CN104744481A - Sandwich-type phthalocyanine metal complex with red-to-yellow weak light upconversion characteristics - Google Patents

Abstract

The invention belongs to the field of triplet annihilation upconversion, and specifically relates to a sandwich-type phthalocyanine metal complex with red-to-yellow weak light upconversion characteristics, which effectively improves the solubility of metal phthalocyanine. The first layer and the third layer of the sandwich-type phthalocyanine metal complex of the present invention are a phthalocyanine macrocycle, and the second layer is the central metal atom Pd/Pt, which are directly connected to each other by a coordination bond. These three planes A three-dimensional molecule in space is formed. The sandwich-type phthalocyanine metal complex of the present invention has a longer triplet state lifetime, and has a strong absorption capacity for visible light and near-infrared light, and is used as a sensitizer in triplet annihilation up-conversion materials, which is beneficial to the up-conversion materials for up-conversion materials. Weak light, especially the use of sunlight; as a sensitizer, the pump light intensity of the bimolecular triplet annihilation upconversion system is less than 50 mW×cm ^-2 , under the excitation of ordinary laser pointers or even sunlight The upconversion fluorescence can be obtained, and the application of the triplet annihilation upconversion system is expanded.

Description

Sandwich-type phthalocyanine metal complexes with red-to-yellow weak-light upconversion properties

technical field

The invention belongs to the field of triplet annihilation upconversion, and specifically relates to a sandwich type phthalocyanine metal complex and its application as a sensitizer material in a triplet annihilation upconversion two-component system.

Background technique

Triplet-triplet annihilation upconversion (TTA-UC) is a multi-quantum process, which usually requires mixing a sensitizer and a luminescent agent together to form a triplet annihilation upconversion two-component system, based on a triplet sensitizer and a triplet Produced by the interaction between the molecules of the luminescent agent, it is a process of converting low-energy (long-wavelength) light into high-energy (short-wavelength) light. The process is: i), the sensitizer first absorbs a photon to reach the excited state and then reaches its triplet state through intersystem crossing (ISC); ii), then a triplet-triplet state occurs between the sensitizer and the luminescent agent energy transfer (TTT); iii), two triplet luminescent agents undergo triplet-triplet annihilation (TTA) and emit upconversion fluorescence. The whole TTA up-conversion process is: when the sensitizer photon is in the ground state, it absorbs energy and is excited to the singlet excited state, which passes through intersystem crossing to the triplet excited state, and passes through the triplet-triplet state energy transfer. When the energy is transferred to the acceptor (luminescent agent) photon (the photon of the sensitizer needs to collide with the luminescent agent to transfer energy), making it reach the triplet excited state, when the photon of the luminescent agent in the triplet excited state reaches a certain concentration, two The luminescent photons in the triplet excited state pass through the triplet-triplet annihilation (mutual collision), and at a certain probability, one luminescent photon in the singlet excited state will be generated, and the other will return to the ground state, at this time in the singlet The photons of the luminescent agent in the excited state emit fluorescence and return to the ground state.

The triplet-triplet annihilation upconversion (TTA-UC) has many advantages. First, the excitation power density required for TTA upconversion is quite low, usually with mW/ ^cm2 order of light intensity density excitation, and sunlight can be used as TTA Excitation light source for upconversion; moreover, excitation and emission wavelengths for TTA upconversion are easily tuned. Therefore, TTA upconversion has attractive application prospects in solar energy utilization (such as photovoltaics, photocatalytic synthesis, and photodegradation, etc.).

In 2006, Baluschev of the Max Planck Institute in Germany reported for the first time that the frequency upconversion of incoherent light (< 10 W×cm ^-2 ) (external quantum efficiency greater than 1%) was achieved by using the metastable triplet state of dye molecules. The research results can convert the low-frequency waves of sunlight into high-frequency light waves, which is a new step for the utilization of sunlight. If this kind of sunlight "up-conversion" system is combined with solar cells, more solar energy can be stored , can benefit organic photovoltaic solar panels (see: S. T. Baluschev, V Miteva, G. Yakutkin, et al, Physical Review Lett., 2006, 6: 143903); The two-component system of excited metal porphyrin/anthracene derivatives obtained an up-conversion with an external quantum efficiency of 3.2%. An upconversion efficiency of 6.8% was obtained; in 2009, Chen from the Chow Research Group of the University of Cambridge irradiated a two-component mixed system of fluorone derivatives/9,10-diphenylanthracene with a laser with a wavelength of 532 nm, and obtained an efficiency of up to 1% upconverted fluorescence (see: M. J. Michael, J. K. M. Mapel, T. D. Heidel et al, Science, 2008, 321: 226; T. Miteva, V. Yakutkin, G. Nelles, S. Baluschev, New Journal of Physics, 2008 , 10: 103002; H. C. Chen, CY. Hung, KH Wang, et al, Chem. Commun., 2009, 4064).

