Application of a cantilevered pyrrole-linked hexaporin dimer in near-infrared photothermal materials

Abstract

This invention discloses the application of cantilevered pyrrole-linked hexaporphyrin dimers in near-infrared photothermal conversion. The cantilevered pyrrole-linked hexaporphyrin fused-ring dimers and hexaporphyrin dimer complexes exhibit strong absorption in the near-infrared II region and demonstrate good photothermal stability. This invention reveals that, compared to hexaporphyrin monomers and directly linked conventional hexaporphyrin dimers, this series of hexaporphyrin dimers can improve photothermal conversion efficiency by 10% to 30% under 1064 nm laser irradiation, with a maximum photothermal efficiency reaching 75.9%. This invention indicates that pyrrole-linked cantilevered hexaporphyrin dimers hold promise for applications in near-infrared photothermal conversion materials, photothermal therapy, and other fields.

Description

Technical Field

[0001] This invention belongs to the field of organic macrocyclic functional materials and photothermal conversion technology, specifically relating to the application of a fused-ring hexaporin dimer and a hexaporin dimer metal complex based on cantilever pyrrole linkage in near-infrared laser-responsive photothermal conversion materials. Background Technology

[0002] Most organic photothermal materials currently on the market and in research have a small absorption cross-section at 1064 nm, resulting in generally low photothermal conversion efficiency. More importantly, organic molecules are prone to photobleaching or structural degradation under continuous high-power laser irradiation, making their cycle stability insufficient for long-term applications. Therefore, finding an organic photosensitive material with a high extinction coefficient, high conversion efficiency, robust framework, and strong resistance at 1064 nm is a bottleneck problem that urgently needs to be solved in the field of functional materials.

[0003] In recent years, porphyrin analogs have been obtained by altering the structure of the porphyrin parent compound, such as extended porphyrins (Chem. Rev. 2017, 117, 2584-2640; Angew. Chem. Int. Ed. 2003, 42, 5134-5175), misaligned porphyrins (Chem. Rev. 2022, 122, 8313−8437; Chem. Soc. Rev. 2023, 52, 2082-2144), and nuclear-modified porphyrins (Chem. Rev. 2017, 117, 3254-3328; Chem. Soc. Rev. 2021, 50). Isoporphyrins (such as 13268-13320) often possess unique structures and diverse conformations, enabling them to achieve near-infrared absorption and other properties, making them a promising class of photoelectric conversion materials. Isoporphyrin dimers, obtained by conjugating two isoporphyrin units, can further expand the conjugated structure of macrocycles and their near-infrared absorption spectra. However, for a long time, the synthesis of isoporphyrin dimers has been difficult, resulting in a limited number of stable isoporphyrin dimers and consequently, relatively limited research on their applications in photothermal conversion and other fields.

[0004] Therefore, developing organic near-infrared II photothermal materials with high extinction, high conversion efficiency, and high stability at 1064nm is a technical bottleneck that needs to be solved in this field. Summary of the Invention

[0005] The purpose of this invention is to develop the application of misaligned hexaporin fused ring dimers and misaligned hexaporin metal complexes based on pyrrole cantilever bonds in photothermal conversion materials.

[0006] Application of a cantilevered pyrrole-linked hexaporin dimer in near-infrared photothermal conversion, the hexaporin dimer including a nickel complex (1-Ni)2, a copper complex (1-Cu)2, a dimer free base (1)2, and a symmetrical dimer (1F)2a and an asymmetrical dimer (1F)2b.

[0007] The structural formula of the hexaporphyrin dimer nickel complex (1-Ni)2 is:

[0008] ;

[0009] The structural formula of the hexaporphyrin dimer copper complex (1-Cu)2 is:

[0010] ;

[0011] The structural formula of the hexaporphyrin demetall dimer (1)2 is:

[0012] ;

[0013] The structural formula of the hexaporphyrin symmetrical dimer (1F)2a is:

[0014] ;

[0015] The structural formula of the hexaporphyrin asymmetric dimer (1F)2b is:

[0016] ;

[0017] As a further improvement of the present invention, the application utilizes the strong absorption characteristics of hexaporphyrin monomers and dimers in the 1000 nm-1350 nm wavelength band to prepare them into a heat-generating material that operates under 1064 nm laser drive.

