Application of rare earth complex material in up-conversion circular polarization luminescence

Abstract

The invention discloses an application of a rare earth complex material in up-conversion circular polarization luminescence, and belongs to the technical field of up-conversion circular polarization luminescence. The rare earth complex fills the blank of the rare earth complex in the field of chiral up-conversion luminescence, and compared with a traditional up-conversion circular polarization luminescent material system, the rare earth complex has the advantages of large luminescence asymmetry factor, excellent solubility, accurate structure, controllable synthesis, high repeatability and the like, so that the rare earth complex can bring better biological compatibility and can be applied to the field of chiral up-conversion luminescence. The chiral upconversion luminescent material is expected to become a novel chiral upconversion luminescent material in biological application, so that understanding is provided for interaction between biological systems, and a new tool and a new method are provided for disease diagnosis and treatment.

Description

Technical Field

[0001] The present application relates to the application of a rare earth complex material in up-conversion circularly polarized luminescence, belonging to the technical field of up-conversion circularly polarized luminescence. Background Art

[0002] Chirality has always been a hot topic in the fields of life sciences and medicine. Chiral luminescent materials have unique optical activity, which can give materials unique chiral characteristics, such as chiral recognition and circularly polarized luminescence. Therefore, the development of chiral luminescent materials can not only expand our understanding of the interaction between chiral molecules and biological systems, but also provide new tools and methods for disease diagnosis and treatment. Among them, chiral materials with circularly polarized luminescence (CPL) properties have broad application prospects in biological probes and chiral optoelectronics. The luminescence asymmetry factor (g lum ) is an important parameter for evaluating CPL materials, which is determined by the difference between left-handed and right-handed polarized emissions. In rare earth complexes, due to the magnetic dipole-allowed transition rules, the luminescence asymmetry factor is significantly higher than that of chiral organic molecules, molecular aggregates, and transition metal complexes.

[0003] In recent years, the research on combining circularly polarized luminescence with upconversion has attracted widespread attention. Upconversion circularly polarized luminescence (UC-CPL) refers to the anti-Stokes optical behavior of converting unpolarized low-energy photons into circularly polarized high-energy photons. Low-energy photons have low photodamage and a large penetration depth in tissues. At the same time, the upconversion process can avoid the autofluorescence interference and light scattering of biological samples. Therefore, UC-CPL has great development potential in the biomedical field. At present, UC-CPL has achieved corresponding CPL in three upconversion processes: triplet-triplet annihilation upconversion, two-photon absorption, and upconversion nanoparticles. The material system is mainly concentrated in inorganic chiral perovskites, or chiral organic-inorganic co-assembly systems, which are co-assembled with inorganic perovskites, quantum dots, and upconversion nanoparticles through chiral gels or MOF matrices. However, the above materials have more or less problems such as low synthetic repeatability, poor solubility, uncontrollable size, and poor biocompatibility. Although organic molecules can achieve CPL in solution through triplet-triplet upconversion, the process involves concentration effects caused by diffusion and the difficulty of organic matter being soluble in water, which limits its prospects for biological applications. Summary of the invention

[0004] In order to solve the many problems in the prior art of UC-CPL that are still caused by materials and limit the prospects of biological applications, the present application provides a rare earth complex material for use in up-conversion circularly polarized luminescence, and the UC-CPL of the rare earth complex is realized by utilizing the large luminescence asymmetry factor associated with the rare earth ions and the higher photostability brought by low-energy near-infrared light radiation, which has great application prospects. However, due to the obstacles of weak up-conversion luminescence itself and the difficulty in controlling the stereochemistry of the rare earth center, it is extremely challenging to realize UC-CPL with rare earth complexes, and there has been no successful report so far. In order to further overcome this obstacle, the technical solution for the application of rare earth complex materials in up-conversion circularly polarized luminescence provided in the present application utilizes stereoselective self-assembly of chiral ligands to obtain enantiomerically pure chiral rare earth tetrahedral cages, and utilizes the triplet state of ligand polymers to mediate up-conversion luminescence, realizing up-conversion circularly polarized luminescence in rare earth complex solutions for the first time.