The solar spectrum covers a wide range of wavelengths, and 99% of the energy in its electromagnetic radiation is concentrated in the infrared and visible light regions. The former accounts for about 50% of the total energy of solar radiation, and the latter accounts for about 43%. It is extremely important to make full use of the near-infrared band in solar energy as an effective light source for weak light up-conversion. Phthalocyanine complexes have good catalytic activity due to their special structure. From the structural point of view, they have the following characteristics: the aromatic π electrons are conjugated on the entire porphyrazine ring, and the hole located in the center of the ring can It accommodates a variety of metal elements, and the metal elements can form complexes with phthalocyanine; the conjugated macromolecule presents a high degree of planarity, and the catalytic reaction can take place in the axial position of the plane. With the development of science and technology, metal phthalocyanine complexes have been gradually synthesized, and have aroused people's research enthusiasm in the fields of electrochromism and semiconductor conductance. However, the solubility of existing phthalocyanines and metallophthalocyanines is very poor, which greatly limits their applications.

At present, there are no reports on palladium/platinum three-dimensional structure phthalocyanine complexes, and there is no report on the application of palladium/platinum three-dimensional structure phthalocyanine complexes in the field of triplet annihilation upconversion.

Contents of the invention

The purpose of the present invention is to provide two kinds of palladium/platinum phthalocyanine complexes with three-dimensional structure, which solves the problem of poor solubility of metal phthalocyanines, while retaining the excellent triplet properties of heavy metal phthalocyanines; this type of metal complexes is disclosed for the first time Sensitizer for triplet annihilation upconversion materials. The triplet annihilation upconversion material prepared by using the three-dimensional palladium/platinum phthalocyanine complex as a sensitizer realizes red-to-yellow weak light upconversion, and has potential application prospects in the field of solar energy utilization.

In order to achieve the above-mentioned purpose of the invention, the technical scheme adopted in the present invention is:

A sandwich type phthalocyanine metal complex, its general structural formula is as follows:

Wherein R is selected from hydrogen, nitro, methyl, carboxyl or chlorine; M is a metal atom selected from palladium or platinum.

In the present invention, the sandwich-type phthalocyanine metal complex is a three-dimensional structure, which can be roughly divided into three plane layers. The first layer and the third layer are a phthalocyanine macrocycle, and the second layer is the central metal atom Pd/Pt. Directly connected to each other by coordination bonds, these three planes form a three-dimensional molecule in space, that is, sandwich-type phthalocyanine metal complexes.

The preparation method of the above-mentioned sandwich-type phthalocyanine metal complex is: in a nitrogen atmosphere, under the action of a catalyst, in an organic solvent, phthalonitrile derivatives are reacted with a metal compound to obtain a sandwich-type phthalocyanine metal complex ;

The metal compound is: palladium acetylacetonate, potassium chloroplatinate;

The catalyst is: 1,8-diazabicycloundec-7-ene;

The boiling point of the organic solvent is 130°C to 150°C;

The structural formula of the phthalonitrile derivatives is: .

In the above preparation method, the reaction conditions are: in a nitrogen atmosphere, using phthalonitrile derivatives as raw materials, under the action of catalyst 1,8-diazabicycloundec-7-ene (DBU) Then, respectively react with palladium acetylacetonate or potassium chloroplatinate under reflux in an organic solvent for 24 hours to obtain a metal phthalocyanine complex with a three-dimensional structure. The solubility of the prepared sandwich-type phthalocyanine Pd/Pt complex is greatly improved compared with that of the single-layer phthalocyanine metal complex.

The organic solvent is n-amyl alcohol.