[0018] The molar extinction coefficients ε of the nickel complex (1-Ni)2, the copper complex (1-Cu)2, the dimer free base (1)2, the symmetrical dimer (1F)2a, and the asymmetrical dimer (1F)2b at 1064 nm are ≥ 0.5 × 10⁻⁶. 4 M - 1 cm -1 .

[0019] As a further improvement of the present invention, this invention discloses the highly efficient photothermal conversion characteristics exhibited by the aforementioned series of hexaporphyrin dimer compounds and their metal complexes under 1064 nm laser driving. This series of compounds achieves precise control of the photothermal conversion efficiency η within the range of 50% to 80% by adjusting the type of central metal and the fusion state of the molecular backbone.

[0020] Specifically, the photothermal conversion performance of the aforementioned series of compounds is as follows:

[0021] The measured photothermal conversion efficiency η of the nickel complex system ((1-Ni)2) reached 66.85%.

[0022] The measured photothermal conversion efficiency η of the copper complex system ((1-Cu)2) reached 61.71%.

[0023] The dimer free base system ((1)2): the measured photothermal conversion efficiency η reached 50.77%;

[0024] Symmetric dimer system ((1F)2a): The measured photothermal conversion efficiency η reached 75.87%;

[0025] The asymmetric dimer system ((1F)2b) achieved a measured photothermal conversion efficiency η of 74.07%.

[0026] As a further improvement of the present invention, the present invention has discovered that the photothermal properties of the series of compounds exhibit a significant parameter dependence law, specifically manifested as follows:

[0027] Concentration regulation: In the concentration range of 25 μM to 100 μM, the equilibrium temperature rise of each compound increased significantly with increasing concentration, which proved the predictability of the material's performance in different application supports;

[0028] Power response law: at 0.5W / cm 2 Up to 1.5 W / cm 2 At the laser power density, all compounds can maintain a stable heat generation rate, and the highest equilibrium temperature increases significantly with increasing power.

[0029] As a further improvement of the present invention, the hexaporphyrin dimer free base (1)2 is formed by the dimerization of hexaporphyrin monomer 1, the hexaporphyrin monomer 1 is formed by the hexaporphyrin monomer precursor 0, the hexaporphyrin dimer nickel complex (1-Ni)2 is formed by the dimerization of the hexaporphyrin monomer nickel complex 1-Ni, the hexaporphyrin dimer copper complex (1-Cu)2 is formed by the dimerization of the hexaporphyrin monomer copper complex 1-Cu, and the near-infrared photothermal conversion material further includes a misaligned hexaporphyrin dimer (2)2 without pyrrole cantilever.

[0030] The structural formula of the pyrrole cantilever hexaporin monomer 1 is as follows:

[0031] ;

[0032] The structural formula of the hexaporphyrin monomer precursor O is:

[0033] ;

[0034] The structural formula of the nickel complex 1-Ni of the hexaporphyrin monomer is:

[0035] ;

[0036] The structural formula of the copper complex 1-Cu of the hexaporphyrin monomer is:

[0037] ;

[0038] The structural formula of the misaligned hexaporin dimer (2)2 without pyrrole cantilevers is:

[0039] ;

[0040] Among them, the molar extinction coefficient ε of the hexaporphyrin monomer 1, the hexaporphyrin monomer precursor 0, the nickel complex 1-Ni of the hexaporphyrin monomer, the copper complex 1-Cu of the hexaporphyrin monomer, and the misaligned hexaporphyrin dimer (2)2 without pyrrole cantilevers at 1064 nm is ≥ 0.5×10 4 M -1 cm -1 .

[0041] As a further improvement of the present invention, this invention discloses the photothermal conversion properties exhibited by the aforementioned series of hexaporphyrin monomers and their metal complexes under 1064nm laser driving. This series of compounds allows for the control of the photothermal conversion efficiency η within the range of 40% to 55%.

