An active oxygen-producing triphenylamine unit heteroleptic iridium (iii) complex, a preparation method and application thereof
By designing cationic heterojunction iridium(III) complexes composed of C^N and N^N bidentate ligands containing triphenylamine units, the problem of luminescence quenching in existing materials in high-concentration or complex media has been solved, achieving the effect of both luminescence performance and reactive oxygen generation, which is suitable for luminescence and photodynamic related fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHANGCHUN UNIV OF SCI & TECH
- Filing Date
- 2026-04-09
- Publication Date
- 2026-06-09
AI Technical Summary
Existing organic or organometallic photosensitive materials are prone to luminescence quenching in high concentrations or complex media, have limited structural tunability, and are difficult to balance luminescence performance and reactive oxygen generation performance.
A cationic heterojunction iridium(III) complex composed of C^N and N^N bidentate ligands containing triphenylamine units is synthesized by coordination with Ir(III) through the main ligand L1 and the auxiliary ligand L2 to form a mononuclear six-coordinate octahedral structure, and the synthetic route is clear.
Under light irradiation, the complex can effectively generate total reactive oxygen species, hydroxyl radicals and superoxide anion radicals, exhibiting good luminescence properties and reactive oxygen species generation ability. It is suitable for dilute solutions, solids and different organic solvents, and the synthetic route is simple.
Smart Images
Figure FT_1 
Figure FT_2 
Figure FT_3
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organometallic luminescent materials and photosensitizers, specifically relating to a triphenylamine-containing heteropolymer luminescent iridium(III) complex that can generate active oxygen, its preparation method and application. Background Technology
[0002] Photosensitive materials have wide applications in luminescence, imaging, sensing, and photodynamic therapy. For photodynamic applications, photosensitizers can transition from the ground state to an excited state under specific illumination conditions, and further generate reactive oxygen species (ROS) through energy transfer or electron transfer processes, thereby exerting their corresponding effects.
[0003] While some existing organic or organometallic photosensitive materials possess certain luminescence properties and reactive oxygen species (ROS) generation capabilities, many molecules, due to their high degree of planar conjugation and strong hydrophobicity, are prone to luminescence quenching in high concentrations, aggregated states, or complex media, leading to a decline in their photophysical properties. Furthermore, the limited structural tunability of some traditional photosensitive materials hinders the synergistic optimization of their luminescence and ROS generation performance.
[0004] Iridium(III) complexes exhibit strong spin-orbit coupling, which typically facilitates intersystem crossing during excited-state processes, thereby improving excited-state utilization efficiency. Triphenylamine structural units possess good electron-donating ability and tunable optical properties; their introduction into iridium(III) complexes holds promise for obtaining novel functional materials that combine luminescence properties with reactive oxygen species generation capabilities.
[0005] However, existing materials still face the challenge of simultaneously achieving luminescence properties and reactive oxygen species (ROS) generation capabilities. Therefore, developing a heterojunction iridium(III) complex with a well-defined structure, excellent luminescence properties, and the ability to effectively generate ROS under illumination is of great significance. Summary of the Invention
[0006] The purpose of this invention is to provide a triphenylamine-containing heteropolymer luminescent iridium(III) complex that can generate reactive oxygen species, its preparation method and application, so as to improve the shortcomings of some existing luminescent or photosensitive materials in terms of structural tunability, luminescence performance and reactive oxygen species generation ability, and to provide a functional material that has both luminescence performance and reactive oxygen species generation ability.
[0007] To achieve the above objectives, the present invention adopts the following technical solution:
[0008] This invention provides a heterogamic iridium(III) complex with the structure shown in formula (I), and the chemical structural formula of the target heterogamic iridium(III) complex is as follows: Figure 3As shown: [Ir(L1)2(L2)]PF6
[0009] The chemical structural formula of the main ligand L1 is as follows: Figure 1 As shown, L1 is 1-(4-(diphenylamino)phenyl)isoquinoline; the chemical structural formula of the auxiliary ligand L2 is as follows. Figure 2 As shown, L2 is 2-[3-methyl-1-(4-(diphenylamino)phenyl)-1H-1,2,4-triazol-5-yl]pyridine. For ease of explanation, the target heterojunction iridium(III) complex [Ir(L1)2(L2)]PF6 shown in formula (I) is referred to herein as Ir-TPA-N.
