WO2022174494A1 - Multi-channel tunable weak light up-conversion luminescence system and application thereof - Google Patents

Multi-channel tunable weak light up-conversion luminescence system and application thereof Download PDF

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WO2022174494A1
WO2022174494A1 PCT/CN2021/083440 CN2021083440W WO2022174494A1 WO 2022174494 A1 WO2022174494 A1 WO 2022174494A1 CN 2021083440 W CN2021083440 W CN 2021083440W WO 2022174494 A1 WO2022174494 A1 WO 2022174494A1
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conversion
light
red
component system
upconversion
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王筱梅
居晓雷
叶常青
李琳
朱琳
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苏州科技大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/20—Polycyclic condensed hydrocarbons
    • C07C15/27—Polycyclic condensed hydrocarbons containing three rings
    • C07C15/28—Anthracenes
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the invention relates to the field of weak light up-conversion, in particular to a multi-channel tunable weak light up-conversion lighting system and its application.
  • Up-conversion means obtaining short-wavelength light (high-energy light) under excitation by long-wavelength light (low-energy light).
  • TPA-UC two-photon absorption upconversion
  • TTA-UC triplet-triplet annihilation upconversion
  • OPA-UC One-photon absorption upconversion
  • TPA-UC needs to be obtained under the excitation of strong light (>MW ⁇ cm -2 ) at MW/cm2, so it is called strong light up-conversion; TTA-UC and OPA-UC need to be excited at the weak light of mW/cm2 It is obtained under excitation by light ( ⁇ mW ⁇ cm -2 ), so it is called weak light upconversion.
  • weak light upconversion has greater application value in the fields of solar photovoltaic, photocatalysis, biomedicine, light-regulated lighting and environmental detection.
  • TTA-UC material is a two-component system
  • OPA-UC is a one-component system
  • TTA-UC requires the participation of two components of photosensitizer-annihilation agent (the medium is usually a solvent).
  • the microscopic mechanism is as follows: the photosensitizer first harvests low-energy excitation light, followed by intersystem crossing (ISC); then the photosensitizer transfers the triplet energy to the annihilating agent; the last two excited triplet annihilating molecules undergo electron spin conversion. A process that emits high-energy photons that are upconverted relative to low-energy excitation light.
  • the material involved in OPA-UC is only the luminescent agent itself (that is, a single component).
  • the mechanism is: the luminescent agent molecule has the characteristic of tropical absorption: the higher vibrational energy level (tropical) from the ground state (S 0 ) (S 0 ). t ) transition to an excited singlet state (S 1 ) excitation followed by emission of photons of higher energy than the absorbed photons.
  • TTA-UC and OPA-UC due to their different microscopic mechanisms, can be classified into the field of low-light up-conversion luminescence, but they are actually two unrelated luminescence mechanisms and systems.
  • the invention discloses for the first time an octaethylporphyrin palladium (PdOEP) single-photon solution to obtain red-to-yellow up-conversion emission; further, the PdOEP and the annihilation agent 9,10-diphenylanthracene (DPA) are prepared into a mixed solution solution, emits red-to-blue upconversion emission.
  • PdOEP octaethylporphyrin palladium
  • DPA 9,10-diphenylanthracene
  • the present invention adopts the following technical scheme: a multi-channel tunable weak light up-conversion two-component system, including octaethyl porphyrin palladium, anthracene derivatives and a solvent; preferably, the weak light up-conversion two-component system is composed of octaethyl porphyrin Palladium, anthracene derivatives and solvent composition.
  • the multi-channel tunable weak light up-conversion one-component system includes octaethyl porphyrin palladium and a solvent; preferably, the weak light up-conversion two-component system is composed of octaethyl porphyrin palladium and a solvent.
  • the invention discloses the application of the above-mentioned multi-channel tunable weak light up-conversion two-component system in preparing red-to-blue up-conversion material or red-to-yellow up-conversion material, or the above-mentioned multi-channel tunable weak light up-conversion Application of two-component system as red-to-blue upconversion material or red-to-yellow upconversion material.
  • the invention discloses the application of the above-mentioned multi-channel tunable weak light up-conversion one-component system in the preparation of red-to-yellow up-conversion materials, or the above-mentioned multi-channel tunable weak light up-conversion one-component system as a red-to-yellow up-conversion one-component system.