[0042] Specifically, the photothermal conversion performance of the aforementioned series of compounds is as follows:

[0043] Hexaporphyrin monomer (1): The measured photothermal conversion efficiency η reached 54.91%;

[0044] Hexaporphyrin monomer precursor (0): The measured photothermal conversion efficiency η reached 40.62%;

[0045] Hexaporphyrin monomer nickel complex (1-Ni): The measured photothermal conversion efficiency η reached 51.40%;

[0046] The hexaporphyrin monomer copper complex (1-Cu): the measured photothermal conversion efficiency η reached 40.13%;

[0047] Conventional misaligned hexaporin dimers without pyrrole cantilever bonds (2)2: The measured photothermal conversion efficiency η reached 41.93%;

[0048] As a further improvement of the present invention, the present invention has discovered that the photothermal properties of the series of compounds exhibit a significant parameter dependence law, specifically manifested as follows:

[0049] Concentration regulation: In the concentration range of 25 μM to 100 μM, the equilibrium temperature rise of each compound increased significantly with increasing concentration, which proved the predictability of the material's performance in different application supports;

[0050] Power response law: at 0.5 W / cm 2 Up to 1.5 W / cm 2 At the laser power density, all compounds can maintain a stable heat generation rate, and the highest equilibrium temperature increases significantly with increasing power.

[0051] Compared to the corresponding hexaporin monomer, the dimer significantly enhances the absorption intensity in the near-infrared II region through the electron delocalization effect mediated by the pyrrole cantilever. By effectively restricting intramolecular vibrations through dimerization, more excited-state energy is converted into heat energy through a non-radioactive decay pathway, thus achieving a leapfrog improvement in photothermal conversion efficiency of 10% to 30% compared to the monomer.

[0052] As a further improvement of this invention, the series of hexaporphyrin dimers and their metal complexes described herein achieve significant optimization of photothermal performance through pyrrole cantilevers. In contrast, the measured photothermal conversion efficiency η of conventional hexaporphyrin dimers without pyrrole cantilevers is only about 40%. This invention discovers that, compared to the conventional hexaporphyrin dimers, the electron delocalization effect mediated by the pyrrole cantilevers significantly enhances the electron transition probability of the molecule in the near-infrared II region, significantly improving the oscillator strength in this band. Simultaneously, the synergistic effect of the pyrrole cantilevers and the dimerization structure effectively restricts harmful vibrations and rotations within the molecule, greatly reducing non-radiative energy loss, allowing more excited-state energy to be efficiently converted into thermal energy through non-radiative decay pathways. Experimental results show that the photothermal conversion efficiency of the series of compounds described in this invention achieves a leapfrog improvement of 10% to 30% from the 40% of the conventional hexaporphyrin dimers, with measured efficiencies reaching 50% to 80%. This significant technological advancement demonstrates the crucial role of pyrrole cantilever in constructing high-performance near-infrared II photothermal materials.

[0053] The beneficial effects of this invention are as follows:

[0054] This invention successfully overcomes the technical bottleneck of insufficient energy conversion efficiency in the near-infrared II region by utilizing the dimerization effect induced by pyrrole cantilever. These compounds exhibit high molar extinction coefficients and excellent photophysical stability. The measured photothermal conversion efficiency η can be precisely controlled within the range of 50% to 80%, representing a significant improvement of 10% to 30% compared to the corresponding hexaporin monomers and conventional hexaporin dimers. This invention comprehensively utilizes ultraviolet and near-infrared absorption spectroscopy, thermocouple temperature measurement, and other methods to systematically explore the mechanism by which molecular configuration regulates energy conversion efficiency, providing important theoretical support and practical solutions for developing high-performance, highly stable, multifunctional near-infrared II active materials.

[0055] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings. Attached Figure Description

[0056] Figure 1 The image shows the ultraviolet and near-infrared absorption spectrum of the hexaporin dimer as presented in this invention.

[0057] Figure 2 The 100 μM hexaporphyrin dimer (1-Ni)2 in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithmic relationship between cooling time and driving force temperature;

[0058] Figure 3 The 100 μM, 50 μM, and 25 μM hexaporphyrin dimer complexes (1-Ni)₂ in Example 1 of this invention are used at 1.0 W / cm². 2 Comparison of heating curves under 1064nm laser;

[0059] Figure 4 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0 W / cm 2 0.5 W / cm 2 Comparison of heating curves of 100 μM hexaporphyrin dimer complex (1-Ni)2 under 1064 nm laser power density;

[0060] Figure 5 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle diagrams of the heating curve and the cooling curve after laser shutdown of 100 μM hexaporphyrin dimer complex (1-Ni)2 under a laser power density of 1064 nm;

