in-situ visualization of their spatiotemporal dynamics. While fluorescence imaging technology possesses advantages such as being non-destructive, highly sensitive, and having high spatiotemporal resolution, developing hole-responsive fluorescent probes suitable for semiconductor systems faces the following three major bottlenecks: (1) Lack of response mechanism: Most existing fluorescent probes are designed for reactive oxygen species / nitrogen species in biological systems, and their response mechanisms (such as π conjugation bond breaking and bond rotation) cannot be applied to the efficient and specific response of semiconductor holes; (2) Severe background interference: Most wide bandgap semiconductor materials (such as TiO2, ZnO, GaN, etc.) will produce strong bulk autofluorescence under ultraviolet-visible light excitation. Their emission spectrum overlaps severely with that of traditional fluorescent probes (emission wavelength <650 nm), resulting in extremely low signal-to-noise ratio and inability to perform effective detection. (3) Excitation light interference problem: In complex semiconductor dispersion systems or on the surface of devices, the excitation light will be scattered in large quantities. The Stokes shift of traditional fluorescent probes is small (<30 nm), which leads to serious overlap between the excitation spectrum and the emission spectrum. The weak fluorescence signal is completely submerged by the strong scattered light and is difficult to separate.

[0003] Therefore, how to provide a fluorescent probe that can specifically respond to semiconductor holes for use in semiconductor hole imaging is a technical problem that urgently needs to be solved. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a type of semiconductor hole fluorescent probe and its application, which can specifically respond to semiconductor holes.

[0005] This invention provides a class of semiconductor hole fluorescent probes having the following general structural formula: or or or or or ; Where R= or or or A= or or or or or or or n is an integer from 0 to 18; Where R1,R2= or or or or or or or or or or or m is an integer between 0 and 18; It is an anion, and the anion is BF4. – or Cl – or Br – Or I – Or NO3 – or SO4 2– or ClO4 – or CH3COO – or CH3SO3 – or CF3SO3 – ; The total number of positive charges carried is equal to the number of anions. The total amount of charge carried.

[0006] Another aspect of the present invention provides the application of the above-mentioned semiconductor hole fluorescent probe in semiconductor hole imaging.

[0007] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows: 1. The semiconductor hole fluorescent probe provided by the present invention has a diarylmethane backbone structure. Utilizing the high electron cloud density of the central carbon atom of the diarylmethane backbone, it can be efficiently oxidized by holes, thereby undergoing an intramolecular cyclization reaction to generate a fluorescent dye with a rigid planar structure, achieving fluorescence "lighting". At the same time, the carbocation active site at the center of the oxidation product can be rapidly and irreversibly quenched by water molecules in the environment, achieving "signal reset", thus providing a specific response to semiconductor holes. 2. The semiconductor hole fluorescence probe provided by the present invention, by expanding the conjugated system and enhancing the push-pull electron effect, redshifts its emission wavelength to 650~850 nm, completely avoiding semiconductor bulk fluorescence and solving the background interference problem caused by semiconductor bulk fluorescence. 3. The semiconductor hole fluorescent probe provided by this invention introduces the intramolecular torsional charge transfer (TICT) effect, which makes its Stokes shift greater than 50nm, thereby achieving effective separation of excitation and emission spectra and fundamentally eliminating excitation light scattering interference. 4. The semiconductor hole fluorescent probe provided by this invention can be applied to semiconductor hole imaging, enabling single-particle level non-destructive imaging of hole behavior in P-type, N-type and PN junctions. It is also expected to be applied to defect diagnosis and process optimization of high-end semiconductor chips, providing detection tools and method support for solving the country's major needs in the field of microelectronics. Attached Figure Description

[0008] Figure 1 The hydrogen NMR spectrum of Hole-1; Figure 2 The hydrogen NMR spectrum of Hole-2; Figure 3 The hydrogen NMR spectrum of Dark-Hole-1; Figure 4 The spectra of Em-Hole-1 dye obtained by oxidation of Hole-1 and Hole-2 in water, dichloromethane and methanol are shown, where (a) is the UV-Vis absorption spectrum and (b) is the fluorescence emission spectrum. Figure 5 The UV-Vis absorption and fluorescence emission spectra of Hole-25 in acetonitrile after oxidation are shown. Figure 6 The results of cyclic voltammetry tests are for Hole-1, Hole-2, and Hole-6. Figure 7The activation capacity tests of Hole-2 and Hole-6 at different oxidation potentials are shown below. (a) is a photograph of the color changes of the cathode and anode of Hole-2 during electrolysis; (b) is the UV-Vis absorption spectrum of the electrolyte of Hole-2 at different oxidation potentials; (c) is the UV-Vis absorption spectrum of Hole-2 at 0.68 V over 2400 s; (d) is a photograph of the color changes of the cathode and anode of Hole-6 during electrolysis; (e) is the UV-Vis absorption spectrum of the electrolyte of Hole-6 at different oxidation potentials; and (f) is the UV-Vis absorption spectrum of Hole-6 at 0.68 V over 2400 s. Figure 8 The results show the stability test of the dye after Hole-6 oxidation at different oxidation potentials. Among them, (a) is the UV-Vis absorption spectrum at 0.68 V for 1600 seconds, (b) is the UV-Vis absorption spectrum at 1.05 V for 1600 seconds, and (c) is the UV-Vis absorption spectrum at 1.25 V for 1600 seconds. Figure 9 The results show the photoactivation ability of Hole-6 in the presence of a conductor catalyst; (a) shows the color change of the mother liquor after irradiation with a 360 nm LED for 100 min for the + TiO2 group and the - TiO2 group; (b) shows the UV-Vis absorption spectra of the + TiO2 group after irradiation for different times. Figure 10 Hole-2 was tested on nano-zinc oxide particles using alternating 405 nm and 561 nm cavitation sites. Figure 11 Images of Hole-2 on single-molecule imaging tests on zinc oxide nanoparticles, where the left image is the bright field and the right image is the fluorescence field, and a in the figure represents the defects on the zinc oxide particles; Figure 12 This is a three-dimensional fluorescence intensity distribution map of the surface of zinc oxide nanoparticles during single-molecule imaging testing of Hole-2 on zinc oxide nanoparticles. Figure 13 The image shows the single-molecule localization super-resolution imaging of zinc oxide nanoparticles in the Hole-2 single-molecule imaging test on zinc oxide nanoparticles. In the image, a is the defect on the zinc oxide particle, b is the magnification of ROI i region in the SR image, and c is the magnification of ROI ii region in the SR image. Figure 14 This is a single-molecule fluorescence trajectory diagram of Hole-2 on nano zinc oxide particles. Detailed Implementation