[0010] Preferably, the two L1 ligands are coordinated with Ir(III) in a C^N bidentate metallization manner, and the L2 ligand is coordinated with Ir(III) in an N^N bidentate manner, forming a cationic heterocyclic iridium(III) complex, PF6. - For anions.
[0011] Preferably, the heterojunction iridium(III) complex has a mononuclear six-coordinate octahedral structure.
[0012] This invention also provides a method for preparing the heterojunction iridium(III) complex, comprising the following steps:
[0013] (1) Iridium trichloride hydrate was reacted with the main ligand L1 in an organic solvent / water mixture to obtain the chlorinated bridged iridium dimer intermediate [Ir(L1)2Cl]2;
[0014] (2) The chlorinated bridged iridium dimer and the neutral auxiliary ligand are heated and reacted in a polar solvent to obtain a cationic heteroligand iridium(III) complex;
[0015] (3) The complex obtained in step (2) is subjected to anion exchange with hexafluorophosphate to obtain the target heterojunction iridium(III) complex [Ir(L1)2(L2)]PF6.
[0016] Preferably, the organic solvent in step (1) is ethylene glycol ethyl ether, and the volume ratio of ethylene glycol ethyl ether to water is 3:1.
[0017] Preferably, the polar solvent in step (2) is ethylene glycol.
[0018] Preferably, the coordination reaction in step (2) is carried out under light-protected conditions.
[0019] Preferably, the hexafluorophosphate in step (3) is potassium hexafluorophosphate, ammonium hexafluorophosphate, or sodium hexafluorophosphate.
[0020] The present invention also provides the use of the heterojunction iridium(III) complex in at least one of the following applications:
[0021] (1) Preparation of luminescent materials;
[0022] (2) Preparation of reactive oxygen species generating materials;
[0023] (3) Preparation of photodynamic photosensitive materials. Beneficial effects
[0024] Compared with the prior art, the present invention has at least the following beneficial effects:
[0025] (1) The present invention introduces aromatic amine structural units containing triphenylamine characteristics into both the main ligand and the auxiliary ligand, which is beneficial to obtaining good light absorption and luminescence performance;
[0026] (2) The present invention adopts a cationic heteroligand iridium(III) coordination structure composed of two C^N main ligands and one N^N auxiliary ligand, which is beneficial to give full play to the role of the iridium center in promoting the excited state transition process, thereby enabling the complex to generate reactive oxygen species under light conditions;
[0027] (3) According to the detection of DCFH-DA, HPF and DHR123 probes, the complex of the present invention can generate total reactive oxygen species, hydroxyl radicals and superoxide anion radicals under LED white light irradiation.
[0028] (4) The complexes described in this invention exhibit luminescent properties in dilute solutions, solids, and different organic solvents, indicating that they have good potential for application as luminescent materials;
[0029] (5) The synthetic route of the complex described in this invention is clear, the raw materials are available, and it is convenient for preparation and subsequent application research. Attached Figure Description
[0030] Figure 1 Here is the chemical structural formula of the main ligand L1 of the present invention; the main ligand L1 is 1-(4-(diphenylamino)phenyl)isoquinoline.
[0031] Figure 2 Here is the chemical structural formula of the auxiliary ligand L2 of the present invention; the auxiliary ligand L2 is 2-[3-methyl-1-(4-(diphenylamino)phenyl)-1H-1,2,4-triazol-5-yl]pyridine.
[0032] Figure 3 The chemical structural formula of the target heterojunction iridium(III) complex [Ir(L1)2(L2)]PF6 (abbreviated as Ir-TPA-N) shown in formula (I) of this invention is given.