[0005] This application adopts the following technical solutions:

[0006] A rare earth complex material is used in up-conversion circularly polarized luminescence, wherein the rare earth metal ion in the rare earth complex material is selected from Yb 3+ , Er 3+ 、Tm 3+ 、Sm 3+ 、Ho 3+ 、Nd 3+ , Pr 3+ 、Eu 3+ , Gd 3+ , Tb 3+ 、Dy 3+ At least one of .

[0007] Optionally, the rare earth complex material is a mononuclear rare earth complex or a polynuclear rare earth complex;

[0008] The rare earth metal ions in the mononuclear rare earth complex or the multinuclear rare earth complex are independently selected from Yb 3+ , Er 3+ 、Tm 3+ 、Sm 3+ 、Ho 3+ 、Nd 3+ 、Dy 3+ , Pr 3+ One of them acts as a sensitizer.

[0009] Optionally, the multi-nuclear rare earth complex includes a mixed metal system of a sensitizer and an activator;

[0010] The mixed metal system is selected from Yb 3+ / Tm 3+ , Yb 3+ / Er 3+ , Yb 3+ / Ho 3+ , Nd 3+ / Tm 3+ , Ce 3+ / Ho 3+ , Ho 3+ / Tm 3+ , Yb 3+ / Eu 3+ , Yb 3+ / Tb 3+ , Yb 3+ / Sm 3+ , Yb 3+ / Pr 3+ One of them.

[0011] Optionally, the rare earth complex material is a chiral rare earth complex;

[0012] In the present application, the chirality of the rare earth complex can come from three aspects: 1. Using stereoselective self-assembly of chiral ligands to form rare earth complexes with absolute stereo configuration. 2. After the achiral ligands and rare earth ions are assembled to form rare earth complexes, the vacant coordination points of the rare earth ions can be coordinated with chiral auxiliary ligands to induce the absolute stereo configuration of the rare earth center. 3. Using chiral counter ions or chiral guest organic small molecules to induce the absolute stereo configuration of the achiral rare earth center.

[0013] For the upconversion process of the two-photon absorption mechanism, it is limited by the small two-photon absorption cross section and virtual energy level transition, so it requires a high-energy pulse light source for excitation; in addition, the excited state of small molecules that absorb photons has a short lifetime (ns or μs order of magnitude). In comparison, the upconversion composed of rare earth complexes (the upconversion process, in which rare earth ions are used to absorb photons.) can be excited using a continuous excitation light source with lower energy, and the forbidden transition of rare earth ions gives rare earth ions long-lived intermediate excited states (ms or even s order of magnitude) and rich energy level structures, which are conducive to the distribution of intermediate excited state energy levels. In addition, the molecular upconversion system composed of rare earth complexes also has the advantages of controllable synthesis, precise structure, and good solubility, and has been vigorously developed in the past decade.

[0014] Optionally, the chiral rare earth complex is obtained by at least one of the following methods:

[0015] The chiral ligand and the rare earth ion are self-assembled to form a rare earth complex with an absolute stereo configuration; or,

[0016] The achiral ligand and the rare earth ion are self-assembled by coordination, and then the chiral auxiliary ligand is coordinated with the vacant coordination point of the rare earth ion to induce the formation of a rare earth complex with an absolute stereo configuration; or,

[0017] The non-chiral ligand and the rare earth ion are self-assembled through coordination, and then the chiral counter ions or chiral guest organic small molecules are used to induce the formation of a rare earth complex with an absolute stereo configuration.

[0018] Optionally, the chiral rare earth complex is an enantiomerically pure tetranuclear rare earth complex obtained by coordination self-assembly of a chiral ligand and a rare earth ion.

[0019] Optionally, the chiral ligand has a structure shown in Formula I;

[0020]

[0021] The preparation method of the chiral ligand having the structure shown in Formula I in the present application is carried out with reference to the patent with publication number CN111484478A previously studied by the applicant.