  • the creativity of the present invention lies in that the octaethyl porphyrin palladium system is disclosed for the first time to realize the red light excited up-conversion material, which overcomes the technical prejudice that the octaethyl porphyrin palladium is the green light excited up-conversion material in the prior art.
  • the invention discloses a method for up-conversion of red light.
  • the red light is used to irradiate a weak-light up-conversion two-component system or a weak-light up-conversion single-component system to obtain yellow light or blue light, and realize the red light up-conversion;
  • the weak light up-conversion two-component system is composed of octaethyl porphyrin palladium, an anthracene derivative and a solvent;
  • the weak light up-conversion one-component system is composed of octaethyl porphyrin palladium and a solvent.
  • the red light up-conversion disclosed in the present invention can obtain blue light and yellow light.
  • the two-component system prepared by the present invention comprises palladium octaethylporphyrin (PdOEP, which can be used as both a photosensitizer and a luminescent agent) and 9,10-diphenylanthracene (DPA, which is used as an annihilating agent), and the solvent is DMF (N,N-dimethylformamide).
  • PdOEP palladium octaethylporphyrin
  • DPA 9,10-diphenylanthracene
  • the solvent is DMF (N,N-dimethylformamide).
  • the excitation light of the weak light up-conversion two-component system or the weak light up-conversion single-component system of the present invention uses a conventional semiconductor laser as a light source, and the excitation light intensity is 0.5-2 W/cm 2 .
  • the octaethylporphyrin palladium can be used as both a photosensitizer and a luminescent agent, and its chemical structural formula is as follows: .
  • DPA 9,10-diphenylanthracene
  • the molar ratio of octaethyl porphyrin palladium and anthracene derivatives is 1: (5-30), preferably 1: 25; the concentration of octaethyl porphyrin palladium It is 50 mM to 125 mM, preferably 100 mM.
  • the concentration of octaethylporphyrin palladium is 80mM-120mM, preferably 100mM.
  • the DMF solution of PdOEP/DPA emits blue up-conversion at 430 nm, and this up-conversion is red-to-blue luminescence, and the maximum anti-Stokes of red-to-blue up-conversion
  • the Sterling shift is 0.99 eV.
  • the red light excited upconversion system of octaethylporphyrin palladium (PdOEP) was disclosed for the first time.
  • Figure 1 shows the absorption and fluorescence spectra of PdOEP (100 mM) and DPA (10 mM) (solvent: DMF).
  • Figure 2 shows the relationship between the upconversion spectral intensity and the excitation light power density of the PdOEP/DPA solution (degassed DMF) binary system under excitation at 532 nm (top) and the corresponding upconversion integral logarithm and power density logarithm Plot (bottom) (PdOEP/DPA at 10 ⁇ M/1 mM).
  • Figure 3 shows the relationship between the intensity of the yellow upconversion spectrum emitted by PdOEP solution (100 mM, no degassed DMF solution) and the excitation light power density under excitation at 655 nm (upper, the inset is the lifetime of the upconversion spectrum) and the corresponding upper
  • the logarithm of the transformation integral is plotted against the logarithm of the power density (bottom).
  • Figure 4 shows the temperature-dependent upconversion spectra of PdOEP (100 mM, without degassing DMF solution) under excitation at 655 nm (where a:195 K; b: 226 K; c: 232 K; d: 244 K; e: 263 K; f: 286 K).
  • Figure 5 shows the relationship between the upconversion spectral intensity of PdOEP/DPA solution and the concentration of annihilating agent (degassed DMF, with a fixed photosensitizer concentration of 100 ⁇ M) under excitation at 655 nm (with oxygen exclusion).
  • Figure 6 shows the relationship between the upconversion spectral intensity of PdOEP/DPA solution and the concentration of photosensitizer under excitation at 655 nm (isolated from oxygen) (degassed DMF, and the concentration of annihilation agent was fixed at 2.5 mM).
  • Figure 7 shows the PdOEP/DPA (100 ⁇ M/2.5 mM) upconversion spectral solvent effects.