[0033] Figure 4The target heterojunction iridium(III) complex Ir-TPA-N of this invention is prepared at a concentration of 1.0 × 10⁻⁶. -5 UV-Vis absorption spectrum of M in CH3CN solution.
[0034] Figure 5 The target heterojunction iridium(III) complex Ir-TPA-N of this invention is prepared at a concentration of 1.0 × 10⁻⁶. -5 Emission spectrum of M in DMSO solution.
[0035] Figure 6 The emission spectrum of the target heterojunction iridium(III) complex Ir-TPA-N in the solid state is shown.
[0036] Figure 7 The emission spectra of the target heterojunction iridium(III) complex Ir-TPA-N of this invention in CDCl3, toluene, acetone, CH3CN and DMSO are shown.
[0037] Figure 8 The target heterojunction iridium(III) complex Ir-TPA-N of this invention in d6-DMSO 1 H NMR spectrum.
[0038] Figure 9 The target heterojunction iridium(III) complex Ir-TPA-N of this invention in d6-DMSO 19 F NMR spectrum.
[0039] Figure 10 The graph shows the fluorescence intensity changes of (A) Ir-TPA-N (B) DCFH-DA (C) RB in DCFH-DA as a function of irradiation time under white light irradiation.
[0040] Figure 11 2′,7′-dichlorodihydrofluorescein diacetate (DCFH-DA) was used for total ROS detection (DCFH-DA, working concentration: 5 μM; I0 and I are the peak values of the photoluminescence intensity of the complex Ir-TPA-N (2 μM) in a DMSO / water mixture).
[0041] Figure 12 The graph shows the fluorescence intensity changes of (A)Ir-TPA-N (B)HPF (C)RB in HPF with irradiation time under white light irradiation.
[0042] Figure 13 The peak photoluminescence intensity of the I0 and I complex Ir-TPA-N (2 μM) in a DMSO / water mixture is shown for the detection of •OH by hydroxyphenyl fluorescein (HPF, working concentration: 5 μM).
[0043] Figure 14 The graph shows the fluorescence intensity changes of (A) Ir-TPA-N (B) DHR123 (C) RB in DHR123 under white light irradiation as a function of irradiation time.
[0044] Figure 15 Dihydrorhodamine 123 (DHR123) was used for O2•− detection (DHR123, working concentration: 5 μM); I0 and I are the peak values of the photoluminescence intensity of the complex Ir-TPA-N (2 μM) in a DMSO / water mixture.
[0045] Figure 16 Dihydrorhodamine 123 (DHR123) and DHR123+Vitamin C (Vc) were used for O2•− detection (DHR123, working concentration: 5 μM); the asterisk (as shown in the figure) indicates the multiple. Detailed Implementation
[0046] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto. Example 1 Preparation of the target heterojunction iridium(III) complex [Ir(L1)2(L2)]PF6 (Ir-TPA-N)
[0047] The structure of the target heterojunction iridium(III) complex [Ir(L1)2(L2)]PF6 (abbreviated as Ir-TPA-N) prepared in this embodiment is as follows: Figure 3 As shown, the structures of the main ligand L1 and the auxiliary ligand L2 used are as follows: Figure 1 and Figure 2 As shown.
[0048] 1) Preparation of chlorine-bridged iridium dimer [Ir(L1)2Cl]2
[0049] Iridium trichloride hydrate (1.0 mmol) and the main ligand L1 (i.e., 1-(4-(diphenylamino)phenyl)isoquinoline, 2.2 mmol) were added to a mixed solvent of ethylene glycol ethyl ether and deionized water, with a volume ratio of ethylene glycol ethyl ether to water of 3:1, for a total volume of 40 mL. The mixture was heated to 135 °C and refluxed for 24 h under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed successively with water and ethanol, and dried under vacuum to obtain an orange-yellow or red solid intermediate [Ir(L1)2Cl]2.