[0009] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0010] Example 1 Hole-1, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0011] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-1 is as follows: under anhydrous and oxygen-free conditions, compound 1 (2.00 g, 5.14 mmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (394.82 mg, 6.16 mmol) was added at -78 ℃ and reacted for 30 min; DMF was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-1 (1.50 g, 4.43 mmol, yield 86.27%).

[0012] The structure of the aforementioned semiconductor hole fluorescent probe Hole-1 is obtained through... 1 H NMR, 13 Identification by C NMR and HRMS. Among them, 1 HNMR (400MHz, Chloroform- d )like Figure 1 As shown, its spectral peaks are as follows: δ 10.28 (s, 1H), 7.15 (d, J=2.8Hz, 1H), 7.10 (d, J=8.5Hz, 1H), 6.97 (d, J=8.0Hz, 2H), 6.84 (dd, J=8.5, 3.0Hz, 1H), 6.59 (d, J=8.1Hz, 2H), 4.19 (s, 2H), 3.37 (q, J=7.1Hz, 4H), 3.30 (q, J=6.9Hz, 4H), 1.18-1.10 (m, 12H). 13 C NMR (101MHz, CDCl3): δ 192.85, 146.56, 146.21, 134.39, 132.53, 131.15, 129.33, 122.44, 117.65, 112.25, 44.33, 35.67, 12.52. HRMS[M+H] + : 339.2458.

[0013] Example 2 Hole-2, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0014] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-2 is as follows: Hole-1 (2.00 g, 5.91 mmol) was dissolved in tetrahydrofuran, sodium borohydride (268.24 mg, 7.09 mmol) was added, and the mixture was stirred at room temperature until the reaction was complete; after quenching the reaction with water, the mixture was extracted with dichloromethane, the organic phase was dried, and the solvent was removed by vacuum distillation. The residue was Hole-2 (1.6 g, 4.70 mmol, yield 79.53%).

[0015] The structure of the aforementioned semiconductor hole fluorescent probe Hole-2 is achieved through... 1 H NMR, 13 Identification by C NMR and HRMS. Among them, 1 HNMR (400MHz, Chloroform- d )like Figure 2 As shown, its spectral peaks are as follows: δ 7.04 (d, J=8.4Hz, 1H), 6.99 (d, J=8.3Hz, 2H), 6.76 (s, 1H), 6.61 (d, J=6.9Hz, 3H), 4.60 (s, 2H), 3.87 (s, 2H), 3.38-3.28 (m, 8H), 1.14 (dt, J=13.4, 7.0Hz, 12H). 13 C NMR (101MHz, CDCl3): δ 146.79, 146.23, 139.58, 131.51, 129.29, 128.51, 126.31, 112.48, 112.40, 111.46, 64.02, 44.43, 36.72, 12.64. HRMS[M+H] + : 341.2593.

[0016] Example 3 Hole-3, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0017] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-3 is as follows: under anhydrous and oxygen-free conditions, compound Hole-1 (500.00 mg, 1.48 mmol) was dissolved in dry tetrahydrofuran, and methyllithium (38.95 mg, 1.77 mmol) was added at -78 ℃ and reacted for 30 min. The system was then moved to room temperature and reacted for 2 h. After quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-3 (300 mg, 0.85 mmol, yield 57.28%).

[0018] The structure of the aforementioned semiconductor hole fluorescent probe Hole-3 is obtained through... 1 H NMR, 13 Identification by C NMR and HRMS. Among them, 1 HNMR (400MHz, Chloroform- d ): δ 6.97 (t, J=8.8Hz, 3H), 6.91 (d, J=2.8Hz, 1H), 6.60 (d, J=8.2Hz, 2H), 6.56 (dd, J=8.2, 2.8Hz, 1H), 5.11 (q, J=6.5Hz, 1H), 3.89-3.78 (m, 2H), 3.42–3.32 (m, 4H), 3.29 (q, J=7.0Hz, 4H), 1.60 (s, 1H), 1.36 (d, J=6.4Hz, 3H), 1.16 (t, J=7.1Hz, 6H), 1.12 (t, J=7.0Hz, 6H). 13 C NMR (101MHz, CDCl3): δ 146.90, 146.17, 144.71, 131.50, 129.26, 128.67, 124.78, 112.41, 111.18, 108.68, 66.63, 44.45, 44.39, 36.62, 24.07, 12.68, 12.55. HRMS[M+H] + : 355.2749.