[0022] Optionally, the method for preparing the chiral ligand having the structure shown in Formula I comprises the process shown in Formula Ia:

[0023]

[0024] Optionally, the chiral rare earth complex is obtained by at least one of the following methods:

[0025] The chiral ligand shown in formula I and Ln(OTf) 3 Add to CD 3 CN / CD 3 OD mixed solution, react, and form a tetranuclear rare earth complex with absolute stereo configuration through coordination self-assembly; Ln(OTf) 3 It is a rare earth trifluoromethanesulfonate compound.

[0026] Wherein, Ln is selected from Yb 3+ , Er 3+ 、Tm 3+ 、Sm 3+ 、Ho 3+ 、Nd 3+ 、Eu 3+ , Tb 3+ , Gd 3+ At least one of .

[0027] Optionally, the tetranuclear rare earth complex has a structure shown in Formula II;

[0028]

[0029] Among them, the sphere represents Ln.

[0030] The preparation of the tetranuclear rare earth complex in the present application is carried out with reference to the patent with publication number CN117050059A previously studied by the applicant.

[0031] Optionally, the method for preparing the tetranuclear rare earth complex having the structure shown in Formula II comprises the process shown in Formula II-a:

[0032]

[0033] Wherein, Ln is selected from Yb 3+ , Er 3+ 、Tm 3+ 、Sm 3+ 、Ho 3+ 、Nd 3+ 、Eu 3+ , Tb 3+ , Gd 3+ At least one of .

[0034] Optionally, the tetranuclear rare earth complex includes a sensitizer Yb 3+ and activator Eu 3+ Composition of Yb 3+ / Eu 3+ Mixed metal systems.

[0035] Optionally, the absolute value of the up-conversion luminescence asymmetry factor of the rare earth complex material is greater than or equal to 0.01.

[0036] The beneficial effects of this application include:

[0037] The rare earth complex materials provided in the present application are used in up-conversion circularly polarized luminescence. Compared with other systems, the chiral rare earth complexes themselves have the advantages of a larger luminescence asymmetry factor, controllable synthesis with high repeatability, precise structure, good solubility, etc., which can bring better biocompatibility and are expected to become new chiral up-conversion luminescent materials in biological applications, thereby providing an understanding of the interactions between biological systems and new tools and methods for disease diagnosis and treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a schematic diagram of the assembly process of the rare earth complex material used for up-conversion circularly polarized luminescence in the present application.

[0039] Figure 2 is the chiral optical performance test result, where Figure 2 (a) is L R / S (30 μM, CHCl 3 ) and Eu 4 (L R / S ) 6 (5 μM, CH 3 CN) UV-vis and CD spectra; Figure 2 (b) is Eu 4 (L R / S ) 6 In CH3 CPL spectra in CN (λ ex =328 nm, 20 μM).

[0040] Figure 3 is the upconversion luminescence test result of the assembly, where Figure 3 (a) is a CD 3 CN / MeOD(4.0mM) (Yb / Eu) 4 (L R / S ) 6 The variable power up-conversion emission spectrum (λ ex =980nm, room temperature), the inset shows the upconversion luminescence photograph (P = 10W). (b) Upconversion emission intensity integral (I UC ) and laser power density P (unit: Wcm -2 ). (c)CD 3 (Yb / Eu) in CN / MeOD solution 4 (L R / S ) 6 Upconversion emission spectra under different atmospheres. (d) Cooperative sensitization upconversion process mediated by the triplet state of the polymer.

[0041] Figure 4 is the test result of the upconversion circularly polarized luminescence performance of the assembly, where Figure 4 (a) Concept map, Figure 4 (b) is a CD 3 CN / MeOD (4.0 mM, λ ex =980nm, room temperature)(Yb / Eu) 4 (L R / S ) 6 Upconversion circularly polarized luminescence spectrum. (c) UCCPL asymmetry factor g lum Relationship with wavelength. DETAILED DESCRIPTION

[0042] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0043] Unless otherwise specified, all chemical reagents and solvents in the examples of this application were obtained from commercial sources and were not further purified before use. Deuterated solvents were purchased from Adamas and J&K Technologies Co., Ltd.

