Pyrrole-modified N-flip porphyrin single-rhodium and double-rhodium complex as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis and optical functional materials, and relates to pyrrole modified N-flip porphyrin single-rhodium and double-rhodium complexes as well as a preparation method and application thereof. According to the complex, 3-(2 '-pyrrole)-5, 10, 15, 20-tetra (4-bromophenyl)-N-flip porphyrin is used as a ligand, a stable monoanion N, N chelation site is constructed through pyrrole modification and strongly coordinated with an Rh (I) center, and the mononuclear (3-Rh) and binuclear (3-Rh2) complex which is clear in structure and high in chemical stability is formed. The series of complexes have wide-spectrum strong absorption from visible light to a near-infrared region (extending to 900nm or above). Under excitation of green light or 808nm near-infrared light, singlet oxygen (for example, phi delta of 3-Rh is equal to 0.58 under the green light) can be efficiently generated, effective photo-thermal conversion (for example, eta of 3-Rh2 is equal to 23.1%) can be achieved, and excellent and adjustable photodynamic / photo-thermal dual-mode activity is shown. The preparation method disclosed by the invention is simple and relatively high in yield. The prepared complex has important application value in the fields of tumor synergistic phototherapy, near-infrared light catalysis, biological imaging and the like.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis and photofunctional materials technology, and relates to N-inverted porphyrin, particularly to a pyrrole-modified N-inverted porphyrin mono- and di-rhodium complex, its preparation method, and its application in photodynamic therapy (PDT), photothermal therapy (PTT), and green oxidation photocatalysis. Background Technology

[0002] N-confused porphyrins (NCPs) are a class of porphyrin analogs with a unique structure in which the nitrogen atom of one pyrrole ring is located outside the ring (i.e., "confused"), thus providing a coordination mode and electronic structure different from conventional porphyrins. Due to their unique macrocyclic structure and electronic properties, N-confused porphyrins and their related porphyrin analogs have become multifunctional molecular dye platforms in fields such as catalysis, photosensitization, photothermal conversion, photoacoustic signal generation, and near-infrared photonics. Their unique confused pyrrole nitrogen atom not only disrupts the aromaticity of the entire macrocycle but also opens up unconventional internal / external coordination modes not found in conventional porphyrins, providing unique opportunities for regulating their redox behavior and optical properties, and thus offering unique opportunities for developing functional applications.

[0003] Rhodium(I) porphyrin complexes, due to the flexibility of rhodium's oxidation states and the rich photophysical properties of porphyrin ligands, have broad application prospects in redox catalysis, molecular devices, small molecule sensing, and photomedicine. The heavy atom characteristics and strong spin-orbit coupling (SOC) of rhodium(I) promote efficient intersystem crossing (ISC), which is beneficial for generating long-lived triplet states, crucial for singlet oxygen photosensitization and photothermal processes. Compared to classic organic photosensitizers, rhodium complexes possess a greater diversity of excited states originating from the metal center and metal-ligand charge-transfer states, providing multiple pathways for reactive oxygen species (ROS) generation or non-radiative decay.

[0004] However, in existing bisrhodium N-inverted porphyrin complexes, the peripheral rhodium center is typically only bound to neutral inverted pyrrole nitrogen. Due to the lack of anion donors in this external coordination environment, the Rh-NCP bond is relatively unstable, and the peripheral rhodium center is easily lost under post-functionalization or reactive conditions, severely limiting the construction and application of stable multi-rhodium structures on the NCP framework. Simultaneously, existing phototherapy materials struggle to simultaneously achieve broad visible-near-infrared absorption, high singlet oxygen yield, and excellent photothermal conversion efficiency, and their insufficient stability restricts their practical application in synergistic photodynamic-photothermal therapy and green catalysis. Therefore, developing structurally stable and tunable bifunctional phototherapy materials is of great significance.