Sandwich-type phthalocyanine metal complexes can realize the conversion of red light (long wavelength) to yellow light (short wavelength) in triplet annihilation up-conversion, so the present invention also discloses the above-mentioned sandwich-type phthalocyanine metal complexes in the preparation of triplet states Applications in annihilation upconversion materials. The triplet annihilation up-conversion material is a triplet annihilation up-conversion material that converts red light into yellow light.

The invention further discloses a triplet annihilation upconversion two-component system, which includes a sensitizer and a luminescent agent, and the sensitizer is the above-mentioned sandwich-type phthalocyanine metal complex.

The luminescent agent is not particularly limited, and those skilled in the art can choose by themselves according to needs. It can be rubrene, and its structural formula is as follows:

It can also be anthracene-boron fluoride, whose structural formula is:

In the above technical solution, the molar ratio of the luminescent agent to the sensitizer is 1:250-2500.

In the triplet annihilation up-conversion two-component system of the present invention, the long-wavelength light is converted into short-wavelength light through the triplet state transfer between the sensitizer and the luminescent agent molecules. This process is called frequency up-conversion (also known as frequency up-conversion) triplet annihilation upconversion), this process can be converted from low-frequency red light to high-frequency yellow light only by excitation of a weak light field (< 100 mW×cm ^-2 ).

Owing to above-mentioned technical scheme uses, the present invention has following advantage compared with prior art:

1. The sandwich-type phthalocyanine metal complex disclosed by the present invention has a longer triplet lifetime, and has a strong absorption capacity for visible light and near-infrared light. As a sensitizer in triplet annihilation upconversion materials, it can realize red- Turn-yellow weak light up-conversion is beneficial to the use of up-conversion materials for low light, especially sunlight.

2. The light intensity of the pump light source of the bimolecular triplet annihilation up-conversion system disclosed by the invention as a sensitizer is less than 100 mW×cm ^-2 , which greatly expands the application of the triplet annihilation up-conversion system .

3. The sandwich-type phthalocyanine metal complex of the present invention has good solubility, and the actual concentration of the prepared solution can reach 1×10 ^-3 mol/L; overcomes the insoluble shortcoming of the phthalocyanine metal complex in the prior art; improves The energy transfer between the luminescent agent and the sensitizer further increases the upconversion efficiency of the triplet annihilation upconversion system.

4. The raw materials such as reactants used in the invention are cheap and easy to obtain, no pollutants are discharged, the requirements and direction of the development of contemporary green chemistry are met, the preparation process is simple, and the method is suitable for industrial production.

Description of drawings

Fig. 1 is the MALDI-TOF mass spectrogram of sandwich type phthalocyanine metal complex in embodiment one;

Fig. 2 is the MALDI-TOF mass spectrogram of sandwich type phthalocyanine metal complex in embodiment two;

Fig. 3 is the thermal weight loss curve figure of sandwich type phthalocyanine metal complex in the embodiment;

Fig. 4 is the infrared spectrogram of sandwich type phthalocyanine metal complex in the embodiment;

Fig. 5 is the normalized absorption and emission spectrogram of the sandwich type phthalocyanine metal complex in the embodiment;

Fig. 6 is the biexponential fitting sensitizer phosphorescence decay curve of the sandwich type phthalocyanine metal complex in the embodiment;

Figure 7 is a diagram showing the solubility properties of sandwich-type phthalocyanine metal complexes in the examples;

Fig. 8 is the actual picture of the up-conversion test of the PdPc ₂ /Rubrene two-component system in Example 3;

Fig. 9 is the upconversion spectrum of the PdPc ₂ /Rubrene two-component system in Example 3 changing with the concentration of the luminescent agent;

Fig. 10 is the upconversion spectrum of the PdPc ₂ /Rubrene two-component system in Example 3 changing with the power density of the excitation light source;

Fig. 11 is the actual picture of the up-conversion test of the PtPc ₂ /Rubrene two-component system in Example 4;

Fig. 12 is the upconversion spectrum of the PtPc ₂ /Rubrene two-component system in Example 4 varying with the concentration of the luminescent agent;

Fig. 13 is the upconversion spectrum of the PtPc ₂ /Rubrene two-component system in Example 4 varying with the power density of the excitation light source;

Fig. 14 is a graph showing the variation of the up-conversion spectrum of the PdPc ₂ /anthracene-boron fluoride two-component system with the power density of the excitation light source in Example 5.