  • Figure 8 shows the PdOEP/DPA (100 ⁇ M/2.5 mM) solution emits blue upconversion at 430 nm and yellow upconversion at 575 nm, and the relationship between the upconversion spectral intensity and the excitation light power density.
  • Figure 9 shows the PdOEP/DPA (100 ⁇ M/2.5 mM) solution emits a blue upconversion intensity at 430 nm plotted against the logarithm of the logarithm of the power density.
  • Figure 10 shows the PdOEP/DPA (100 ⁇ M/2.5 mM) solution emits a yellow upconversion intensity at 575 nm plotted against the logarithm of the logarithm of the power density.
  • Figure 11 shows the excitation spectra of the PdOEP solution (100 mM, DMF solvent) and the reference ZnPc solution (0.5 mM, DMSO solvent), where the ZnPc intensity is 50 times smaller than the measured data (the emission wavelength is fixed at 575 nm).
  • Figure 12 shows the red-to-yellow upconversion spectrum (a) of PdOEP solution (100mM, DMF solvent, without oxygen removal) and the fluorescence spectrum (b) of ZnPc solution (0.5mM, DMSO solvent) under excitation at 655 nm, Among them, the intensity of ZnPc is 100 times smaller than the measured data.
  • Figure 13 shows the DPA/PdOEP solution (2.5 mM/100 mM, degassed DMF) red-to-blue upconversion spectrum (a) and fluorescence spectrum (b) of ZnPc solution (0.5 mM, DMSO solvent), where the ZnPc intensity is 100-fold smaller than the observed data.
  • the determination of ultraviolet-visible absorption spectrum is carried out on SHIMADZU UV2600 type ultraviolet spectrophotometer; measured on a fluorescence spectrometer.
  • the up-conversion spectrum test is performed with semiconductor lasers at 532 nm and 655 nm as the light source (the excitation light intensity is 0.5 ⁇ 2W/cm 2 , if there is no special instruction, choose 1718.9mW/cm 2 ) (the solvent is DMF), using PR655
  • the spectrometer records the spectrum.
  • the raw materials of the present invention are all conventional commercial products, and the specific preparation methods and testing methods are conventional techniques; unless otherwise specified, all operations are performed at room temperature.
  • the preparation method of the weak light up-conversion two-component system is as follows: according to the mole ratio of photosensitizer/annihilation agent is 1:25, the concentration of photosensitizer is 100 mM, and the concentration of annihilating agent is 100 mM.
  • the test was performed on a 2.5 mM upconversion two-component solution (solvent: DMF); the photosensitizer and annihilation agent were added to DMF to obtain a weak light upconversion two-component system.
  • the preparation method of the weak light up-conversion one-component system is as follows: prepare a single-component solution with a concentration of 100 mM photosensitizer for testing (solvent: DMF); add the photosensitizer to DMF to obtain a weak light up-conversion one-component system.
  • the chemical structural formula of the annihilation agent 9,10-diphenylanthracene (DPA) is as follows: .
  • the absorption and fluorescence spectra of the photosensitizer PdOEP (100 mM) and the annihilation agent DPA (10 mM) are shown in Figure 1. It can be seen that the Soret band of PdOEP is at 391 nm, and the Q-band absorption peaks are at 511 nm and 544, respectively. nm; the double emission bands at 559 nm and 598 nm recorded under excitation at 544 nm are fluorescence emission (see the circle in Figure 1), and the emission at 665 nm and the shoulder at 734 nm are both phosphorescence emission.
  • the absorption peaks of the annihilating agent DPA are at 356 nm, 375 nm and 395 nm, and the fluorescence peaks are at 411 nm and 434 nm.
  • the specific operation of the green - to - blue spectral test is as follows : add the low-light up-conversion two-component system into a quartz cuvette, pass nitrogen for 15 minutes to remove oxygen, and then tighten the cap of the cuvette to obtain a two-component system. Placed on an optical table, and then irradiated the two-component system with a 532nm semiconductor laser, Figure 2 can be recorded.
  • Figure 2 is the blue upconversion spectrum (peak at 430 nm) of the PdOEP/DPA (10 ⁇ M/1 mM, degassed, DMF) binary system under excitation at 532 nm.