[0005] Pyrrole modification is an effective modification strategy for NCPs. By introducing pyrrole units at the periphery or interior of the flipped porphyrin, the selective reactivity of the flipped pyrrole α-position can be utilized. This modification not only introduces new coordination sites but also expands the π-backbone. In this invention, pyrrole modification transforms the peripheral donor into a formally monoanionic N,N chelate, enabling the modified pyrrole and the flipped pyrrole nitrogen atom to co-coordinate with a peripheral Rh(I) center. This chelation mode significantly enhances Rh-ligand bonding, increases metal-ligand covalentity, and strengthens d-π interactions, collectively reducing the HOMO-LUMO band gap and improving near-infrared absorption performance. These combined effects make the pyrrole-modified NCP-Rh complex a structurally stable and electronically tunable dual-mode phototherapy platform suitable for visible light and 808 nm near-infrared excitation. Summary of the Invention

[0006] To address the technical shortcomings of existing N-inverted porphyrin rhodium complexes (especially polynuclear rhodium complexes) such as poor stability, easy breakage of Rh-ligand linkages, and difficulty in synergistic optimization of photodynamic / photothermal properties, and to meet the need for developing efficient and stable visible-near-infrared dual-mode phototherapy agents, this invention provides pyrrole-modified N-inverted porphyrin mono- and di-rhodium complexes. By constructing stable anion N,N chelating sites through pyrrole modification, the stability of the complexes is improved, while simultaneously achieving precise regulation of broad visible-near-infrared absorption and dual-mode phototherapy activity.

[0007] Technical solution

[0008] A pyrrole-modified N-inverted porphyrin monorhodium complex (3-Rh), wherein the complex uses 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-inverted porphyrin as a ligand, and the ligand forms a square-planar Rh-N2(CO)2 coordination environment with Rh(I), wherein the N atom comes from the inverted pyrrole nitrogen of the ligand and the modified pyrrole nitrogen, respectively, and CO is a carbonyl ligand. The molecular formula is:

[0009] A pyrrole-modified N-invertorporphyrin bisrhodium complex (3-Rh2), wherein the complex uses 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-invertorporphyrin as a ligand, and the two Rh(I) centers form a square planar Rh-N2(CO)2 at the N,N chelating sites on the periphery and the N,N sites on the inside of the ligand, respectively. The molecular formula is:

[0010]

[0011] Ligand 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-invertorporphyrin (C 48 H 29The molecular formula of Br4N5 is as follows:

[0012]

[0013] A second objective of this invention is to disclose a method for preparing the above-mentioned pyrrole-modified N-inverted porphyrin mono- and di-rhodium complexes.

[0014] A method for preparing a pyrrole-modified N-inverted porphyrin monorhodium complex (3-Rh) includes the following steps: a) under nitrogen protection, Rh2(CO)4Cl2 is dissolved in anhydrous dichloromethane to obtain an Rh reagent solution; the molar ratio of Rh2(CO)4Cl2 to 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-inverted porphyrin is 0.5:1;

[0015] b. Dissolve the ligand 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-inverted porphyrin in anhydrous dichloromethane, and slowly add the above Rh reagent solution dropwise. Stir at room temperature for 1 h.

[0016] c. Remove the solvent under reduced pressure. Purify the residue by silica gel column chromatography using a 1:2 volume ratio of dichloromethane to n-hexane as the eluent. Recrystallization yields the target product.

[0017] The reaction equation is:

[0018]

[0019] A method for preparing a pyrrole-modified N-inverted porphyrin bisrhodium complex (3-Rh2) includes the following steps:

[0020] (1) Under nitrogen protection, 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-inverted porphyrin and Rh2(CO)4Cl2 were dissolved in anhydrous dichloromethane and stirred at room temperature for 4 h. The reaction was monitored by thin-layer chromatography. The molar ratio of Rh2(CO)4Cl2 to the ligand was 2.5:1.

[0021] (2) Remove the solvent under reduced pressure, and purify the residue by silica gel column chromatography. The eluent is a mixed solvent of dichloromethane / n-hexane in a volume ratio of 1:4. After recrystallization, the target product is obtained.

[0022] The reaction equation is:

[0023]

[0024] A third objective of this invention is to disclose the application of the above-mentioned pyrrole-modified N-inverted porphyrin monorhodium and dirhodium complexes in the preparation of photodynamic and / or photothermal therapeutic agents, particularly in the visible light field.

[0025] Applications of generating singlet oxygen and / or photothermal effects under excitation by (e.g., green light) and / or near-infrared light (e.g., 808nm laser).

[0026] Specifically,

[0027] Highly efficient singlet oxygen generation: The complex exhibits high efficiency under green light (10 mW / cm²). 2 ) or 808nm near-infrared laser (60mW / cm) 2 Singlet oxygen is generated under excitation. The singlet oxygen quantum yield ΦΔ of the single rhodium complex (3-Rh) is 0.58 under green light and 0.15 under 808 nm, while that of the double rhodium complex (3-Rh2) is 0.48 under green light and 0.08 under 808 nm.