[0019] Example 4 The synthetic route of Hole-4, a semiconductor hole fluorescent probe, is shown in the following formula:

[0020] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-4 is as follows: under anhydrous and oxygen-free conditions, compound 1 (1.50 g, 3.85 mmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (296.11 mg, 4.62 mmol) was added at -78 °C and reacted for 30 min; dimethyl carbonate (694.01 mg, 7.70 mmol) was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-4 (0.95 g, 2.58 mmol, yield 66.92%).

[0021] The structure of the aforementioned semiconductor hole fluorescent probe Hole-4 is obtained through... 1 H NMR, 13 Identification by C NMR and HRMS. Among them, 1 HNMR (400MHz, Chloroform- d ): δ 7.15 (d, J=2.7Hz, 1H), 7.03 (d, J=8.6Hz, 1H), 6.99 (d, J=8.2Hz, 2H), 6.73 (dd, J=8.6, 2.7Hz, 1H), 6.6 0 (d, J=8.1Hz, 2H), 4.10 (s, 2H), 3.82 (s, 3H), 3.32 (dd, J=16.1, 7.2Hz, 8H), 1.13 (td, J=7.1Hz, 12H). 13 C NMR (101MHz, CDCl3): δ 169.20, 146.05, 145.92, 132.20, 130.61, 129.60, 129.05, 115.63, 113.62, 112.28, 51.78, 44.34, 37.65, 12.55. HRMS[M+H] + : 369.2541.

[0022] Example 5 Hole-5, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0023] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-5 is as follows: Hole-4 (0.50 g, 1.36 mmol) was dissolved in ethanol, lithium hydroxide (32.49 mg, 1.36 mmol) was added, and the mixture was stirred at room temperature until the reaction was complete; after quenching the reaction with water, the mixture was extracted with dichloromethane, the organic phase was dried, and the solvent was removed by vacuum distillation. The residue was Hole-5 (0.25 g, 0.71 mmol, yield 51.98%).

[0024] The structure of the aforementioned semiconductor hole fluorescent probe Hole-5 was identified using HRMS, HRMS[M+H] + :355.2386.

[0025] Example 6 Hole-6, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0026] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-6 is as follows: under anhydrous and oxygen-free conditions, compound Hole-4 (3.00 g, 8.14 mmol) was dissolved in dry tetrahydrofuran, and methyllithium (429.34 mg, 19.54 mmol) was added at -78 ℃ and reacted for 30 min. The system was then moved to room temperature and reacted for 2 h. After quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-6 (2.40 mg, 6.51 mmol, yield 79.99%).

[0027] The structure of the aforementioned semiconductor hole fluorescent probe Hole-6 is achieved through... 1 H NMR, 13 Identification by C NMR and HRMS. Among them, 1 HNMR (400MHz, Chloroform- d ): δ 6.98 (t, J=7.6Hz, 3H), 6.83 (s, 1H), 6.61 (d, J=7.1Hz, 2H), 6.56 (d, J=6.8Hz, 1H), 4.17 (s, 2 H), 3.33 (dq, J=14.2, 7.0Hz, 8H), 1.80 (s, 1H), 1.64 (s, 6H), 1.15 (dt, J=14.2, 7.0Hz, 12H). 13 C NMR (101MHz, CDCl3): δ 146.74, 146.01, 134.09, 130.09, 129.48, 125.54, 112.34, 110.95, 109.67, 74.19, 44.45, 37.95, 31.77, 12.61. HRMS[M+H] + : 369.2608.

[0028] Example 7 Hole-7, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0029] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-7 is as follows: under anhydrous and oxygen-free conditions, compound 2 (0.10 g, 259.51 μmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (19.95 mg, 311.41 μmol) was added at -78 °C and reacted for 30 min; 1 mL of anhydrous DMF was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-7 (56.00 mg, 167.43 μmol, yield 64.52%).

[0030] The structure of the aforementioned semiconductor hole fluorescent probe Hole-7 was identified using HRMS, HRMS[M+H] + : 335.2126.

[0031] Example 8 Hole-8, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0032] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-8 is as follows: under anhydrous and oxygen-free conditions, compound 3 (0.05 g, 119.80 μmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (9.21 mg, 143.77 μmol) was added at -78 °C and reacted for 30 min; 1 mL of anhydrous DMF was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-8 (20.00 mg, 119.80 μmol, yield 45.55%).

[0033] The structure of the aforementioned semiconductor hole fluorescent probe Hole-8 was identified using HRMS, HRMS[M+H] + :367.2012.

[0034] Example 9 Hole-9, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0035] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-9 is as follows: under anhydrous and oxygen-free conditions, compound 4 (0.20 g, 45.10 μmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (14.45 mg, 225.51 μmol) was added at -78 °C and reacted for 30 min; 1 mL of anhydrous DMF was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-9 (10.00 mg, 25.47 μmol, yield 56.48%).

[0036] The structure of the aforementioned semiconductor hole fluorescent probe Hole-9 was identified using HRMS, HRMS[M+H] + : 393.2644.

[0037] Example 10 Hole-10, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0038] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-10 is as follows: 2,6-bis(trifluoromethyl)bromobenzene (100.00 mg, 341.29 μmol) was added to dry tetrahydrofuran under argon protection, and n-butyllithium (26.23 mg, 409.55 μmol) was added at -78 °C and reacted for 30 min; a tetrahydrofuran solution containing compound Hole-9 (133.97 mg, 341.29 μmol) was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-10 (160 mg, 263.74 μmol, yield 77.82%).

[0039] The structure of the aforementioned semiconductor hole fluorescent probe Hole-10 was identified using HRMS, HRMS[M+H] + : 607.2878.