[0044] Unless otherwise specified, the test method adopts conventional methods, and the instrument settings adopt the settings recommended by the manufacturer. The analysis method in the embodiment is as follows: one-dimensional and two-dimensional nuclear magnetic spectra are measured by German Bruker Biospin Avance III (400MHz) nuclear magnetic analyzer. The determination of hydrogen spectrum chemical shift value is based on the residual peak of deuterated solvent. High-resolution mass spectrum is measured by German Bruker Impact II UHR-TOF mass spectrometer. UV-visible spectrum test is carried out on Shimadzu UV-2700 UV-visible spectrophotometer. Circular dichroism spectrum (CD) was recorded with MOS-450 circular dichroism spectrometer. Circular polarization luminescence (CPL) test is carried out on JASCO CPL-200 spectrometer. Up-conversion spectral data test is carried out on FLS1000 spectrometer in Edinburgh, UK, using JASCO CPL-200 spectrophotometer to record up-conversion circular polarization luminescence spectrum, external 980nm laser.

[0045] Example 1 Ligand L R / S Synthesis

[0046] Ligand L R / S It is obtained by the process of formula A, and the specific process is as follows:

[0047]

[0048] Synthesis of 2,6-naphthaleneazide (2): Sodium nitrite aqueous solution (674 mg, 9.77 mmol, 3.0 eq) was added to naphthalene-2,6-diamine (515 mg, 3.26 mmol, 1.0 eq) in an ice-water bath, and dilute hydrochloric acid (2M, 30 mL) was added. After stirring for half an hour, sodium azide aqueous solution (849 mg, 13.04 mmol, 4.0 eq) was added dropwise to the diazonium salt. The resulting precipitate was recovered by filtration and further purified by column chromatography on silica gel using petroleum ether as the eluent. After vacuum drying, 2,6-naphthaleneazide (570 mg, yield 83%) was obtained as a yellow powder. 1 H NMR (400 MHz, CDCl 3 ,298K)δ=7.73(d,J=8.7Hz,2H),7.40(d,J=1.8Hz,2H),7.17(dd,J=8.7,1.8Hz,2H). 13 C NMR (101 MHz, CDCl 3 ,298K)δ=137.27,131.6,129.0,120.0,116.0.

[0049] Ligand L SSynthesis: To a solution of 2,6-naphthaleneazide (570 mg, 2.71 mmol, 1.0 eq) and (S)-6-ethynyl-N-(1-phenylethyl)picolinamide (1.63 g, 6.51 mmol, 2.4 eq) in DMF (50 mL) were added sodium ascorbate (1.09 g, 5.69 mmol, 2.1 eq) and CuSO 4 ·5H 2 O (610 mg, 2.44 mmol, 0.9 eq). The mixture was stirred at 60 ° C for 24 hours to produce a dark red solution. After the reaction mixture was cooled to room temperature, it was concentrated under reduced pressure. Subsequently, the crude product was treated with saturated EDTA aqueous solution (200 mL) for 1 hour, filtered, and purified by column chromatography (silica gel, with DCM / MeOH = 50 / 1 as eluent) to obtain a yellow powder ligand L S (1.4 g, 73% yield). 1 H NMR (400 MHz, CDCl 3 ,298K)δ=8.68(s,2H),8.42(d,J=7.8Hz,2H),8.37(s,2H),8.27(d,J=8.4Hz,2H ),8.23(d,J=7.8Hz,2H),8.16(d,J=8.7Hz,2H),8.11(d,J=8.7Hz,2H),8.01(t,J 1 =15.6Hz,J 2 =7.8Hz,2H),7.48(d,J=7.6Hz,4H),7.40(t,J=7.6Hz,4H),7.31(t,J 1 =15.2Hz,J 2 =7.6Hz,2H),5.52-5.38(m,2H),1.71(d,J=6.9Hz,6H). 13 C NMR (101 MHz, CDCl 3 ,298K)δ=163.4,150.0,148.6,143.3,138.7,135.3,133.0,130.7,128.9,127.57,126.5,123.4,122.3,120.7,120.3,118.8,48.7,21.9.C 42 H 34 N 10 O 2 High resolution mass spectrometry [M+Na] + :calcd,m / z=733.2758; found 733.2754.