[0050] 2) Preparation of cationic heterojunction iridium(III) complexes
[0051] The above intermediate (0.10 mmol) and auxiliary ligand L2 (i.e., 2-[3-methyl-1-(4-(diphenylamino)phenyl)-1H-1,2,4-triazol-5-yl]pyridine, 0.25 mmol) were added to ethylene glycol (10 mL) solvent, and heated under reflux for 12–18 h under nitrogen protection and in the dark. After the reaction was completed, the solvent was removed, and the residue was dissolved in dichloromethane, washed with water, dried over anhydrous sodium sulfate, and concentrated to obtain the crude product of the cationic hetero-iridium(III) complex.
[0052] (3) Hexafluorophosphate exchange
[0053] The crude product obtained in step (2) was dissolved in a suitable solvent, and anion exchange was performed by adding ammonium hexafluorophosphate solution to precipitate the target product. After separation, washing and purification, the target heterojunction iridium(III) complex [Ir(L1)2(L2)]PF6 was obtained.
[0054] Yield: 70%.
[0055] The obtained target complex was structurally characterized using 1H NMR and fluorine NMR spectroscopy, among which... 1 H NMR spectrum as follows Figure 8 As shown, 19 F NMR spectrum as follows Figure 9 As shown.
[0056] 1 H NMR (500 MHz, d6-DMSO, δ [ppm]): 4.74-4.79 (m, 1H), 8.15-8.18 (m,1H), 8.11-8.14 (m, 2H), 7.88-7.93 (m, 2H), 7.73-7.82 (m, 5H), 7.66 (d, J =6.5 Hz, 1H), 7.61 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.5 Hz, 1H), 7.40-7.43(m, 7H), 7.18-7.26 (m, 11H), 7.09-7.16 (m, 5H), 7.02-7.08 (m, 7H), 6.87-6.92(m, 6H), 6.83 (d, J = 7.5 Hz, 3H), 6.62 (d, J = 12.0 Hz, 1H), 5.58 (d, J =22.0 Hz, 1H), 1.76 (s, 3H).
[0057] 19 F NMR (470 MHz, d6-DMSO, ppm): -69.38 (s, 3F), -70.89 (s, 3F).
[0058] MS (MALDI-TOF) [m / z]: 1338.4520 (calcd: 1338.4523) for [M-PF6](C 80 H 59 IrN9). Example 2: Photophysical property testing
[0059] The target complex Ir-TPA-N obtained in Example 1 was prepared into a concentration of 1.0 × 10⁻⁶. -5 The UV-Vis absorption spectrum of a CH3CN solution of M was measured. The test results are as follows: Figure 4 As shown, the complex has a distinct absorption band in the ultraviolet-visible region, indicating that it has good light absorption capabilities.
[0060] The target complex Ir-TPA-N obtained in Example 1 was formulated to a concentration of 1.0 × 10⁻⁶. -5 The emission spectrum of a DMSO solution of M was measured. The test results are as follows: Figure 5 As shown, the complex exhibits luminescent properties in a dilute DMSO solution.
[0061] Solid-state emission tests were performed on the target complex Ir-TPA-N obtained in Example 1. The test results are as follows: Figure 6 As shown, the complex continues to emit light in the solid state, indicating that it has solid-state luminescence properties.
[0062] Dilute solutions of the target complex Ir-TPA-N were prepared in CDCl3, toluene, acetone, CH3CN, and DMSO, respectively, and their emission spectra were measured. The test results are as follows: Figure 7 As shown in the figure. The results indicate that the complex exhibits luminescence behavior in different solvents and displays certain solvent-dependent luminescence characteristics. Example 3: Detection of Total Reactive Oxygen Species
[0063] 2',7'-dichlorodihydrofluorescein diacetate (DCFH-DA) was used as the total reactive oxygen species (ROS) detection probe. The ROS generation capacity of the target complex Ir-TPA-N under white light irradiation was tested in a DMSO / water mixture system, with (RB) used as the control photosensitizer.
[0064] The working concentration of DCFH-DA was 5 μM, and the working concentration of the target complex Ir-TPA-N was 2 μM. The white light source was an LED lamp with a power of 30 W, a color temperature of 6000–6500 K, an illumination distance of 5 cm, and illumination times set to 0, 30, 60, 90, 120, 150, 180, 210, 240, 270, and 300 s.