[0028] Excellent photothermal conversion performance: The complex exhibits excellent photothermal conversion performance under 808nm laser (500mW / cm²) conditions. 2 Photothermal conversion is achieved under irradiation. The photothermal conversion efficiency of the single rhodium complex is η = 18%, and that of the double rhodium complex is η = 23.1%. The performance remains stable after three laser switching cycles.

[0029] Mononuclear and binuclear complexes exhibit differences in photodynamic and photothermal properties (3-Rh is biased towards photodynamic properties).

[0030] 3-Rh2 is photothermal biased, which provides a basis for selecting or designing compounds based on actual application needs.

[0031] Calculations using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), combined with hole-electron analysis and spin-orbit coupling constant calculations, clarified the different excited-state properties of the two complexes (3-Rh is mainly ligand center π-π* excitation, while 3-Rh2 has stronger metal-ligand mixing characteristics), thus rationalizing their different energy dissipation pathways (preferring to generate reactive oxygen species or non-radiative thermal relaxation).

[0032] The pyrrole-modified N-inverted porphyrin single-rhodium and double-rhodium complexes disclosed in this invention have simple preparation processes, high yields, and good chemical and photostable stability. Their broad visible-near-infrared absorption characteristics and tunable photodynamic / photothermal properties make them widely applicable in:

[0033] 1. Tumor-synergistic photodynamic-photothermal therapy reagent;

[0034] 2. Green oxidation photocatalysts driven by visible or near-infrared light;

[0035] 3. Photothermal imaging and photoacoustic imaging probes;

[0036] 4. Photoresponsive drug delivery systems, etc.

[0037] This complex solves the problems of poor stability, poor spectral matching, and limited performance of existing phototherapy materials, and has significant industrial application value and clinical translation potential.

[0038] Beneficial effects

[0039] This invention constructs a monoanion N,N chelate pocket around an N-inverted porphyrin through pyrrole modification, significantly enhancing the coordination strength with the rhodium(I) center and successfully obtaining structurally well-defined and stable mononuclear and binuclear rhodium(I) complexes. X-ray single-crystal diffraction confirmed that the two rhodium centers in 3-Rh2 are located at stable coordination sites inside and outside the macrocycle, respectively. The rhodium(I) complexes exhibit strong absorption in the visible to near-infrared region (extending above 900 nm), making them particularly suitable for the therapeutic window of biological tissues (e.g., around 808 nm), thus providing possibilities for phototherapy applications in deep tissues. Attached Figure Description

[0040] Figure 1 Partial concentrations of complexes 3-Rh(a) and 3-Rh2(b) in CDCl3 at 298 K 1 1H NMR spectrum, asterisks indicate peaks with residual solvent;

[0041] Figure 2 Crystal structure diagram of complex 3-Rh2 (top view and side view, thermal ellipsoid probability 50%). For clarity, the 4-bromophenyl in the middle position is omitted in the side view.

[0042] Figure 3 Absorption spectra of complexes 3-Rh (black line) and 3-Rh2 (red line) in CH2Cl2;

[0043] Figure 4 In CH3CN solution, with (a) 3-Rh, (b) 3-Rh2 and (c) RB as photosensitizers, green light irradiation (power density: 10 mW cm⁻¹) -2 (d) The changes in the UV-Vis absorption spectrum of DPBF recorded during the process; (d) The curve of the decrease in absorbance of DPBF at 410 nm at different irradiation times at room temperature.

[0044] Figure 5 In CH3CN solution, under the presence of (a) 3-Rh, (b) 3-Rh2, and (c) ICG as photosensitizers, irradiation with an 808 nm laser (power density: 60 mW / cm²) -2 (d) The changes in the UV-Vis absorption spectrum of DPBF recorded during the process; (d) The curve of the decrease in absorbance of DPBF at 410 nm at different irradiation times at room temperature.

[0045] Figure 6Temperature changes of toluene solutions of complexes (a) 3-Rh and (b) 3-Rh2 under 808 nm NIR laser on / off cycling;

[0046] Figure 7 Infrared thermal images of (a) 3-Rh and (b) 3-Rh2 solutions under different illumination times, respectively. Detailed Implementation

[0047] The present invention will be described in detail below with reference to embodiments to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following embodiments. Unless otherwise specified, the raw materials and equipment involved in the embodiments are all conventional commercially available products in the art.