[0061] Figure 6 The 100 μM hexaporphyrin dimer complex (1-Cu)2 in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0062] Figure 7 The 100 μM, 50 μM, and 25 μM hexaporphyrin dimer complexes (1-Cu)₂ in Example 1 of this invention are at 1.0 W / cm². 2 Comparison of heating curves under 1064nm laser;

[0063] Figure 8 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm 2 0.5 W / cm 2 100 μM hexaporphyrin dimer complex (1-Cu) at a laser power density of 1064 nm 2 A comparison chart of heating curves;

[0064] Figure 9 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle diagrams of the heating curve and the cooling curve after laser shutdown of 100 μM hexaporphyrin dimer complex (1-Cu)2 under a laser power density of 1064 nm;

[0065] Figure 10 The 100 μM hexaporphyrin dimer (1)2 in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0066] Figure 11 The 100 μM, 50 μM, and 25 μM hexaporphyrin dimer (1)2 in Example 1 of this invention is at 1.0 W / cm 2 Comparison of heating curves under 1064nm laser;

[0067] Figure 12 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm 2 0.5 W / cm 2 A comparison of the heating curves of 100 μM hexaporin dimer (1)2 under a laser power density of 1064 nm;

[0068] Figure 13 In Embodiment 1 of the present invention, at 1.0 W / cm 2Three-cycle diagrams of heating curves and cooling curves after laser shutdown of 100 μM hexaporin dimer (1)2 under 1064 nm laser power density;

[0069] Figure 14 The 100 μM hexaporphyrin dimer (1F)2a in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0070] Figure 15 The 100 μM, 50 μM, and 25 μM hexaporphyrin dimer (1F)2a in Example 1 of this invention are at 1.0 W / cm 2 Comparison of heating curves under 1064nm laser;

[0071] Figure 16 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm 2 0.5W / cm 2 A comparison of the heating curves of 100 μM hexaporphyrin dimer (1F)2a under a laser power density of 1064 nm;

[0072] Figure 17 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle plots of heating curves and cooling curves after laser shutdown for 100 μM hexaporphyrin dimer (1F)2a at a laser power density of 1064 nm;

[0073] Figure 18 The 100 μM hexaporphyrin dimer (1F)2b in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0074] Figure 19 The 100 μM, 50 μM, and 25 μM hexaporphyrin dimer (1F)2b in Example 1 of this invention are at 1.0 W / cm 2 Comparison of heating curves under 1064nm laser;

[0075] Figure 20 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm 2 0.5W / cm 2 A comparison of the heating curves of 100 μM hexaporphyrin dimer (1F)2b under a laser power density of 1064 nm;

[0076] Figure 21 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle plots of heating curves and cooling curves after laser shutdown for 100 μM hexaporphyrin dimer (1F)2b at a laser power density of 1064 nm;

[0077] Figure 22 The 100 μM hexaporphyrin monomer nickel complex 1-Ni in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0078] Figure 23 The 100 μM, 50 μM, and 25 μM hexaporphyrin monomer nickel complexes 1-Ni in Example 1 of this invention are at 1.0 W / cm². 2 Comparison of heating curves under 1064nm laser;

[0079] Figure 24 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm 2 0.5W / cm 2 A comparison of the heating curves of 100 μM hexaporphyrin monomer nickel complex 1-Ni under a laser power density of 1064 nm;

[0080] Figure 25 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle diagrams of the heating curve and the cooling curve after laser shutdown of 100 μM hexaporphyrin monomer nickel complex 1-Ni under a laser power density of 1064 nm.

[0081] Figure 26 The 100 μM hexaporphyrin monomer copper complex 1-Cu in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0082] Figure 27 The 100 μM, 50 μM, and 25 μM hexaporphyrin monomer copper complexes 1-Cu in Example 1 of this invention are at 1.0 W / cm². 2 Comparison of heating curves under 1064nm laser;

[0083] Figure 28 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm 2 0.5W / cm 2A comparison of the heating curves of 100 μM hexaporphyrin monomer copper complex 1-Cu under a laser power density of 1064 nm.

[0084] Figure 29 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle diagrams of the heating curve and the cooling curve after laser shutdown of 100 μM hexaporphyrin monomer copper complex 1-Cu under a laser power density of 1064 nm.