Detailed ways

Below in conjunction with accompanying drawing and embodiment the present invention will be further described:

In this example, the measurement of thermogravimetric performance: measured on Beijing constant rapid temperature rise thermogravimetric analyzer HKG, the temperature corresponding to the intersection point of the horizontal tangent line of thermogravity loss and the tangent line at the time of fastest weight loss is the critical decomposition temperature. Determination of infrared spectrum: measured on ATR-FTAK Nicolet Fourier transform infrared spectrometer. Determination of excitation, emission spectra and lifetime: measured on Edinburgh FLS 920 fluorophotometer, the thickness of the cuvette is 1 cm, and the test solvents are spectral grade chloroform.

Example 1 Preparation of sandwich palladium phthalocyanine complex (PdPc ₂ )

Weigh 0.9 g of phthalonitrile and 40 mL of n-amyl alcohol into a three-necked flask, and heat with stirring until they are completely dissolved. Then weigh 0.25 g of palladium acetylacetonate and add it to the three-necked flask, and finally add the catalyst DBU with a volume of 0.4 mL. Under the protection of nitrogen, it was heated to reflux temperature and reacted for 24 hours. The reaction system turned blue-black. Spot plate traced the complete reaction of phthalonitrile and palladium acetylacetonate. The solvent n-pentanol was distilled off under reduced pressure, separated by column chromatography, and the mobile phase was CHCl3:Hexane=5:1. After purification, 0.68 g of blue-black solid powder was obtained, with a yield of about 59%. Accompanying drawing 1 is the MALDI-TOF mass spectrogram of the above-mentioned sandwich-type phthalocyanine metal complex, and the molecular mass obtained by the MALDI-TOF mass spectrometry is 1130. Lifetime: 3.0099μs accounted for 15.82%, 16.8535μs accounted for 84.18%.

Example 2 Preparation of Sandwich Platinum Phthalocyanine Complex (PtPc ₂ )

Weigh 0.9 g of phthalonitrile and 40 mL of n-amyl alcohol into a three-necked flask, and heat with stirring until they are completely dissolved. Then weigh 0.29 g of potassium chloroplatinate and add it to the three-necked flask, and finally add the catalyst DBU with a volume of 0.4 mL. Under the protection of nitrogen, it was heated to reflux temperature and reacted for 24 hours. The reaction system turned blue-black. The solvent n-pentanol was distilled off under reduced pressure, separated by column chromatography, and the mobile phase was CHCl ₃ :Hexane=5:1. After purification, 0.52 g of blue-black solid powder was obtained, with a yield of about 43.6%. Accompanying drawing 2 is the MALDI-TOF mass spectrogram of above-mentioned sandwich type phthalocyanine metal complex; MALDI-TOF mass spectrometry obtains molecular mass 1219. Lifetime: 2.3474 μs accounted for 7.91%, 14.7226 μs accounted for 92.09%.

Accompanying drawing 3 is the thermal weight loss curve figure of above-mentioned sandwich type phthalocyanine palladium/platinum complex; It can be seen that PdPc ₂ initial decomposition temperature and complete decomposition temperature are 435 ℃, 524 ℃ respectively; PtPc ₂ initial decomposition temperature and complete decomposition temperature The decomposition temperatures are 415°C and 475°C respectively. It can be seen that the decomposition temperature is much higher than that of ordinary organic compounds, and when the critical decomposition temperature is reached, the complex of the present invention remains the same, indicating that the complex has excellent thermal stability.

Accompanying drawing 4 is the infrared spectrogram of the above-mentioned sandwich-type phthalocyanine palladium/platinum complex; it can be seen that in PdPc ₂ , 1513 is C=C, 1615 is C=N, and 3289 is CH. 723, 754, 866, 1012, and 1126 belong to the vibration absorption peaks of the phthalocyanine ring skeleton. In PtPc ₂ , 1513 is C=C, 1645 is C=N, and 3430 is CH. 709, 730, 873, 1002, and 1118 belong to the vibration absorption peaks of the phthalocyanine ring skeleton.

Accompanying drawing 5 is the absorption and emission spectrum of the above-mentioned sandwich-type phthalocyanine palladium/platinum complex (trichloromethane solvent, 10 mM). It can be seen that the B-band absorption peak of PdPc ₂ is at 340 nm, the Q-band absorption is at 597-656 nm, and the fluorescence emission peak is at 697 nm. The B-band absorption peak of PtPc ₂ is at 340 nm, the Q-band absorption peak is at 595-656 nm, and the fluorescence emission peak is at 692 nm.