[0050] Ligand L R The synthesis method of LS Identical except that (S)-6-ethynyl-N-(1-phenylethyl)picolinamide is replaced with (R)-6-ethynyl-N-(1-phenylethyl)picolinamide.

[0051] Example 2 Rare Earth Complex Yb 4 (L R / S ) 6 Synthesis

[0052] Rare earth complex Yb 4 (L R / S ) 6 The schematic diagram of the synthesis process is as follows Figure 1 As shown, the specific process is: L R / S (20 mg, 28.2 μmol) suspended in CD 3 CN / CD 3 OD mixed solution (v / v=4 / 1, 500 μL), and then Yb(OTf) 3 (11.6 mg, 18.8 μmol). The suspension was heated at 50 °C for 1 h to give a homogeneous yellow solution which was characterized without further treatment. NMR spectroscopy showed quantitative formation of Yb 4 (L R / S ) 6 . 1 H NMR (400MHz, CD 3 CN / CD 3 OD v / v=4 / 1,298K)δ=11.75(br,1H),11.13(s,1H),10.70(br,1H),10.41(s,1H),10.16(br,1H ),7.96(s,1H),6.08-5.93(m,3H),5.86(br,2H),5.37(br,1H),5.14(br,2H),3.86(s,3H). 13 C NMR (101 MHz, CD 3 CN / CD 3 OD v / v=4 / 1,298K)δ=143.0,140.1,139.1,136.7,135.0,128.2,127.1,126.7,1 25.1,123.5,123.5,121.9,121.2,120.3,118.1,117.1,112.8,55.1,24.3.Yb 4 (L S ) 6 (OTf) 12 High-resolution mass spectrometry: m / z[Yb 4 (L S )6 (OTf) 8 ] 4+ Calculated value 1537.2734, simulated value 1537.2735; [Yb 4 (L S ) 6 (OTf) 7 ] 5+ Calculated value 1200.0283, simulated value 1200.0291; [Yb 4 (L S ) 6 (OTf) 6 ] 6+ Calculated value 975.1982, simulated value 975.1986; [Yb 4 (L S ) 6 (OTf) 5 ] 7+ Calculated value 814.6053, simulated value 814.6055; [Yb 4 (L S ) 6 (OTf) 4 ] 8+ Calculated value 694.1606, simulated value 694.1611; [Yb 4 (L S ) 6 (OTf) 3 ] 9+ Calculated value 600.3701, simulated value 600.3707.

[0053] Using the synthesis method of Example 2, Ln with different Ln selections can be prepared. 4 (L R / S ) 6 , the only difference is that Yb(OTf) 3 Replace with other Ln and select the corresponding Ln(OTf) 3 .

[0054] Example 3 Chiral optical properties test of ligand and assembly

[0055] CD and CPL spectra confirmed the chiral characteristics of the ligand and the assembly. The absorption spectrum of the ligand between 240-350nm belongs to the π→π* transition, corresponding to a weak and broad circular dichroism (CD) signal ( Figure 2 a). In sharp contrast, Eu 4 (L R / S ) 6 The CD spectrum of Eu2O3 shows multiple split peaks (250, 279 and 320 nm) with obvious Cotton effect. 4 (LS ) 6 Negative exciton coupling between 295 and 360 nm is consistent with the delta helicity of the metallic stereocenter observed in the crystal structure. CPL spectroscopy was used to determine the chiral nature of the excited states, Eu 4 (L R / S ) 6 The CPL spectrum shows a perfect mirror image pattern ( Figure 2 b), the emission at 592 nm complies with the magnetic dipole transition selection law, showing the highest luminescence asymmetry factor up to ±0.058.