[0085] Figure 30 In Example 1 of this invention, 100 μM hexaporphyrin monomer 1 was used at 1.0 W / cm². 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0086] Figure 31 The 100μM, 50μM, and 25μM hexaporphyrin monomers 1 in Example 1 of this invention are at 1.0 W / cm 2 Comparison of heating curves under 1064nm laser;

[0087] Figure 32 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm 2 0.5 W / cm 2 A comparison of the heating curves of 100 μM hexaporphyrin monomer 1 under a laser power density of 1064 nm;

[0088] Figure 33 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle plots of heating curves and cooling curves after laser shutdown for 100 μM hexaporphyrin monomer 1 at a laser power density of 1064 nm.

[0089] Figure 34 The 100 μM hexaporphyrin monomer precursor in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0090] Figure 35 The 100 μM, 50 μM, and 25 μM hexaporphyrin monomer precursors in Example 1 of this invention were prepared at 1.0 W / cm². 2 Comparison of heating curves under 1064nm laser;

[0091] Figure 36 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm2 0.5W / cm 2 A comparison of heating curves of 100 μM hexaporphyrin monomer precursor 0 under 1064 nm laser power density;

[0092] Figure 37 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle diagrams of the heating curve and the cooling curve after laser shutdown of 100μM hexaporphyrin monomer precursor 0 under a laser power density of 1064nm.

[0093] Figure 38 The 100 μM hexaporphyrin dimer (2)2 in Example 1 of this invention is at 1.0 W / cm 2 Heating curves under 1064nm laser and cooling curves after laser shutdown, as well as the negative natural logarithm relationship between cooling time and driving force temperature;

[0094] Figure 39 The 100μM, 50μM, and 25μM hexaporphyrin dimers (2)2 in Example 1 of this invention are at 1.0W / cm 2 Comparison of heating curves under 1064nm laser;

[0095] Figure 40 In Embodiment 1 of the present invention, at 1.5 W / cm 2 1.0W / cm 2 0.5W / cm 2 A comparison of heating curves of 100 μM hexaporphyrin dimer (2)2 under 1064 nm laser power density;

[0096] Figure 41 In Embodiment 1 of the present invention, at 1.0 W / cm 2 Three-cycle diagrams of heating curves and cooling curves after laser shutdown of 100 μM hexaporin dimer (2)2 under 1064 nm laser power density;

[0097] Figure 42 This is a bar chart comparing the photothermal conversion efficiency η of the compounds of this invention with that of conventional hexaporphyrin dimers and monomers under 1064 nm excitation. Detailed Implementation

[0098] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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.

[0099] Example 1

[0100] This invention provides the following technical solution: a pyrrole cantilever-linked fused-ring hexaporin monomer, comprising hexaporin monomer 1, hexaporin monomer precursor 0, nickel complex 1-Ni, and copper complex 1-Cu.

[0101] The structural formula of hexaporphyrin monomer 1 is:

[0102] ;

[0103] The precursor structure of the hexaporphyrin monomer is:

[0104] ;

[0105] The structural formula of the nickel complex 1-Ni of the hexaporphyrin monomer is as follows:

[0106] ;

[0107] The structural formula of the copper complex 1-Cu of the hexaporphyrin monomer is as follows:

[0108] ;

[0109] Dimers based on hexaporphyrin monomers include nickel complex (1-Ni)2, copper complex (1-Cu)2, free base dimer (1)2, as well as symmetrical dimer (1F)2a and asymmetrical dimer (1F)2b.

[0110] The structural formula of the nickel complex (1-Ni)2 is:

[0111] ;

[0112] The structural formula of the copper complex (1-Cu)₂ is:

[0113] ;

[0114] The structural formula of the free base dimer (1)2 is:

[0115] ;

[0116] The structural formula of the symmetrical dimer (1F)2a is:

[0117] ;

[0118] The structural formula of the asymmetric dimer (1F)2b is:

[0119] ;

[0120] The structural formula of a conventional directly linked misaligned hexaporin dimer (2)2 is as follows:

[0121] .

[0122] Example 2

[0123] This invention also provides the following technical solution: Preparation and absorption spectral characterization experimental methods for a series of hexaporphyrin dimer solutions:

[0124] A series of compounds were prepared: nickel complex (1-Ni)2, copper complex (1-Cu)2, free base dimer (1)2, symmetrical dimer (1F)2a, and asymmetric dimer (1F)2b. Each compound was dissolved in N,N-dimethylformamide (DMF) to prepare a 100 μM solution. Spectroscopic scanning was performed in the range of 300 nm to 1600 nm using a UV-Vis-NIR spectrophotometer.