[0048] Example 1

[0049] Ligand 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-invertorporphyrin (C 48 H 29 The preparation of Br4N5 was carried out according to the methods in existing literature (References: Geier, GR et al., Org. Lett. 1999, 1(9): 1455-1458; Wojaczyński, J. et al., Chem.-Asian J. 2017, 12(6): 643-647).

[0050] The specific steps are as follows: 5,10,15,20-tetra(4-bromophenyl)-N-invertorporphyrin (50 mg, 0.08 mmol) and 5 equivalents of pyrrole are dissolved in N,N-dimethylformamide (50 mL). 0.125 equivalents of boron trifluoride diethyl ether are added as a catalyst. The mixture is refluxed in air for 1 hour. After removing the solvent, the target product is obtained by alumina column chromatography. The reaction equation is:

[0051]

[0052] The structure of the ligand has been characterized and confirmed by NMR, mass spectrometry and other methods.

[0053] Example 2

[0054] Synthesis of a single rhodium (I) complex (3-Rh)

[0055] Under a nitrogen atmosphere, 5.86 mg (15 μmol, 0.5 equiv) of [RhCl(CO)2]2 was dissolved in 15 mL of dichloromethane; the solution was then slowly added dropwise to 30 mL of dichloromethane solution containing ligand 3 with stirring; the reaction was stirred at room temperature for 1 h, and the reaction progress was monitored by thin-layer chromatography (TLC).

[0056] After the reaction was complete, the solvent was removed by vacuum distillation, and the residue was purified by silica gel column chromatography using dichloromethane:n-hexane (1:2, v / v) as the eluent.

[0057] The target component was collected and recrystallized from dichloromethane / n-hexane to give a black solid product 3-Rh (10.72 mg, yield 31%).

[0058] The reaction equation is:

[0059]

[0060] Characterization data:

[0061] 1 H NMR (400MHz, CDCl3): δ=8.62(d,J=5.1Hz,1H),8.53(d,J=4.9Hz,1H),8.48(d,J=8.5H z,2H),8.36(d,J=8.4Hz,2H),8.25(d,J=4.7Hz,1H),8.20(dd,J=8.0,4.9Hz,2H),8.11 -8.06(m,3H), 8.00(d,J=8.2Hz,4H), 7.95-7.86(m,8H), 6.98(s,1H,modified pyrrole H), 6.04(dd,J=4.1,1.8Hz,1H,modified pyrrole H), 5.56(dd,J=4.2,0.9Hz,1H,modified pyrrole H), -4.03(s,1H, inverted pyrrole CH).

[0062] UV-Vis(CH2Cl2):λmax / nm(ε / M-1cm-1)=421(19730),564(21990),571

[0063] (23360),730(4810),839(3640).

[0064] MALDI-TOF-MS: m / z=1096.139[M] + (Calculated value C) 48 H 28 Br4N5Rh, without CO ligand: 1096.8092).

[0065] FT-IR: at 2066 and 1999 cm -1 A strong C≡O stretching vibration peak was observed at the location.

[0066] Example 3

[0067] Synthesis of bisrhodium(I) complex (3-Rh2)

[0068] Under a nitrogen atmosphere, ligand 3 (30 mg, 30 μmol) and [RhCl(CO)2]2 (29.1 mg, 75 μmol, 2.5 equiv) were dissolved in 15 mL of dichloromethane and stirred at room temperature for 4 h. The reaction was monitored by TLC.

[0069] After the reaction was complete, the solvent was removed by vacuum distillation; the residue was purified by silica gel column chromatography using dichloromethane:n-hexane (1:4, v / v) as the eluent.

[0070] The target component was collected and recrystallized from dichloromethane / n-hexane to give a black solid product 3-Rh2 (30 mg, yield 76%).

[0071] The reaction equation is:

[0072]

[0073] Characterization data:

[0074] 1 ¹H NMR (400MHz, CDCl₃): δ = 8.59–8.50 (m, 3H), 8.39 (dd, J = 11.8, 3.9Hz, 2H), 8.28 (d, J = 7.9Hz, 2H), 8.15–8.03 (m, 4H), 7.97 (d, J = 8.1Hz, 3H), 7.88–7.76 (m, 7H), 7.41 (d, J = 4.6Hz, 1H), 7.06 (s, 1H, modified pyrrole H), 6.12 (dd, J = 4.1, 1.8Hz, 1H, modified pyrrole H), 5.71 (dd, J = 4.1, 0.9Hz, 1H, modified pyrrole H), -3.52 (s, 1H, inverted pyrrole CH).