[0056] Example 4: Test of upconversion luminescence and upconversion circularly polarized luminescence performance of the assembly

[0057] At room temperature, under 980nm continuous laser excitation, heterometallic (Yb / Eu) 4 (L S ) 6 (By N Yb / N Eu =3 / 1 assembly, N represents the amount of substance) 3 Characteristic Eu was observed at 580, 595, 616, 650, and 695 nm in CN / MeOD solution (4.0 mM). 3+ Emission peak ( Figure 3 a). When the power of 980nm laser reaches 10W, the upconverted red light is visible to the naked eye. UC The quadratic dependence of (integrated from 605 to 630 nm) on Log P confirms the two-photon upconversion mechanism ( Figure 3 b).

[0058] For qualitative research from Yb 3+ To Eu 3+ The energy transfer process of UC was monitored in air and oxygen atmospheres. Molecular oxygen is an efficient triplet quencher, which leads to 75% quenching of upconversion emission ( Figure 3 c), indicating that (Yb / Eu) 4 (L S ) 6 There is an intramolecular triplet-mediated cooperative sensitization upconversion ( Figure 3 d). It is worth mentioning that this triplet state is not the triplet state of the ligand monomer (energy level is about 25,000 cm -1 ), but rather, in the process of supramolecular assembly, since supramolecular assembly fixes the distance, orientation and vibration of the ligands, the assembly-induced polymer triplet state (energy level of about 20,000cm -1 ) happens to be with two Yb 3+ The ions can reach quasi-virtual energy levels.

[0059] The quantum yield of the triplet-mediated cooperative upconversion luminescence of the polymer was calculated to be 1.9×10 -7 (P=36Wcm -2 ). This encouraged us to further examine the upconversion circularly polarized luminescence properties of this enantiomerically pure mixed-metal supramolecular complex, which, to our knowledge, has never been reported in rare earth complexes before. 3 CN / CD 3 OD mixed solution, under 980nm laser excitation (10W), (Yb / Eu) 4 (L R / S ) 6 The obvious upconversion circularly polarized luminescence spectrum is almost a complete mirror image mode, respectively 5 D 0 → 7 F 1 (about 590nm) and 5 D 0 → 7 F 2 (about 615nm) transition shows significant CPL activity ( Figure 4 a- Figure 4 b) Visible area 5 D 0 → 7 F 1 The upconversion asymmetry factor is as large as ±0.015, which exceeds that of most chiral upconversion systems ( Figure 4 c). Due to the weak upconversion signal, the asymmetry factor of the upconverted circularly polarized luminescence is slightly lower than that of the downconversion process, but it is still within the same order of magnitude.

[0060] The rare earth complex material provided in the present application is used in up-conversion circularly polarized luminescence. The up-conversion circularly polarized luminescence effect of the rare earth complex has the following advantages compared with other systems: 1. The up-conversion luminescence asymmetry factor of the rare earth complex is within 10 -2 level, which is much larger than most chiral organic molecules and perovskites (luminescence asymmetry factor is 10 -3level); 2. Compared with perovskites, quantum dots, and upconversion nanoparticles, rare earth complexes have good solubility and can bring better biocompatibility. In one embodiment, upconversion circularly polarized luminescence is achieved in a solution system composed of acetonitrile and methanol; 3. Although chiral organic molecules achieve upconversion circularly polarized luminescence through triplet-triplet annihilation, they can only be dissolved in non-polar toluene solvents, while charged rare earth complexes can be dissolved in polar solvents with very good solubility. In one embodiment, a mixed solvent composed of acetonitrile and methanol is selected. In addition, it can be foreseen that when chiral carboxylic acids and tetrazole ligands are used to coordinate with rare earths, more stable water-soluble and water-stable rare earth complexes can be formed, which will have extremely high biological application potential, which is unmatched by systems such as chiral organic molecules, perovskites, quantum dots, and upconversion nanoparticles; 4. Triplet-triplet annihilation UC-CPL is affected by diffusion and requires energy transfer in concentrated solutions. Generally, at higher concentrations (10 -3 As long as the up-conversion luminescence efficiency is high, the UC-CPL of rare earth complexes can be achieved at very low concentrations (10 -4 M even 10 -5 M) conditions; 5. Compared with the two-photon absorption process, the upconversion process of rare earth complexes has the advantages of low excitation light energy, good photostability, and long intermediate excited state lifetime. In short, rare earth complex materials can have the above five advantages at the same time.