[0125] Experimental results: Please refer to Figure 1 Experiments revealed that this series of compounds exhibits significant absorption characteristics in the near-infrared II region. Specifically, the molar extinction coefficient at 1064 nm consistently reaches 0.5 × 10⁻⁶. 4 M -1 cm -1 This demonstrates the physical basis of this series of compounds as 1064nm laser-responsive materials.

[0126] Example 3

[0127] This invention also provides the following technical solution: an experimental method for evaluating the photothermal conversion efficiency of a series of compounds under 1064 nm excitation:

[0128] A series of compounds were taken: hexaporphyrin monomer 1, hexaporphyrin monomer precursor 0, nickel complex 1-Ni, copper complex 1-Cu, hexaporphyrin dimer nickel complex (1-Ni)2, hexaporphyrin dimer copper complex (1-Cu)2, dimer free base (1)2, symmetrical dimer (1F)2a, asymmetrical dimer (1F)2b, and conventional misaligned hexaporphyrin dimer (2)2 without pyrrole cantilevers. These were dissolved in N,N-dimethylformamide (DMF) as solvent to prepare 100 μM test solutions. A 1064 nm laser was used at 1.0 W / cm². 2 The solution was continuously irradiated with a power density. The temperature change of the solution from the initial room temperature to thermal equilibrium was recorded in real time using a thermocouple thermometer, and its natural cooling curve was recorded after the laser was turned off.

[0129] This embodiment uses compound (1-Ni)2 as an example to explain in detail the calculation process of photothermal conversion efficiency. The calculation methods for the other compounds (0, 1, 1-Ni, 1-Cu, (1)2, (1-Cu)2, (1F)2a, (1F)2b, (2)2) are the same.

[0130] According to the principle of energy balance, the photothermal conversion efficiency η is calculated using the following formula:

[0131] ;

[0132] The meanings of each parameter are as follows:

[0133] h: heat transfer coefficient;

[0134] A: Surface area of ​​the container;

[0135] The highest equilibrium temperature reached by the solution;

[0136] Ambient temperature;

[0137] The heat generated by the solvent (dichloromethane) and the quartz cuvette was obtained by separately testing the temperature rise of the pure solvent under the same conditions.

[0138] I: Output power of the laser;

[0139] : The absorbance of the solution to be tested at 1064 nm.

[0140] To obtain the value of hA, this invention introduces a system time constant. During the cooling phase after the laser is turned off, the system satisfies the following linear relationship:

[0141] ;

[0142] The dimensionless parameter θ is defined as follows:

[0143] ;

[0144] By analyzing the cooling curve Perform linear fitting with time t, see details. Figure 4 The negative reciprocal of the slope is the system time constant. Then calculate according to the following formula. :

[0145] ;

[0146] in, and The amounts of the solvent DMF used were 0.948 g and the specific heat capacity was 2.38 J / (g·℃), respectively.

[0147] The calculation example and results use a 100 μM (1-Ni)₂ solution as an example. The measured parameters are as follows: ambient temperature. =20.9 ℃, highest equilibrium temperature = 57.3 ℃; absorbance = 0.372; obtained by fitting the cooling curve. =187.65s; calculated = 12.02 mW / ℃.

[0148] Substituting the above parameters into the efficiency calculation formula, the efficiency evaluation results of this series of compounds are shown in the table below:

[0149]

[0150] Experimental data: Please refer to Figure 2 , Figure 6 , Figure 10 , Figure 14 , Figure 18 , Figure 22 , Figure 26 , Figure 30 , Figure 34 and Figure 38 Based on the heating-cooling curves and energy balance equations, the photothermal conversion efficiencies of each compound under 1064 nm excitation were calculated as follows:

[0151] The measured photothermal conversion efficiency η of the nickel complex system ((1-Ni)2) reached 66.85%.

[0152] The measured photothermal conversion efficiency η of the copper complex system ((1-Cu)2) reached 61.71%.