[0040] Example 11 The synthetic route of Hole-11, a semiconductor hole fluorescent probe, is shown in the following formula:

[0041] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-11 is as follows: Hole-9 (10.00 mg, 25.47 μmol) was dissolved in dry dichloromethane, iodomethane (36.16 mg, 254.75 μmol) was added, the reaction was carried out at room temperature for 24 h, and the solvent was removed by vacuum evaporation to obtain Hole-11 (9.00 mg, 13.27 μmol, yield 52.07%).

[0042] The structure of the aforementioned semiconductor hole fluorescent probe Hole-11 was identified using HRMS, HRMS[M+H] + :211.1516.

[0043] Example 12 The synthetic route of Hole-12, a semiconductor hole fluorescent probe, is shown in the following formula:

[0044]

[0045] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-12 is as follows: Compound 6 (500.00 mg, 2.18 mmol) and Compound 7 (596.89 mg, 2.62 mmol) were added to 20 mL of anhydrous acetonitrile, and a catalytic equivalent of boron trifluoride diethyl ether complex was added. The reaction was carried out at 80 °C for 4 h. After quenching the reaction with saturated sodium bicarbonate solution, the mixture was extracted with dichloromethane, the organic phases were combined, dried with anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the residue was subjected to column chromatography to obtain Compound 8 (562.00 mg, 1.28 mmol, yield 58.66%). Under anhydrous and oxygen-free conditions, Compound 8 (200.00 mg, 455.12 μmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (34.98 mg, 546.15 μmol) was added at -78 °C and reacted for 30 min. 1 mL of anhydrous DMF was added, and the system was moved to room temperature and reacted for 2 h. After quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-12 (102.00 mg, 262.51 μmol, yield 57.68%).

[0046] The structure of compound 8 was identified by HRMS, HRMS[M] + : 439.1746.

[0047] The structure of the aforementioned semiconductor hole fluorescent probe Hole-12 was identified using HRMS, HRMS[M+H] + : 389.2593.

[0048] Example 13 The synthetic route of Hole-13, a semiconductor hole fluorescent probe, is shown in the following formula:

[0049] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-13 is as follows: 2,6-bis(trifluoromethyl)bromobenzene (100.00 mg, 341.29 μmol) was added to dry tetrahydrofuran under argon protection, and n-butyllithium (26.23 mg, 409.55 μmol) was added at -78 °C and reacted for 30 min; a tetrahydrofuran solution containing compound Hole-12 (132.61 mg, 341.29 μmol) was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-13 (150 mg, 248.89 μmol, yield 72.93%).

[0050] The structure of the aforementioned semiconductor hole fluorescent probe Hole-13 was identified using HRMS, HRMS[M+H] + : 603.2810.

[0051] Example 14 The synthetic route of Hole-14, a semiconductor hole fluorescent probe, is shown in the following formula:

[0052] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-14 is as follows: under anhydrous and oxygen-free conditions, compound 8 (1.00 g, 2.28 mmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (174.92 mg, 2.73 mmol) was added at -78 ℃ and reacted for 30 min; 1 mL of dimethyl carbonate was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-14 (0.65 g, 1.55 mmol, yield 68.24%).

[0053] The structure of the aforementioned semiconductor hole fluorescent probe Hole-14 was identified using HRMS, HRMS[M+H] + : 419.2669.

[0054] Example 15 The synthetic route of Hole-15, a semiconductor hole fluorescent probe, is shown in the following formula:

[0055] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-15 is as follows: under nitrogen protection, compound Hole-14 (50.00 mg, 119.45 μmol) was dissolved in dry tetrahydrofuran, and methyllithium (26.25 mg, 1.19 mmol) was added at -78 °C. The reaction was then moved to room temperature and allowed to proceed until complete. The reaction was quenched with methanol, and the solvent was evaporated under reduced pressure. The residue was compound Hole-15 (20.00 mg, 47.78 μmol, yield 40%).

[0056] The structure of the aforementioned semiconductor hole fluorescent probe Hole-15 was identified using HRMS, HRMS[M+H] + : 419.3066.

[0057] Example 16 The synthetic route of Hole-16, a semiconductor hole fluorescent probe, is shown in the following formula:

[0058] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-16 is as follows: under anhydrous and oxygen-free conditions, compound 9 (1.00 g, 1.67 mmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (128.18 mg, 2.00 mmol) was added at -78 ℃ and reacted for 30 min; 1 mL of dimethyl carbonate was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-16 (450 mg, 777.42 μmol, yield 46.62%).

[0059] The structure of the aforementioned semiconductor hole fluorescent probe Hole-16 was identified using HRMS, HRMS[M+H] + : 579.3951.

[0060] Example 17 The synthetic route of Hole-17, a semiconductor hole fluorescent probe, is shown in the following formula:

[0061] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-17 is as follows: under nitrogen protection, compound Hole-16 (50.00 mg, 86.38 μmol) was dissolved in dry tetrahydrofuran, and methyllithium (37.96 mg, 1.73 mmol) was added at -78 °C. The reaction was then moved to room temperature and allowed to proceed until complete. The reaction was quenched with methanol, and the solvent was evaporated under reduced pressure. The residue was compound Hole-17 (25.00 mg, 43.19 μmol, yield 50%).

[0062] The structure of the aforementioned semiconductor hole fluorescent probe Hole-17 was identified using HRMS, HRMS[M+H] + : 579.4319.