[0061] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A rare earth complex material is used in up-conversion circularly polarized luminescence, characterized in that: The rare earth metal ions in the rare earth complex material are selected from Yb 3+ , Er 3+ 、Tm 3+ 、Sm 3+ 、Ho 3+ 、Nd 3+ , Pr 3+ 、Eu 3+ , Gd 3+ , Tb 3+ 、Dy 3+ At least one of .

2. The use according to claim 1, characterized in that: The rare earth complex material is a mononuclear rare earth complex or a polynuclear rare earth complex; The rare earth metal ions in the mononuclear rare earth complex or the multinuclear rare earth complex are independently selected from Yb 3+ , Er 3+ 、Tm 3+ 、Sm 3+ 、Ho 3+ 、Nd 3+ 、Dy 3+ , Pr 3+ One of them acts as a sensitizer.

3. The use according to claim 2, characterized in that: The multi-nuclear rare earth complex includes a mixed metal system of a sensitizer and an activator; The mixed metal system is selected from Yb 3+ / Tm 3+ , Yb 3+ / Er 3+ , Yb 3+ / Ho 3+ , Nd 3+ / Tm 3+ , Ce 3+ / Ho 3+ , Ho 3+ / Tm 3+ , Yb 3+ / Eu 3+ , Yb 3+ / Tb 3+ , Yb 3+ / Sm 3+ , Yb 3+ / Pr 3+ One of them.

4. The use according to claim 1, characterized in that: The rare earth complex material is a chiral rare earth complex; The chiral rare earth complex is obtained by at least one of the following methods: The chiral ligand and the rare earth ion are self-assembled to form a rare earth complex with an absolute stereo configuration; or, The achiral ligand and the rare earth ion are self-assembled by coordination, and then the chiral auxiliary ligand is coordinated with the vacant coordination point of the rare earth ion to induce the formation of a rare earth complex with an absolute stereo configuration; or, The non-chiral ligand and the rare earth ion are self-assembled through coordination, and then the chiral counter ions or chiral guest organic small molecules are used to induce the formation of a rare earth complex with an absolute stereo configuration.

5. The use according to claim 4, characterized in that: The chiral rare earth complex is an enantiomerically pure tetranuclear rare earth complex obtained by coordination self-assembly of a chiral ligand and a rare earth ion.

6. The use according to claim 5, characterized in that: The chiral ligand has a structure shown in Formula I; 7. The use according to claim 6, characterized in that: The chiral rare earth complex is obtained by at least one of the following methods: Adding the chiral ligand shown in formula I and Ln(OTf)3 to a CD3CN / CD3OD mixed solution, reacting, and forming a tetranuclear rare earth complex with an absolute stereo configuration through coordination self-assembly; Wherein, Ln is selected from Yb 3+ , Er 3+ 、Tm 3+ 、Sm 3+ 、Ho 3+ 、Nd 3+ 、Eu 3+ , Tb 3+ , Gd 3+ At least one of .

8. The use according to claim 7, characterized in that: The tetranuclear rare earth complex has the structure shown in Formula II; Among them, the sphere represents Ln.

9. The use according to claim 7, characterized in that: The tetranuclear rare earth complex comprises a sensitizer Yb 3+ and activator Eu 3+ Composition of Yb 3+ / Eu 3+ Mixed metal systems.

10. The use according to claim 1, characterized in that: The absolute value of the up-conversion luminescence asymmetry factor of the rare earth complex material is greater than or equal to 0.01.

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