[0153] The dimer free base system ((1)2): the measured photothermal conversion efficiency η reached 50.77%;

[0154] Symmetrical fused-ring dimer system ((1F)2a): The measured photothermal conversion efficiency η reached 75.87%; Asymmetric fused-ring dimer system ((1F)2b): The measured photothermal conversion efficiency η reached 74.07%;

[0155] Hexaporphyrin monomer (1): The measured photothermal conversion efficiency η reached 54.91%;

[0156] Hexaporphyrin monomer precursor (0): The measured photothermal conversion efficiency η reached 40.62%;

[0157] Hexaporphyrin monomer nickel complex (1-Ni): Measured photothermal conversion efficiency η reaches 51.40%.

[0158] The hexaporphyrin monomer copper complex (1-Cu): the measured photothermal conversion efficiency η reached 40.13%;

[0159] Conventional misaligned hexaporin dimer without pyrrole cantilever (2)2: The measured photothermal conversion efficiency η reached 41.93%.

[0160] Experimental results show that the dimers of this series of compounds have excellent photothermal conversion capabilities, with an overall photothermal conversion efficiency that is about 10% to 30% higher than that of monomers and conventional misaligned hexaporin dimers without pyrrole cantilevers.

[0161] Example 4

[0162] Concentration dependence of photothermal performance and power response experiments; concentration gradient experiments: please refer to [link / reference]. Figure 3 , Figure 7 , Figure 11 , Figure 15 , Figure 19 , Figure 23 , Figure 27 , Figure 31 , Figure 35 and Figure 39 Prepare solutions of 100 μM, 50 μM, and 25 μM respectively. (The solution is then dissolved in water at a concentration of 1.0 W / cm².) 2 At a laser power of 1064 nm, a significant increase in equilibrium temperature was observed with increasing concentration in all cases.

[0163] Power gradient experiment: Please refer to Figure 4 , Figure 8 , Figure 12 , Figure 16 , Figure 20 , Figure 24 , Figure 28 , Figure 32 , Figure 36 and Figure 40 With the solution concentration fixed at 100 μM, the 1064 nm laser power density was adjusted to 0.5, 1.0, and 1.5 W / cm², respectively. 2 Experimental results show that the heating rate and the maximum equilibrium temperature increase significantly with increasing laser power, proving that the materials all have good light intensity response sensitivity.

[0164] Example 5

[0165] Experimental method for evaluating the photothermal cycling stability under high-intensity excitation: 100 μM of a series of compounds including hexaporphyrin monomer 1, hexaporphyrin monomer precursor 0, nickel complex 1-Ni, copper complex 1-Cu, hexaporphyrin dimer nickel complex (1-Ni)2, hexaporphyrin dimer copper complex (1-Cu)2, dimer free base (1)2, symmetrical fused-ring dimer (1F)2a, asymmetric fused-ring dimer (1F)2b, and conventional hexaporphyrin dimer (2)2 without pyrrole cantilevers were subjected to a photothermal cycling reaction at 1.0 W / cm². 2 Three consecutive heating-cooling cycles were conducted at the specified power density. During each cycle, the solution was heated to thermal equilibrium and then allowed to cool naturally to room temperature.

[0166] Experimental data: Please refer to Figure 5 , Figure 9 , Figure 13 , Figure 17 , Figure 21 , Figure 25 , Figure 29 , Figure 33 , Figure 37 and Figure 41 During the three cycles, the maximum temperature rise of the solution fluctuated within 2°C. Conclusion: This experiment demonstrates that the materials of this invention possess excellent physical stability and can withstand repeated irradiation by high-power lasers without performance degradation.

[0167] Example 6

[0168] Under the same conditions, the photothermal conversion efficiency η of the compounds of this invention compared with that of conventional hexaporphyrin dimers and monomers under 1064 nm excitation was evaluated: Please refer to [link to relevant documentation]. Figure 42 The bar chart visually illustrates the photothermal conversion performance of the series of compounds described in this invention under 1064nm laser driving. As can be seen from the figure, the photothermal conversion efficiency η of the series of compounds described in this invention is between 50% and 80%. Compared with conventional hexaporin dimers and hexaporin monomers without pyrrole cantilever linkages, the energy conversion capability of the dimer system of this invention achieves a significant improvement of 10% to 30%.

[0169] The bar chart clearly shows that the hexaporin dimers linked by pyrrole cantilever bonds have high photothermal conversion efficiency, indicating that increased molecular skeleton conjugation significantly enhances photothermal conversion efficiency. Among them, the fused-ring hexaporin dimers (1F)2a and (1F)2b have the highest photothermal conversion efficiency, reaching 77.07% and 75.87%, respectively.