[0063] Example 18 Hole-18, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0064]

[0065] The specific preparation method of the aforementioned semiconductor hole fluorescent probe Hole-18 is as follows: Compound 10 (1.00 g, 5.58 mmol) and Compound 11 (1.86 g, 6.69 mmol) were added to 20 mL of anhydrous acetonitrile, and a catalytic equivalent of boron trifluoride diethyl ether complex was added. The reaction was carried out at 80 °C for 4 h. After quenching the reaction with saturated sodium bicarbonate solution, the mixture was extracted with dichloromethane, the organic phases were combined, dried with anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the residue was subjected to column chromatography to obtain Compound 12 (2.45 g, 2.96 mmol, yield 53.03%). Under anhydrous and oxygen-free conditions, Compound 12 (0.12 g, 273.07 μmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (20.99 mg, 327.69 μmol) was added at -78 °C and reacted for 30 h. min; add 1 mL of anhydrous DMF and move the system to room temperature for 2 h; quench the reaction with methanol, remove the solvent under reduced pressure, and purify the residue by column chromatography to obtain compound Hole-18 (60.00 mg, 154.42 μmol, yield 56.55%).

[0066] The structure of compound 12 was identified by HRMS, HRMS[M] + : 439.1766.

[0067] The structure of the aforementioned semiconductor hole fluorescent probe Hole-18 was identified using HRMS, HRMS[M+H] + : 389.2593.

[0068] Example 19 The synthetic route of Hole-19, a semiconductor hole fluorescent probe, is shown in the following formula:

[0069] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-19 is as follows: 2,6-bis(trifluoromethyl)bromobenzene (90.00 mg, 307.16 μmol) was added to dry tetrahydrofuran under argon protection, and n-butyllithium (23.61 mg, 368.59 μmol) was added at -78 °C and reacted for 30 min; a tetrahydrofuran solution containing compound Hole-18 (120 mg, 307.16 μmol) was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-19 (86 mg, 173.83 μmol, yield 63.66%).

[0070] The structure of the aforementioned semiconductor hole fluorescent probe Hole-19 was identified using HRMS, HRMS[M+H] + : 603.2877.

[0071] Example 20 The synthetic route of Hole-20, a semiconductor hole fluorescent probe, is shown in the following formula:

[0072] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-20 is as follows: under anhydrous and oxygen-free conditions, compound 12 (1.00 g, 2.28 mmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (174.92 mg, 2.73 mmol) was added at -78 ℃ and reacted for 30 min; 1 mL of dimethyl carbonate was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-20 (585.00 mg, 1.40 mmol, yield 61.42%).

[0073] The structure of the aforementioned semiconductor hole fluorescent probe Hole-20 was identified using HRMS, HRMS[M+H] + : 419.2687.

[0074] Example 21 Hole-21, a semiconductor hole fluorescent probe, is synthesized via the following route:

[0075] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-21 is as follows: under nitrogen protection, compound Hole-20 (60.00 mg, 143.34 μmol) was dissolved in dry tetrahydrofuran, and methyllithium (31.50 mg, 1.43 mmol) was added at -78 °C. The reaction was then moved to room temperature and allowed to proceed until complete. The reaction was quenched with methanol, and the solvent was evaporated under reduced pressure. The residue was compound Hole-21 (28.00 mg, 66.89 μmol, yield 46.66%).

[0076] The structure of the aforementioned semiconductor hole fluorescent probe Hole-21 was identified using HRMS, HRMS[M+H] + : 419.3068.

[0077] Example 22 The synthetic route of Hole-22, a semiconductor hole fluorescent probe, is shown in the following formula:

[0078] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-22 is as follows: under anhydrous and oxygen-free conditions, compound 13 (0.13 g, 200.07 μmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (15.38 mg, 240.09 μmol) was added at -78 °C and reacted for 30 min; 1 mL of anhydrous DMF was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-22 (60.00 mg, 100.19 μmol, yield 50.08%).

[0079] The structure of the aforementioned semiconductor hole fluorescent probe Hole-22 was identified using HRMS, HRMS[M+H] + : 599.4001.

[0080] Example 23 The synthetic route of Hole-23, a semiconductor hole fluorescent probe, is shown in the following formula:

[0081] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-23 is as follows: Hole-22 (20.00 mg, 41.74 μmol) was dissolved in methanol, sodium borohydride (31.59 mg, 834.90 μmol) was added, and the mixture was stirred at room temperature until the reaction was complete; after quenching the reaction with water, the mixture was extracted with dichloromethane, the organic phase was dried, and the solvent was removed by vacuum distillation. The residue was Hole-23 (20.00 mg, 33.28 μmol, yield 79.53%).

[0082] The structure of the aforementioned semiconductor hole fluorescent probe Hole-23 was identified using HRMS, HRMS[M+H] + : 601.4155.

[0083] Example 24 The synthetic route of Hole-24, a semiconductor hole fluorescent probe, is shown in the following formula:

[0084] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-24 is as follows: under anhydrous and oxygen-free conditions, compound 13 (500.00 mg, 769.51 μmol) was dissolved in dry tetrahydrofuran, and n-butyllithium (59.15 mg, 923.42 μmol) was added at -78 °C and reacted for 30 min; 1 mL of dimethyl carbonate was added, and the system was moved to room temperature and reacted for 2 h; after quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-24 (320.00 mg, 508.82 μmol, yield 66.12%).

[0085] The structure of the aforementioned semiconductor hole fluorescent probe Hole-24 was identified using HRMS, HRMS[M+H] + : 629.4107.

[0086] Example 25 The synthetic route of Hole-25, a semiconductor hole fluorescent probe, is shown in the following formula:

[0087] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-25 is as follows: under nitrogen protection, compound Hole-24 (20.00 mg, 31.80 μmol) was dissolved in dry tetrahydrofuran, and methyllithium (13.98 mg, 636.03 μmol) was added at -78 °C. The reaction was then moved to room temperature and allowed to proceed until complete. The reaction was quenched with methanol, and the solvent was evaporated under reduced pressure. The residue was compound Hole-25 (20.00 mg, 19.08 μmol, yield 60%).