  • the relationship between the excitation light power density, the lower figure is the corresponding logarithm of the upconversion integral and the logarithm of the power density (excitation light intensity). It can be seen that with the increase of the excitation light intensity, the blue up-conversion intensity also increases. The log value of the up-conversion intensity and the log value of the power density of the excitation light are plotted (below), and a slope value is obtained. ⁇ 2 curves. Since the excitation light source used is a 532 nm green light source, this upconversion is green-to-blue emission, and the anti-Stokes shift of green-to-blue upconversion is 0.55 eV.
  • the upper figure is the relationship between the up-conversion spectral intensity and the excitation light power density
  • the upconversion undergoes a single-photon absorption process. Since the excitation light source used is a 655 nm red light source, this upconversion is red-to-yellow emission, and the maximum anti-Stokes shift of red-to-yellow upconversion is 0.26 eV.
  • the specific operation of the red - to - blue luminescence test is as follows: add the low-light up-conversion two-component system into a quartz cuvette, pass nitrogen for 15 minutes to remove oxygen, and then tighten the cap of the cuvette to obtain a two-component system. Place it on an optical table, and then irradiate the two-component system with a 655nm semiconductor laser, and the following spectrum can be recorded.
  • Figure 5 is the relationship between the upconversion intensity of PdOEP/DPA and DPA concentration under excitation at 655 nm (deoxygenation, DMF, photosensitizer concentration fixed at 100 ⁇ M); it can be seen that when the concentration of DPA is 2.5 mM, the Conversion intensity is maximum.
  • Figure 6 is the relationship between the upconversion intensity of PdOEP/DPA and the concentration of PdOEP under excitation at 655 nm (deoxygenation, DMF, and the annihilating agent concentration was fixed at 2.5 mM); it can be seen that when the concentration of PdOEP is 100 mM, the upconversion maximum strength.
  • Figure 7 shows the concentration of immobilized PdOEP/DPA at 100 under excitation at 655 nm (isolated from oxygen). ⁇ M/2.5 mM, in different solvents (ethyl acetate, toluene, dichloromethane, N,N-dimethylformamide, and n-propanol), the relationship between the upconversion spectral intensity and solvent species; it can be seen that when The upconversion intensity is the largest when the solvent is DMF.
  • solvents ethyl acetate, toluene, dichloromethane, N,N-dimethylformamide, and n-propanol
  • PdOEP/DPA 100 ⁇ M/2.5 mM, DMF
  • the upconversion spectral intensity varies with the excitation light power density enhance and enhance. Since the excitation light source used is a 655 nm red light source, the spectrum at 430 nm is red-to-blue emission, and the maximum anti-Stokes shift of red-to-blue up-conversion is 0.99 eV.
  • the spectrum at ⁇ 575 nm is red-to-yellow up-conversion luminescence, the highest intensity of blue light is 4.4 ⁇ 10 -5 , and the highest intensity of yellow light is 6 ⁇ 10 -6 .
  • the intensity of the former is 7.3 times that of the latter.
  • Figure 10 shows the PdOEP/DPA (100 ⁇ M/2.5 mM, DMF) solution emits yellow at 570 nm.
  • Red - to - yellow upconversion efficiency For the measurement of one-photon absorption upconversion (OPA-UC), a PdOEP solution (100 mM) without degassing DMF was prepared. A semiconductor solid-state laser (655 nm) was used. The OPA-UC spectrum was recorded with a PR655 spectral scanner (655 nm) located on the back of the filter, and the net red-to-yellow upconversion efficiency (F OPA-UC ) relative to ZnPc was calculated according to equation (2).
  • OPA-UC one-photon absorption upconversion
  • Fs and Fr are the integrated emission of PdOEP and ZnPc at the excitation wavelength of 655 nm, respectively.
  • Is (655) and Ir(655) are the excitation intensities of PdOEP and ZnPc at the wavelength of 655 nm, respectively.
  • the excitation intensity (I ex ) is used here, rather than the absorbance (A) commonly used. This is because the absorbance (A) of PdOEP at 655 nm is not available, while the excitation intensity of PdOEP at 655 nm is available ( Figure 11).
  • n s and n r are the refractive indices of the sample solution and the reference solution, respectively. See Figure 11 and Figure 12 for detailed data. From this, the red-to-yellow up-conversion efficiency was calculated to be 0.38%.