[0065] Under the above conditions, the fluorescence intensity ratio I / I0 of the Ir-TPA-N system changes with irradiation time as follows: Figure 10 As shown, the fluorescence intensity ratio of the system containing Ir-TPA-N gradually increases with the extension of illumination time, indicating that the system can induce the generation of total reactive oxygen species under illumination conditions.
[0066] The total reactive oxygen species (ROS) generation capacity was further evaluated using the DCFH-DA probe, and the results are as follows: Figure 11 As shown in the figure. Where I0 represents the initial peak photoluminescence intensity of the system at 525 nm, and I represents the peak photoluminescence intensity of the system at 525 nm after illumination for different times.
[0067] Depend on Figure 11 It was observed that with prolonged illumination time, the fluorescence intensity ratio I / I0 of the system containing the target complex Ir-TPA-N at 525 nm gradually increased; when the illumination time reached 300 s, the fluorescence enhancement factor approached 12-fold. Compared with the RB control group and the blank probe group, the system corresponding to the target complex exhibited higher fluorescence response intensity and a faster growth trend.
[0068] The above results indicate that the target complex Ir-TPA-N can effectively induce the generation of total reactive oxygen species (ROS) under illumination, and has a good ROS generation capacity, thus demonstrating its application potential in ROS generation materials and photodynamic photosensitive materials. Example 4: Detection of Hydroxyl Radicals
[0069] Hydroxyphenylfluorescein (HPF) was used as a hydroxyl radical detection probe to test the hydroxyl radical generation ability of the target complex Ir-TPA-N under white light irradiation in a DMSO / water mixture, with RB as a control photosensitizer.
[0070] The working concentration of HPF was 5 μM, and the working concentration of the target complex Ir-TPA-N was 2 μM. The white light source was an LED lamp with a power of 30 W, a color temperature of 6000–6500 K, an illumination distance of 5 cm, and illumination times set to 0, 30, 60, 90, 120, 150, 180, 210, 240, 270, and 300 s.
[0071] Under the above conditions, the fluorescence intensity ratio I / I0 of the Ir-TPA-N system changes with irradiation time as follows: Figure 12 As shown, the fluorescence intensity ratio of the system containing Ir-TPA-N gradually increases with the extension of illumination time, indicating that the system can induce the generation of hydroxyl radicals under illumination conditions.
[0072] The ability to generate hydroxyl radicals was further evaluated using an HPF probe, and the results are as follows: Figure 13 As shown in the figure. Where I0 represents the initial peak photoluminescence intensity of the system at 515 nm, and I represents the peak photoluminescence intensity of the system at 515 nm after illumination for different times.
[0073] Depend on Figure 13 It can be seen that with the extension of illumination time, the fluorescence intensity ratio I / I0 of the system containing the target complex Ir-TPA-N at 515 nm continuously increases; when the illumination time reaches 300 s, its fluorescence enhancement factor exceeds 100 times. In contrast, RB has a lower fluorescence enhancement factor under the same conditions, while the fluorescence response of the blank probe group is weaker.
[0074] The above results indicate that the target complex Ir-TPA-N can effectively induce the generation of hydroxyl radicals under light irradiation, demonstrating good hydroxyl radical generation capacity. This suggests its potential application in reactive oxygen species (ROS) generating materials and photodynamic photosensitive materials. Example 5: Detection of Superoxide Anion Radicals
[0075] Dihydrorhodamine 123 (DHR123) was used as a superoxide anion radical detection probe to test the superoxide anion radical generation capacity of the target complex Ir-TPA-N under white light irradiation in a DMSO / water mixture.
[0076] The working concentration of DHR123 was 5 μM, and the working concentration of the target complex Ir-TPA-N was 2 μM; a DHR123 + vitamin C (Vc) system was also set as a control. The white light source was an LED lamp with a power of 30 W, a color temperature of 6000–6500 K, an illumination distance of 5 cm, and illumination times of 0, 30, 60, 90, 120, 150, 180, 210, 240, 270, and 300 s.