[0088] The structure of the aforementioned semiconductor hole fluorescent probe Hole-25 was identified using HRMS, HRMS[M+H] + : 629.4470.

[0089] Example 26 The synthetic route of Hole-26, a semiconductor hole fluorescent probe, is shown in the following formula:

[0090] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-26 is as follows: under nitrogen protection, compound 1 (100.00 mg, 256.82 μmol) and compound 14 (2-hydroxyphenylboronic acid ester, 67.82 mg, 308.18 μmol) were added to tetrahydrofuran, and a catalytic equivalent of tetra-triphenylphosphine palladium was added. The reaction was carried out at 70 °C for 24 h. The solvent was removed by vacuum distillation, and the residue was subjected to column chromatography to obtain compound Hole-26 (50.00 mg, 124.20 μmol, yield 48.36%).

[0091] The structure of the aforementioned semiconductor hole fluorescent probe Hole-26 was identified using HRMS, HRMS[M+H] + : 403.2750.

[0092] Example 27 The synthetic route of Hole-27, a semiconductor hole fluorescent probe, is shown in the following formula:

[0093] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-27 is as follows: under nitrogen protection, compound 1 (200.00 mg, 455.12 μmol) and compound 14 (2-hydroxyphenylboronic acid ester, 120.19 mg, 546.15 μmol) were added to tetrahydrofuran, and a catalytic equivalent of tetra-triphenylphosphine palladium was added. The reaction was carried out at 70 °C for 24 h. The solvent was removed by vacuum distillation, and the residue was subjected to column chromatography to obtain compound Hole-27 (120.00 mg, 265.11 μmol, yield 58.25%).

[0094] The structure of the aforementioned semiconductor hole fluorescent probe Hole-27 was identified using HRMS, HRMS[M+H] + : 453.2942.

[0095] Example 28 The synthetic route of Hole-28, a semiconductor hole fluorescent probe, is shown in the following formula:

[0096] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-28 is as follows: under anhydrous and oxygen-free conditions, compound Hole-1 (200.00 mg, 590.85 μmol) was dissolved in dry tetrahydrofuran, and 2-methylphenyllithium (69.54 mg, 709.02 μmol) was added at -78 °C and reacted for 30 min. The system was then moved to room temperature and reacted for 2 h. After quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-28 (155.00 mg, 359.93 μmol, yield 60.92%).

[0097] The structure of the aforementioned semiconductor hole fluorescent probe Hole-28 is obtained through... 1 H NMR, 13 Identification by C1NMR and HRMS. Among them, 1H NMR (400MHz, Chloroform- d ): δ 7.46 (d, J =8.3Hz, 1H), 7.22–7.15 (m, 2H), 7.11 (d, J =6.8Hz, 1H), 7.05 (d, J =8.4Hz, 1H), 7.01 (d, J =8.5Hz, 2H), 6.62 (d, J =8.4Hz, 2H), 6.58 (dd, J =8.7, 2.5Hz, 1H), 6.50 (d, J =2.4Hz, 1H), 6.12 (d, J =3.5Hz, 1H), 3.86 (s, 2H), 3.31 (q, J =6.9Hz, 4H), 3.21 (dq, J =21.8, 7.4Hz, 4H), 2.09 (s, 3H), 1.82 (d, J =4.0Hz, 1H), 1.13 (t, J =7.0Hz, 6H), 1.03 (t,J =7.0Hz, 6H). 13 C NMR (101MHz, CDCl3): δ 146.57, 146.28, 141.52, 141.23, 135.70, 131.63, 130.18, 129.43, 128.55, 127.15, 126.58, 126.26, 125.70, 112.55, 111.63, 111.20, 70.06, 44.48, 44.43, 36.97, 19.09, 12.56, 12.50. HRMS[M+H] + : 431.3066.

[0098] Example 29 The synthetic route of Hole-29, a semiconductor hole fluorescent probe, is shown in the following formula:

[0099] The specific preparation method of the above-mentioned semiconductor hole fluorescent probe Hole-29 is as follows: under anhydrous and oxygen-free conditions, compound Hole-1 (500.00 mg, 1.48 mmol) was dissolved in dry tetrahydrofuran, and 2,6-dimethylphenyllithium (165.59 mg, 1.48 mmol) was added at -78 °C and reacted for 30 min. The system was then moved to room temperature and reacted for 2 h. After quenching the reaction with methanol, the solvent was removed by vacuum distillation, and the residue was purified by column chromatography to obtain compound Hole-29 (560.00 mg, 1.26 mmol, yield 85.26%).

[0100] The structure of the aforementioned semiconductor hole fluorescent probe Hole-29 is obtained through... 1 H NMR, 13 Identification by C NMR and HRMS. Among them, 1 H NMR (400MHz, Chloroform- d ): δ 7.06–6.95 (m, 6H), 6.61 (d, J =8.1Hz, 2H), 6.54 (d, J =8.1Hz, 1H), 6.46 (s, 1H), 6.26 (d, J =4.3Hz, 1H), 4.03–3.83 (m, 2H), 3.30 (q, J =7.0Hz, 4H), 3.21–3.11 (m, 4H), 2.19 (s, 6H), 1.86 (d, J =4.5Hz, 1H), 1.12 (t, J =7.0Hz, 6H), 1.00 (t,J =7.0Hz, 6H). 13 C NMR (101MHz, CDCl3): δ 146.23, 140.04, 138.51, 136.97, 132.00, 129.51, 129.19, 128.66, 127. 31, 127.08, 112.65, 112.29, 111.16, 71.55, 44.48, 37.05, 21.30, 12.52. HRMS[M+H] + : 445.3220.