[0075] UV-Vis(CH2Cl2):λmax / nm(ε / M -1 cm -1 =371(17000),585(22740),841(8240).

[0076] MALDI-TOF-MS: m / z=1197.023[M] + (Calculated value C) 48 H 26 Br4N5Rh2, without CO ligand: 1197.6991).

[0077] FT-IR: at 2077, 2061, 2012 and 1991 cm⁻¹ -1 A strong C≡O stretching vibration peak was observed at the location.

[0078] Example 4

[0079] Singlet oxygen generation performance test

[0080] Using 1,3-diphenylisobenzofuran (DPBF) as the singlet oxygen ( 1 O2) scavengers were tested in acetonitrile solution. The complex was evaluated by monitoring the decay of the characteristic absorption peak of DPBF at 410 nm. 1 O2 generation capability.

[0081] Green light excitation (~540 nm): Prepare an acetonitrile solution containing 3-Rh or 3-Rh2 (10 μM) and DPBF (~60 μM), and use a green LED (10 mW cm⁻¹). -2 Irradiation was performed, and the UV-Vis spectrum was recorded every 10 seconds. The DPBF absorbance at 410 nm was monitored. Using Bengal rose red (RB, ΦΔ=0.53in CH3CN) as a reference, the ΦΔ of 3-Rh was calculated to be 0.58 and the ΦΔ of 3-Rh2 was 0.48.

[0082] Near-infrared excitation (808nm): A similar method was used, employing an 808nm laser (60mW cm⁻¹). -2 Irradiation. Using indocyanine green (ICG) in acetonitrile as a reference, the ΦΔ of 3-Rh was calculated to be 0.15, and the ΦΔ of 3-Rh2 was calculated to be 0.08.

[0083] Test results show that both 3-Rh and 3-Rh2 can efficiently generate singlet oxygen under green light and near-infrared light excitation, meeting the needs of photodynamic therapy.

[0084] Example 5

[0085] Photothermal conversion performance test

[0086] Prepare a 165 μmol / L toluene solution (2 mL), place it in a quartz cuvette, and dilute with 500 mW / cm² water. 2 The solution was continuously irradiated with an 808nm laser, and the temperature was recorded every 30 seconds using an infrared thermal imager until a steady-state temperature was reached. After irradiation was stopped, the cooling curve was recorded, and the photothermal conversion efficiency was calculated using a formula.

[0087] The 3-Rh solution increased from approximately 24.5°C to 43.6°C within 10 minutes (ΔT = 19.1°C).

[0088] The 3-Rh2 solution rose to 49.4℃ (ΔT=26.1℃) within the same time period.

[0089] The temperature rise of pure toluene solvent is negligible under the same conditions.

[0090] Test results showed that the photothermal conversion efficiencies of 3-Rh and 3-Rh2 were 18% and 23.1%, respectively, and they had good photothermal stability, making them suitable for photothermal therapy.

[0091] Figure 1 In Figures a and b, the 1H NMR spectra of monorhodium 3-Rh and dirhodium 3-Rh2 in deuterated chloroform are respectively. Their chemical shift characteristics indicate that both complexes retain the aromatic characteristics of the porphyrin macrocycle. Based on the compound shift in their strong shielding region, it can be determined that the rhodium neutrality of the monorhodium complex is located on the outside of the additional pyrrole and the N-inverted pyrrole forming the coordination cavity.

[0092] Figure 2 The image shows the crystal structure of the rhodium-2 complex 3-Rh2. As can be seen, the peripherally coordinated rhodium ions coordinate with the nitrogen atoms of the modified pyrrole and the inverted pyrrole, supplemented by two carbonyl ligands, forming a coplanar tetragonal coordination pattern. This planar tetragonal coordination pattern restricts the rotational freedom of the additional pyrrole, enhances molecular rigidity, and thus expands the conjugated system of the molecule, thus exhibiting… Figure 3 The absorption spectral characteristics show a significant redshift.