[0077] Under the above conditions, the fluorescence intensity ratio I / I0 of the Ir-TPA-N system changes with irradiation time as follows: Figure 14 As shown, the fluorescence intensity ratio of the system containing Ir-TPA-N gradually increases with the extension of illumination time, indicating that the system can induce the generation of superoxide anion radicals under illumination conditions.
[0078] The ability to generate superoxide anion radicals was further evaluated using the DHR123 probe, and the results are as follows: Figure 15 As shown in the figure. Where I0 represents the initial peak photoluminescence intensity of the system, and I represents the peak photoluminescence intensity of the system after illumination for different times.
[0079] The ability of DHR123 and DHR123+vitamin C (Vc) systems to generate superoxide anion radicals was compared, and the results are as follows: Figure 16 As shown in the figure. The asterisks in the figure indicate fold changes. After the addition of vitamin C, the fluorescence response of the system was significantly suppressed, further demonstrating that the target complex can effectively generate superoxide anion radicals under light conditions.
[0080] The above embodiments demonstrate that the heterojunction iridium(III) complexes of the present invention not only have good luminescent properties, but also can generate total reactive oxygen species, hydroxyl radicals and superoxide anion radicals under LED white light irradiation conditions. Therefore, they have application potential in luminescent materials, reactive oxygen species generating materials and photodynamic photosensitive materials.
[0081] The above embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. All equivalent substitutions, improvements, or variations made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A heterogamic iridium(III) complex, Its features are, The heterojunction iridium(III) complex has the structure shown in formula (I): [Ir(L1)2(L2)]PF6 in, L1 is 1-(4-(diphenylamino)phenyl)isoquinoline; L2 is 2-[3-methyl-1-(4-(diphenylamino)phenyl)-1H-1,2,4-triazol-5-yl]pyridine.
2. The heterojunction iridium(III) complex according to claim 1, Its features are, The two L1 ligands are coordinated with Ir(III) via C^N bidentate metallization, and the L2 ligand is coordinated with Ir(III) via N^N bidentate metallization. The complex is a mononuclear six-coordinate octahedral iridium(III) cationic complex, PF6. - For anions.
3. A method for preparing the heterojunction iridium(III) complex according to claim 1 or 2, Its features are, Includes the following steps: (1) Iridium trichloride hydrate was reacted with the main ligand L1 in an organic solvent / water mixture to obtain the chlorinated bridged iridium dimer intermediate [Ir(L1)2Cl]2; (2) The chlorinated bridged iridium dimer reacts with a neutral auxiliary ligand in a polar solvent by heating to obtain a cationic heteroligand iridium(III) complex; (3) The complex obtained in step (2) is subjected to anion exchange with hexafluorophosphate to obtain the target heterojunction iridium(III) complex [Ir(L1)2(L2)]PF6.
4. The preparation method according to claim 3, Its features are, The organic solvent mentioned in step (1) is ethylene glycol ethyl ether, and the volume ratio of ethylene glycol ethyl ether to water is 3:
1.
5. The preparation method according to claim 3 or 4, Its features are, The polar solvent in step (2) is ethylene glycol, and step (2) is carried out under light-protected conditions.
6. The preparation method according to any one of claims 3 to 5, Its features are, The hexafluorophosphate mentioned in step (3) is potassium hexafluorophosphate, ammonium hexafluorophosphate or sodium hexafluorophosphate.
7. The use of the heterojunction iridium(III) complex according to claim 1 or 2 in the preparation of luminescent materials.
8. The use of the heterojunction iridium(III) complex according to claim 1 or 2 in the preparation of reactive oxygen species generating materials.
9. The application according to claim 8, Its features are, The reactive oxygen species include total reactive oxygen species, hydroxyl radicals and / or superoxide anion radicals.
10. The use of the heterojunction iridium(III) complex according to claim 1 or 2 in the preparation of photodynamic photosensitive materials.