[0101] Example 30: Hole Response Mechanism Verification Experiment This embodiment verifies the response mechanism (OFF-ON-OFF mechanism) of the semiconductor hole fluorescent probe provided by the present invention to holes as follows:

[0102] The experiment used Hole-1 prepared in Example 1 and Hole-2 prepared in Example 2 as examples. The changes in their molecular structure were characterized by 1H NMR, 1C NMR, and mass spectrometry. Specifically, Hole-1 (20 mmol) and Hole-2 (20 mmol) were dissolved in ultra-dry acetonitrile solution, and 20 mg of titanium dioxide solid was added. After irradiation with 360 nm light for 60 min, the colorless Hole-1 and Hole-2 solutions gradually turned deep red. Mass spectrometry characterization identified them as Em-Hole-1 (HRMS[M]). + (337.2264); Deionized water was added dropwise to the solution, and the solution gradually changed from red to yellow. The solution was characterized by NMR and mass spectrometry as Dark-Hole-1. The 1H NMR spectrum of Dark-Hole-1 is shown in the attached figure. Figure 3 As shown, HRMS[M+H] + 353.2228. This indicates that Hole-1 or Hole-2 molecules can be oxidized by electron holes and then cyclized to generate the dye form Em-Hole-1, which is subsequently attacked by water molecules to generate the non-fluorescent Dark-Hole-1 molecule.

[0103] This demonstrates that the semiconductor hole fluorescent probe provided by the present invention has the property of OFF-ON-OFF type fluorescence on and off, which can realize in-situ imaging of holes.

[0104] Example 31 Spectroscopic Experiment Because the dyes generated by the cyclization of the semiconductor hole fluorescent probe provided by this invention after oxidation by electron holes have similar conjugated frameworks and exhibit extremely high spectral similarity, this embodiment tested the UV absorption and fluorescence emission spectra of Em-Hole-1 (10 μmol) obtained after the oxidation of Hole-1 and Hole-2 in different solvents (water, dichloromethane, and methanol), as shown below. Figure 4 As shown, Em-Hole-1 exhibits excellent photophysical properties in both aqueous and organic phases, meeting the requirements for fluorescence imaging.

[0105] Furthermore, using 470nm light as excitation light, full-spectrum photons were collected, and the absolute fluorescence quantum yield of Em-Hole-1 in dichloromethane was calculated to be 24.74%, indicating that the dye obtained after the semiconductor hole fluorescent probe provided by the present invention is oxidized by electron holes has excellent fluorescence emission properties.

[0106] Furthermore, the UV-Vis absorption and fluorescence emission spectra of Hole-25 after oxidation in acetonitrile were tested, and the results are as follows: Figure 5 As shown, its maximum absorption wavelength and emission wavelength are 747 nm and 813 nm, respectively, and the Stokes shift reaches 66 nm. This indicates that after the semiconductor hole fluorescent probe provided by the present invention is oxidized by electron holes, due to the asymmetry of its molecules and the TICT state within the molecules, its Stokes shift is greater than 50 nm, achieving effective separation of the excitation and emission spectra and fundamentally eliminating excitation light scattering interference.

[0107] Example 32 Oxidation Potential Test Experiment Hole-1 (0.5 mmol), Hole-2 (0.5 mmol), and Hole-6 (0.5 mmol) were dissolved in ultra-dry acetonitrile solution, respectively. Cyclic voltammetry was performed using 1 mol / L tetrabutylammonium hexafluoride as the electrolyte, platinum as the electrode, and silver / silver chloride as the reference electrode. The results are as follows: Figure 6 As shown. By Figure 6 As can be seen, Hole-1, Hole-2, and Hole-6 have similar framework structures and oxidation sites, and therefore have the same redox potential. Their oxidation potentials in the visible light region are all +0.68 V, which translates to +1.29 V for a standard hydrogen electrode, lower than the valence band potential of most photocatalytic semiconductors. This indicates that the semiconductor hole fluorescent probe provided by this invention can be oxidized by holes generated by most photocatalytic semiconductors.

[0108] Example 33: Activation Ability Test Experiment at Different Oxidation Potentials Hole-2 (0.5 mmol) and Hole-6 (0.5 mmol) were dissolved separately in ultra-dry acetonitrile solution. Using 1 mol / L tetrabutylammonium hexafluoride phosphate as the electrolyte, platinum as the electrode, and silver / silver chloride as the reference electrode, Hole-2 and Hole-6 were electro-oxidized at different oxidation potentials (0.68 V, 1.05 V, and 1.25 V). The electrolytes after electrolysis at 0.68 V, 1.05 V, and 1.25 V for 400 s were measured, and their UV-Vis spectra were analyzed. The results are as follows: Figure 7 As shown.

[0109] Depend on Figure 7 As shown in (b) and (e), Hole-2 and Hole-6 can be effectively electro-oxidized at 0.68 V, 1.05 V, and 1.25 V. Among them, [the following is a partial translation of the original text, which is incomplete and requires further context]. Figure 7 (a) It is evident that Hole-2 first forms a blue compound during electrolysis, suggesting that Hole-2 is preferentially oxidized to the cationic salt form of diarylmethane (Hole-2+), followed by ring closure to form the Em-Hole-1 structure; the UV-Vis spectrum of the Hole-2 electrolysis process also verifies this speculation. Figure 7 (b) It can be seen that the absorption peak formed at 620 nm by the Hole-2 electrolyte is the absorption peak of the cationic diarylmethane (Hole-2+), while the absorption peak formed at 520 nm is the absorption peak of the ring-closed Em-Hole-1 cationic salt. Figure 7 (d) It can be seen that during the electrolysis of Hole-6, a pink compound is directly generated at the anode, suggesting that it directly forms the cyclically closed Em-Hole-6 cationic salt form; Figure 7 (e) As can be seen, the UV-Vis spectrum of the Hole-6 electrolyte shows an absorption peak only at 520 nm, without a peak at 620 nm. This may be because Hole-6 contains two methyl groups, and the geminal dimethyl effect makes the oxidized Hole-6 more prone to ring closure. The structural formula of the Em-Hole-6 cation salt is as follows: .