[0093] Figure 3 The absorption spectra of ligands 3, 3-Rh, and 3-Rh2 in dichloromethane are shown. After coordination with mono- and di-rhodium compounds, the long-wavelength Q absorption band of ligand 3 exhibits a significant red shift of approximately 60 nm, extending into the near-infrared region. Furthermore, the main absorption bands red-shift to 571 nm (3-Rh) and 585 nm (3-Rh2), respectively. Therefore, it is evident that the mono- and di-rhodium compounds exhibit significant light absorption in the near-infrared and green light regions, respectively.

[0094] Figure 4 and Figure 5 The photosensitization of DPBF as a singlet oxygen probe was demonstrated under both green light and 808 nm laser excitation sources. Both single and double rhodium complexes exhibited high singlet oxygen generation efficiency under both green light and near-infrared laser excitation.

[0095] Figure 6 and Figure 7 The photothermal conversion phenomenon of single and double rhodium complexes under 808nm laser irradiation was demonstrated. Under laser irradiation with a light intensity of 60 mW / cm², the toluene solutions of both complexes showed rapid heating, and no decay was observed after three heating-cooling cycles, proving that the two complexes have excellent near-infrared laser-driven photothermal conversion capability and good photostability.

[0096] The above results indicate that the pyrrole-modified N-inverted porphyrin rhodium(I) complexes 3-Rh and 3-Rh2 provided by this invention have well-defined and stable structures, excellent broad-spectrum absorption characteristics and dual-mode (photodynamic / photothermal) phototherapy functions, and their performance can be regulated by mononuclear / dual-nuclear structures. They have potential application value in the fields of biomedicine (such as combined phototherapy for tumors) and photocatalysis.

[0097] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A pyrrole-modified N-inverted porphyrin monorhodium or dirhodium complex, characterized in that, The complex has a single-rhodium complex structure as shown in molecular formula (I) or a double-rhodium complex structure as shown in molecular formula (II): In molecular formula (I), one Rh(I) center forms an outer N,N chelate structure with the flipped pyrrole nitrogen atom of the ligand and the modified pyrrole nitrogen atom; in molecular formula (II), the two Rh(I) centers are located at the outer N,N chelate site of the ligand and the inner N,N coordination site of the macrocycle, respectively.

2. The pyrrole-modified N-inverted porphyrin monorhodium or dirhodium complex according to claim 1, characterized in that: The complex has a square planar coordination configuration, with two N atoms and two CO ligands coordinated at the center of each Rh(I).

3. The pyrrole-modified N-inverted porphyrin monorhodium or dirhodium complex according to claim 1, characterized in that, The ligand is 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-invertorporphyrin, and its structure is shown in molecular formula (III):

4. A method for preparing a pyrrole-modified N-inverted porphyrin monorhodium or dirhodium complex according to any one of claims 1-3, characterized in that, Includes the following steps: a. The ligand 3-(2'-pyrrole)-5,10,15,20-tetra(4-bromophenyl)-N-inverted porphyrin was reacted with the rhodium reagent Rh2(CO)4Cl2 in an anhydrous dichloromethane under an inert atmosphere; b. By controlling the molar ratio of the rhodium reagent to the ligand, single-rhodium complexes or double-rhodium complexes can be selectively obtained; c. After the reaction is complete, the target product is obtained through separation and purification.

5. The method for preparing pyrrole-modified N-inverted porphyrin monorhodium or dirhodium complexes according to claim 4, characterized in that: When preparing the single rhodium complex, the molar ratio of the rhodium reagent to the ligand is 0.5:1, and the reaction time is 0.5-2 hours.

6. The method for preparing pyrrole-modified N-inverted porphyrin monorhodium or dirhodium complexes according to claim 4, characterized in that: When preparing the bis-rhodium complex, the molar ratio of the rhodium reagent to the ligand is 2.0:1 to 3.0:1, and the reaction time is 3-6 hours.

7. The use of the pyrrole-modified N-inverted porphyrin monorhodium complex or bisrhodium complex according to any one of claims 1-3 in the preparation of photodynamic therapy agents.

8. The use of the pyrrole-modified N-inverted porphyrin monorhodium complex or bisrhodium complex according to any one of claims 1-3 in the preparation of photothermal therapeutic agents.

9. The use of the pyrrole-modified N-inverted porphyrin monorhodium complex or bisrhodium complex according to any one of claims 1-3 in the preparation of photodynamic and photothermal synergistic therapeutic agents.

10. The application of the pyrrole-modified N-inverted porphyrin monorhodium complex or bisrhodium complex according to any one of claims 1-3 in green or near-infrared light-driven green oxidation photocatalytic reactions.

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