  • F s and F r are the integrated emission of DPA and reference ZnPc at excitation wavelength of 655 nm, respectively.
  • Parameters such as I s(655) , I r(655) , ns and n r are the same as the calculation of the red-to-yellow efficiency. See Figure 11 and Figure 13 for detailed data. From this, the red-to-blue up-conversion efficiency was calculated to be 1.23%.
  • Comparative example Add tetraphenylporphyrin palladium (PdTPP) to DMF to prepare a PdTPP (100mM) DMF solution, add it to a quartz cuvette, tighten the cap of the cuvette (without deoxygenation), and obtain a single component system; placed on the optical platform, directly irradiated with a 655nm semiconductor laser, no emission light, that is, no up-conversion occurs.
  • PdTPP tetraphenylporphyrin palladium
  • PdTPP Tetraphenylporphyrin palladium
  • DPA 9,10-diphenylanthracene
  • phenothiazine to DMF to prepare a phenothiazine (100mM) DMF solution, add it to a quartz cuvette, tighten the cap of the cuvette (without deoxygenation) to obtain a one-component system; place it on an optical table , directly irradiated with a 655nm semiconductor laser, no emission light, that is, no up-conversion occurs.
  • the triplet-triplet annihilation upconversion test was performed using the azaanthene derivative PSF as a photosensitizer (concentration of 10 ⁇ M) and luminescent agent DPA (concentration of 1 mM).
  • the structural formula of the azaanthene derivative PSF is as follows: .
  • the invention achieves tunable up-conversion luminescence under excitation of different wavelengths of light through various excitation mechanisms, and creatively discloses a single-photon luminescence system of palladium octaethylporphyrin (PdOEP) to obtain red-to-yellow up-conversion emission; Palladium ethyl porphyrin (PdOEP) two-photon luminescence system to obtain red-to-blue up-conversion emission; overcome the technical prejudice that octaethyl porphyrin palladium (PdOEP) can only achieve green-to-blue up-conversion in the prior art; It has application value in the field of anti-counterfeiting and biological detection.
  • PdOEP palladium octaethylporphyrin

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Abstract

Disclosed in the present application are a multi-channel tunable weak light up-conversion luminescence system and an application thereof. A weak light up-conversion two-component system consists of palladium octaethylporphyrin, an anthracene derivative, and a solvent; and a weak light up-conversion single-component system consists of palladium octaethylporphyrin and the solvent. The weak light up-conversion two-component system or the weak light up-conversion single-component system is irradiated by using red light, so as to obtain yellow light or blue light, thereby achieving red light up-conversion. The inventiveness of the present invention is that: it is disclosed for the first time that a palladium octaethylporphyrin system achieves a red light excitation up-conversion material, and the technical bias in the prior art that palladium octaethylporphyrin is considered to be a green light excitation up-conversion material is overcome.

Description

多通道可调谐弱光上转换发光体系及其应用Multi-channel tunable low-light upconversion light-emitting system and its application 技术领域technical field
本发明涉及弱光上转换领域，具体涉及多通道可调谐弱光上转换发光体系及其应用。The invention relates to the field of weak light up-conversion, in particular to a multi-channel tunable weak light up-conversion lighting system and its application.
背景技术Background technique
上转换意指在长波长的光（低能量的光）激发下获得短波长的光（高能量的光）。基于有机材料的上转换目前有三类：强双光子吸收上转换（two-photon absorption upconversion，简称TPA-UC）、三线态-三线态湮灭上转换（triplet-triplet annihilation upconversion，简称TTA-UC）和单光子吸收上转换（one-photon absorption upconversion，简称OPA-UC）。TPA-UC需要在兆瓦/平方厘米的强光（>MW×cm -2）激发下获得，故称为强光上转换；TTA-UC和OPA-UC则需要在毫瓦/平方厘米的弱光（~mW×cm -2）激发下获得，故称为弱光上转换。显然，弱光上转换在太阳能光伏、光催化、生物医学、光调控照明及环境检测等领域具有更大的应用价值。 Up-conversion means obtaining short-wavelength light (high-energy light) under excitation by long-wavelength light (low-energy light). There are currently three types of upconversion based on organic materials: two-photon absorption upconversion (TPA-UC), triplet-triplet annihilation upconversion (TTA-UC) and One-photon absorption upconversion (OPA-UC). TPA-UC needs to be obtained under the excitation of strong light (>MW×cm -2 ) at MW/cm2, so it is called strong light up-conversion; TTA-UC and OPA-UC need to be excited at the weak light of mW/cm2 It is obtained under excitation by light (~mW×cm -2 ), so it is called weak light upconversion. Obviously, weak light upconversion has greater application value in the fields of solar photovoltaic, photocatalysis, biomedicine, light-regulated lighting and environmental detection.