Figure 6 shows the phosphorescence decay curve of the above-mentioned sandwich-type phthalocyanine palladium/platinum complex; the long phosphorescence lifetime of PdPc ₂ is 16.85 μs (accounting for 84.18%), and the long phosphorescence lifetime of PdPc ₂ is 14.72 μs (accounting for 92.09%).

Accompanying drawing 7 is the comparison test of the solubility of single-layer structure PdPc (that is, a complex formed by a phthalocyanine ring and a palladium ion) and the sandwich structure palladium/platinum phthalocyanine (PdPc ₂ and PtPc ₂ ) provided by the present invention. It can be seen that at the same molar concentration, the monolayer structure of PdPc is insoluble in chloroform solvent and is in a dispersed state; the sandwich structure of palladium/platinum phthalocyanine (PdPc ₂ and PtPc ₂ ) has good solubility in chloroform solvent , to obtain a uniform and stable solution with a maximum dissolved concentration of 1mM.

Example 3 Preparation and testing of sensitizer/luminescent agent binary triplet annihilation system

PdPc ₂ acts as a triplet sensitizer, while rubrene (Rubrene) acts as a triplet luminescent agent. The solvent used in the test is chloroform.

A mixed upconversion solution was prepared, in which PdPc ₂ was 4×10 ^-6 mol/L, Rubrene was 1×10 ^-2 mol/L, mixed and dissolved in spectral grade chloroform.

The mixed solution was placed in a quartz cuvette with a light path of 1 cm. After degassing pretreatment, under the excitation of a red laser (634 nm, power density 35 mW/cm ² ), the red fluorescence of the two-component system was tested. Upconversion spectra of ene/ _PdPc2 . Figure 8 is a view of triplet annihilation upconversion of the two-component system PdPc ₂ /Rubrene after removing the excitation light source through a 634 nm monochromatic filter, and the yellow fluorescence can be clearly seen, showing that the two-component system has achieved red conversion Yellow weak light up conversion.

Figure 9 is the measurement of the two-component system of the sensitizer PdPc ₂ (4×10 ^-6 mol/L) and different concentrations of rubrene (increased from 0 mM to 9 mM) in the deoxygenated chloroform under the incident laser Upconversion relationship under source (634 nm) excitation. As the concentration of rubrene increases from 0 mM to 9 mM, it can be observed that the intensity of upconversion from red (634 nm) to yellow photons (600 nm) increases sequentially.

By changing the power density of the excitation light source from 10.89 mW/cm ² to 34.13 mW/cm ² , the relationship between the power density of the incident light source (634 nm) and the upconversion intensity of the two-component system was measured. Accompanying _drawing ¹⁰ is to measure in the incident light source ⁽ 634 nm) power density versus upconversion intensity. As the power density of the excitation light source increases from 10.89 mW/cm ² to 34.13 mW/cm ² , it can be observed that the intensity of the upconverted photons from red (634 nm) to yellow (600 nm) increases sequentially.

Example 4 Preparation and testing of sensitizer/luminescent agent binary triplet annihilation system

PtPc ₂ acts as a triplet sensitizer, while rubrene (Rubrene) acts as a triplet luminescent agent. The solvent used in the test is chloroform.

Prepare a mixed upconversion solution, in which PtPc ₂ is 4×10 ^-6 mol/L, Rubrene is 1×10 ^-2 mol/L, mixed and dissolved in spectral grade chloroform.

The mixed solution was placed in a quartz cuvette with a light path of 1 cm. After degassing pretreatment, under the excitation of a red laser (634 nm, power density 35 mW/cm ² ), the red fluorescence of the two-component system was tested. Upconversion spectra of ene/ _PtPc2 . Accompanying drawing 11 is the physical picture of the triplet annihilation upconversion of the two-component system PtPc ₂ /Rubrene. After removing the excitation light source through a 634 nm monochromatic filter, the yellow upconversion fluorescence can be clearly seen, showing that the two-component system has achieved low-light up-conversion.

Accompanying drawing ₁₂ is the ^measurement of the incident laser Upconversion relationship under source (634 nm) excitation. As the concentration of rubrene increases from 0 mM to 9 mM, it can be observed that the intensity of upconversion from red (634 nm) to yellow photons (600 nm) increases sequentially.