[0170] In summary, by comparing the efficiency of conventional hexaporin, cantilevered pyrrole hexaporin monomers and their complexes, the following conclusions can be drawn:

[0171] 1. The efficiency of hexaporin monomers containing pyrrole cantilevers is better than that of conventional hexaporin monomers, indicating that the introduction of cantilever pyrrole units leads to increased molecular flexibility, which is beneficial to improving the proportion of nonradiative transitions.

[0172] 2. The free base efficiency of hexaporphyrin monomers and directly linked dimers is not significantly different because the two monomers of the dimer are orthogonally linked, which has little impact on electron transport performance.

[0173] 3. The efficiency of fused-ring hexaporphyrin dimer: Since the dimer is free base, it indicates that the rigid fused-ring structure within the molecule can effectively suppress energy loss during nonradiative transitions.

[0174] 4. Hexaporphyrin dimer complexes are more efficient than dimer free bases, while hexaporphyrin monomer free bases are more efficient than their corresponding complexes. This is because energy dissipation in dimers is mainly due to nonradiative transitions, and metal coordination promotes molecular rigidity and electron transfer, thus reducing energy dissipation. In contrast, energy dissipation in hexaporphyrin monomers includes nonradiative transitions and triplet intersystem crossings. Metal coordination increases the proportion of triplet intersystem crossings while decreasing the proportion of nonradiative transitions, ultimately reducing photothermal conversion efficiency.

[0175] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0176] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. The application of a cantilevered pyrrole-linked hexaporin dimer in near-infrared photothermal conversion, characterized in that: The hexaporphyrin dimer and its metal complex are selected from at least one of the following compounds: nickel complex (1-Ni)2, copper complex (1-Cu)2, hexaporphyrin dimer free base (1)2, and symmetrical dimer (1F)2a and asymmetrical dimer (1F)2b.

2. The structural formula of the hexaporphyrin dimer nickel complex (1-Ni)2 is: ； The structural formula of the hexaporphyrin dimer copper complex (1-Cu)2 is: ； The structural formula of the hexaporphyrin dimer free base (1)2 is: ； The structural formula of the symmetrical hexaporphyrin fused-ring dimer (1F)2a is: ； The structural formula of the asymmetric hexaporphyrin fused-ring dimer (1F)2b is: 。 3. The application according to claim 1, characterized in that: The hexaporphyrin dimer free base (1)2 is formed by the dimerization of hexaporphyrin monomer 1, the hexaporphyrin dimer nickel complex (1-Ni)2 is formed by the dimerization of the nickel complex 1-Ni of the hexaporphyrin monomer, and the hexaporphyrin dimer copper complex (1-Cu)2 is formed by the dimerization of the copper complex 1-Cu of the hexaporphyrin monomer. The structural formula of the hexaporphyrin monomer 1 is: ； The structural formula of the hexaporphyrin monomer precursor 0 of the hexaporphyrin monomer 1 is as follows: ； The structural formula of the nickel complex 1-Ni of the hexaporphyrin monomer is: ； The structural formula of the copper complex 1-Cu of the hexaporphyrin monomer is: 。 4. The application according to claim 1, characterized in that: The photothermal conversion material is a photoresponsive material that has a certain absorption capacity for lasers with wavelengths of 1000nm-1350nm.

5. The application according to claim 3, characterized in that: The preferred response wavelength of the photothermal conversion material is 1064 nm.

6. The application according to claim 2, characterized in that: The photothermal conversion material has a photothermal conversion efficiency η of 40%~60% under 1064 nm laser irradiation.

7. The application according to claim 1, characterized in that: The photothermal conversion material has a photothermal conversion efficiency η of 50%~80% under 1064nm laser irradiation.

8. The hexaporphyrin dimer according to claim 1, characterized in that: The photothermal conversion efficiency of the hexaporin dimer at 1064 nm is 10% to 30% higher than that of conventional hexaporin dimers with similar structures but without pyrrole cantilever bonds under the same test conditions.

9. The application according to claim 7, characterized in that: The structural formula of the conventional misaligned hexaporin dimer (2)2 without pyrrole cantilever bonds is: 。

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