[0110] The structure of Em-Hole-6 cationic salt is obtained through... 1 H NMR, 13 Identification was performed using C10 NMR and HRMS. Specifically, 1H NMR (400 MHz, Chloroform- d): δ 8.16 (dd, J=9.3, 4.7Hz, 3H), 6.94 (dd, J=9.4, 2.2Hz, 1H), 6.83 (d, J=9.4Hz, 2H ), 6.57 (d, J=2.2Hz, 1H), 3.62–3.55 (m, 8H), 1.76 (s, 6H), 1.33–1.29 (m, 12H). 13 CNMR (101MHz, CDCl3): δ 179.01, 162.52, 154.73, 154.70, 134.69, 131.14, 115.47, 114.41, 112.90, 112.56, 102.46, 94.88, 45.98, 45.58, 26.73, 12.56, 12.41. HRMS[M+H] + : 365.2577.

[0111] Furthermore, the electrolytes from Hole-2 and Hole-6 were electrolyzed at 0.68 V for 400s, 800s, 1200s, 1600s, 2000s, and 2400s, respectively, and the UV-Vis spectra of the electrolytes were measured. The results are as follows: Figure 7 As shown in (c) and (f), both Hole-2 and Hole-6 exhibit excellent activation properties.

[0112] Example 34 Stability test experiment at different oxidation potentials The dye EM-Hole-6, obtained by complete electrolysis of Hole-6 at 1.25 V, was dissolved in ultra-dry acetonitrile solution. Using 1 mol / L tetrabutylammonium hexafluoride phosphate as the electrolyte, platinum as the electrode, and silver / silver chloride as the reference electrode, the stability of EM-Hole-6 over electrolysis time was tested at voltages of 0.68 V, 1.05 V, and 1.25 V. The results are as follows: Figure 8 As shown. By Figure 8 As can be seen, Em-Hole-6 exhibits excellent stability at 0.68 V, 1.05 V, and 1.25 V.

[0113] Example 35: Photoactivation capability test experiment in the presence of semiconductor catalyst Hole-6 (20 mmol) was dissolved in ultra-dry acetonitrile solution, and 20 mg of nano-TiO2 was added as a semiconductor catalyst, forming the experimental group, denoted as the +TiO2 group; the -TiO2 group without added TiO2 served as the control group; both the +TiO2 and -TiO2 groups were irradiated using a 360 nm LED as the excitation source, and their UV absorption spectra were measured every 10 min until irradiation for 100 min. The results are as follows: Figure 9 As shown. By Figure 9It is evident that TiO2, as a semiconductor catalyst, can effectively oxidize Hole-6 under 360 nm LED irradiation. This demonstrates that the semiconductor hole fluorescent probe provided by this invention can achieve hole imaging of semiconductor catalysts.

[0114] Example 36: Hole disappearance ability and single-molecule imaging ability test experiment Rod-shaped zinc oxide nanoparticles were used as the semiconductor material. 1 mg of rod-shaped zinc oxide nanoparticles were dissolved in 2 mL of deionized water to prepare a low-concentration suspension. Hole-2 probe was then added, and the dye concentration was diluted to 0.5 μmol / L, and the mixture was stirred thoroughly. 10 μL of the suspension containing the Hole-2 probe was pipetted onto a glass slide, covered with a coverslip, and observed under a microscope objective. A 405 nm laser was used as the excitation light to trigger the separation of holes and electrons in the zinc oxide particles, and a 561 nm laser was used as the excitation light for the dye. The effect of hole generation on the onset of dye fluorescence was verified by alternating between 405 nm and 561 nm lasers. The results are as follows: Figure 10 As shown.

[0115] Depend on Figure 10 It is evident that the nano-zinc oxide rod can be illuminated when both 405 nm and 561 nm lasers are present, while no fluorescence of the dye is observed when only the 405 nm or 561 nm laser is activated. This indicates that the holes generated by the semiconductor can effectively oxidize Hole-2. Therefore, the semiconductor hole fluorescent probe provided by this invention possesses hole tracing capabilities.

[0116] Single-molecule imaging tests were performed under the above conditions, and the results are as follows: Figures 11-13 As shown, by extracting the fluorescence intensity of a single frame, it was found that the fluorescence intensity of the dye is mainly distributed on the zinc oxide nanoparticles, and it can indicate defects and other structures on the zinc oxide surface. Further extraction of single-molecule trajectories, such as... Figure 14 As shown, dense and intense single-molecule signals were captured. This demonstrates that the semiconductor hole fluorescent probe provided by this invention possesses single-molecule imaging capabilities.

Claims

1. A type of semiconductor hole fluorescent probe, characterized in that, It has the following general structural formula: or or or or or ; Where R= or or or A= or or or or or or or n is an integer from 0 to 18; Where R1,R2= or or or or or or or or or or or m is an integer between 0 and 18; The anion is BF4. – or Cl – or Br – Or I – Or NO3 – or SO4 2– or ClO4 – or CH3COO – or CH3SO3 – or CF3SO3 – ; The total number of positive charges carried is equal to the number of anions. The total amount of charge carried.

2. The application of the semiconductor hole fluorescent probe according to claim 1 in semiconductor hole imaging.

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