By changing the power density of the excitation light source from 10.89 mW/cm ² to 34.13 mW/cm ² , the relationship between the power density of the incident light source (634 nm) and the upconversion intensity of the two-component system was measured. Accompanying drawing 13 is the measurement of the two-component system of rubrene (10×10 ^-3 mol/L) and sensitizer PtPc ₂ (4×10 ^-6 mol/L) in deoxygenated chloroform under the incident light source ( 634 nm) power density versus upconversion intensity. As the power density of the excitation light source increases from 10.89 mW/cm ² to 34.13 mW/cm ² , it can be observed that the intensity of the upconverted photons from red (634 nm) to yellow (600 nm) increases sequentially.

Example 5 Preparation and testing of sensitizer/luminescent agent binary triplet annihilation system

PdPc ₂ acts as a triplet sensitizer, while anthracene-boron fluoride acts as a triplet emitter. The solvent used in the test is chloroform.

A mixed upconversion solution was prepared, in which the concentration of PdPc ₂ was 4×10 ^-6 mol/L, and the concentration of anthracene-boron fluoride was 1×10 ^-3 mol/L, which were mixed and dissolved in spectral grade chloroform.

The mixed solution was placed in a quartz cuvette with an optical path of 1 cm. After degassing pretreatment, the ^two -component system anthracene- Upconversion spectra of boron fluorine derivatives/PdPc ₂ , measured at 600 nm. And by changing the power density of the excitation light source from 10.89 mW/cm ² to 34.13 mW/cm ² , the relationship between the power density of the incident light source (634 nm) and the upconversion intensity of the two-component system was measured. Accompanying drawing 14 is the measurement of the two-component system of anthracene-boron fluorine derivative (10×10 ^-3 mol/L) and sensitizer PdPc ₂ (4×10 ^-6 mol/L) in deoxygenated chloroform in The power density of the incident light source (634 nm) as a function of the upconversion intensity. As the power density of the excitation light source increases from 10.89 mW/cm ² to 34.13 mW/cm ² , it can be observed that the intensity of the upconverted photons from red (634 nm) to yellow (600 nm) increases sequentially.

Replace phthalonitrile with the remaining phthalonitrile derivatives:

According to the preparation method of Example 1 or Example 2, sandwich-type phthalocyanine metal complexes with different substituents can be obtained:

Wherein R is nitro, methyl, carboxyl or chlorine; M is palladium or platinum.

Example 6 Preparation and testing of sensitizer/luminescent agent binary triplet annihilation system

PtPc ₂ acts as a triplet sensitizer, while rubrene (Rubrene) acts as a triplet luminescent agent. The solvent used in the test is chloroform. The structural formula of PtPc ₂ is:

Prepare a mixed upconversion solution, in which PtPc ₂ is 4×10 ^-6 mol/L, Rubrene is 1×10 ^-2 mol/L, mixed and dissolved in spectral grade chloroform.

The mixed solution was placed in a quartz cuvette with a light path of 1 cm. After degassing pretreatment, under the excitation of a red laser (634 nm, power density 35 mW/cm ² ), the red fluorescence of the two-component system was tested. Upconversion spectra of ene/ _PtPc2 . According to the physical map of the triplet annihilation upconversion of the two-component system PtPc ₂ /Rubrene, after removing the excitation light source through a 634 nm monochromatic filter, the yellow upconversion fluorescence can be clearly seen, showing that the two-component system achieves weak light upconversion.

Example 7 Preparation and testing of sensitizer/luminescent agent binary triplet annihilation system

PtPc ₂ acts as a triplet sensitizer, while rubrene (Rubrene) acts as a triplet luminescent agent. The solvent used in the test is chloroform. The structural formula of PtPc ₂ is:

Prepare a mixed upconversion solution, in which PtPc ₂ is 4×10 ^-6 mol/L, Rubrene is 1×10 ^-2 mol/L, mixed and dissolved in spectral grade chloroform.

The mixed solution was placed in a quartz cuvette with a light path of 1 cm. After degassing pretreatment, under the excitation of a red laser (634 nm, power density 35 mW/cm ² ), the red fluorescence of the two-component system was tested. Upconversion spectra of ene/ _PtPc2 . According to the physical map of the triplet annihilation upconversion of the two-component system PtPc ₂ /Rubrene, after removing the excitation light source through a 634 nm monochromatic filter, the yellow upconversion fluorescence can be clearly seen, showing that the two-component system achieves weak light upconversion.

Example 8 Preparation and testing of sensitizer/luminescent agent binary triplet annihilation system

PdPc ₂ acts as a triplet sensitizer, while rubrene (Rubrene) acts as a triplet luminescent agent. The solvent used in the test is chloroform. The structural formula of PdPc ₂ is:

A mixed upconversion solution was prepared, in which PdPc ₂ was 4×10 ^-6 mol/L, Rubrene was 1×10 ^-2 mol/L, mixed and dissolved in spectral grade chloroform.

The mixed solution was placed in a quartz cuvette with a light path of 1 cm. After degassing pretreatment, under the excitation of a red laser (634 nm, power density 35 mW/cm ² ), the red fluorescence of the two-component system was tested. Upconversion spectra of ene/ _PdPc2 . According to the physical map of triplet annihilation upconversion of the two-component system PdPc ₂ /Rubrene, after the excitation light source is removed through a 634 nm monochromatic filter, yellow upconversion fluorescence can be clearly seen, showing that the two-component system achieves weak light upconversion.

Example 9 Preparation and testing of sensitizer/luminescent agent binary triplet annihilation system

PdPc ₂ acts as a triplet sensitizer, while rubrene (Rubrene) acts as a triplet luminescent agent. The solvent used in the test is chloroform. The structural formula of PdPc ₂ is:

A mixed upconversion solution was prepared, in which PdPc ₂ was 4×10 ^-6 mol/L, Rubrene was 1×10 ^-2 mol/L, mixed and dissolved in spectral grade chloroform.

The mixed solution was placed in a quartz cuvette with a light path of 1 cm. After degassing pretreatment, under the excitation of a red laser (634 nm, power density 35 mW/cm ² ), the red fluorescence of the two-component system was tested. Upconversion spectra of ene/ _PdPc2 . According to the physical map of triplet annihilation upconversion of the two-component system PdPc ₂ /Rubrene, after the excitation light source is removed through a 634 nm monochromatic filter, yellow upconversion fluorescence can be clearly seen, showing that the two-component system achieves weak light upconversion.

Claims (10)

1. a sandwich type phthalocyanine metal complex, is characterized in that, the general structural formula of this sandwich type phthalocyanine metal complex is as follows: Wherein R is selected from hydrogen, nitro, methyl, carboxyl or chlorine; M is a metal atom selected from palladium or platinum. 2 . The sandwich-type phthalocyanine metal complex according to claim 1 , characterized in that: the metal atoms and the phthalocyanine are connected to each other in a coordination bond. 3 . 3. the preparation method of the described sandwich type phthalocyanine metal complex of claim 1, is characterized in that, comprises the following steps: in nitrogen atmosphere, under the effect of catalyst, in organic solvent, the phthalonitrile derivative React with a metal compound to obtain a sandwich-type phthalocyanine metal complex; The structural formula of the phthalonitrile derivatives is: ; The metal compound is palladium acetylacetonate or potassium chloroplatinate; The catalyst is 1,8-diazabicycloundec-7-ene; The boiling point of the organic solvent is 130°C to 150°C. 4. The method for preparing the sandwich-type phthalocyanine metal complex according to claim 3, characterized in that: the reaction temperature is the reflux temperature of the organic solvent; the reaction time is 24 hours. 5. The method for preparing the sandwich-type phthalocyanine metal complex according to claim 3, characterized in that: the organic solvent is n-amyl alcohol. 6. The application of the sandwich-type phthalocyanine metal complex according to claim 1 in the preparation of triplet annihilation upconversion materials. 7. The application according to claim 6, wherein the triplet annihilation up-conversion material is a triplet annihilation up-conversion material that converts red light into yellow light. 8. A triplet annihilation upconversion two-component system, comprising a sensitizer and a luminescent agent, characterized in that: the sensitizer is the sandwich-type phthalocyanine metal complex according to claim 1. 9. The triplet annihilation upconversion two-component system according to claim 8, characterized in that: the triplet annihilation upconversion two-component system is a triplet annihilation upconversion two-component system that converts red light into yellow light system. 10. The triplet annihilation upconversion two-component system according to claim 8, characterized in that: the molar ratio of the sensitizer to the luminescent agent is 1:250-2500.