TTA-UC和OPA-UC所涉及的材料不同。TTA-UC材料为双组份体系，而OPA-UC则为单组份体系。TTA-UC需要光敏剂-湮灭剂双组份共同参与（介质通常为溶剂）。微观机制如下：光敏剂首先收获低能量激发光，进而系间窜越（ISC）；然后光敏剂将三线态能量传递到湮灭剂；最后两个激发的三线态湮灭剂分子经历电子自旋转换的过程，发射出相对于低能激发光的高能光子上转换。而OPA-UC涉及的材料仅为发光剂自身（即单组份），其机理为：发光剂分子具有热带吸收特性：即可从基态（S 0）的较高振动能级（热带）（S t）跃迁至激发单线态（S 1）激发，随后发出比吸收的光子更高的能量的光子。由上可见，TTA-UC和OPA-UC由于它们的微观机理不同，虽可同归于弱光上转换发光领域，实则为毫无关联的两种发光机制和体系。 The materials involved in TTA-UC and OPA-UC are different. TTA-UC material is a two-component system, while OPA-UC is a one-component system. TTA-UC requires the participation of two components of photosensitizer-annihilation agent (the medium is usually a solvent). The microscopic mechanism is as follows: the photosensitizer first harvests low-energy excitation light, followed by intersystem crossing (ISC); then the photosensitizer transfers the triplet energy to the annihilating agent; the last two excited triplet annihilating molecules undergo electron spin conversion. A process that emits high-energy photons that are upconverted relative to low-energy excitation light. The material involved in OPA-UC is only the luminescent agent itself (that is, a single component). The mechanism is: the luminescent agent molecule has the characteristic of tropical absorption: the higher vibrational energy level (tropical) from the ground state (S 0 ) (S 0 ). t ) transition to an excited singlet state (S 1 ) excitation followed by emission of photons of higher energy than the absorbed photons. It can be seen from the above that TTA-UC and OPA-UC, due to their different microscopic mechanisms, can be classified into the field of low-light up-conversion luminescence, but they are actually two unrelated luminescence mechanisms and systems.
现有技术存在能同时适用双组份体系与单组份体系进行上转换发光的材料，但是存在反斯托克斯位移小、双组份体系与单组份体系激发光不同的问题。In the prior art, there are materials that can be applied to both the two-component system and the one-component system for up-conversion luminescence, but there are problems that the anti-Stokes shift is small and the excitation light of the two-component system and the one-component system is different.
技术问题technical problem
本发明首次公开了八乙基卟啉钯(PdOEP)单光子溶液，获得红-转-黄上转换发射；进一步的，将PdOEP与湮灭剂9,10-二苯基蒽（DPA）配制成混合溶液，发出红-转-蓝上转换发射。从而实现在不同波长光激发下，获得可调谐上转换发光体系，在防伪和生物探测领域具有应用价值。The invention discloses for the first time an octaethylporphyrin palladium (PdOEP) single-photon solution to obtain red-to-yellow up-conversion emission; further, the PdOEP and the annihilation agent 9,10-diphenylanthracene (DPA) are prepared into a mixed solution solution, emits red-to-blue upconversion emission. Thus, a tunable up-conversion luminescence system can be obtained under the excitation of light of different wavelengths, which has application value in the fields of anti-counterfeiting and biological detection.
技术解决方案technical solutions
本发明采用如下技术方案：多通道可调谐弱光上转换双组份体系，包括八乙基卟啉钯、蒽衍生物与溶剂；优选的，弱光上转换双组份体系由八乙基卟啉钯、蒽衍生物与溶剂组成。The present invention adopts the following technical scheme: a multi-channel tunable weak light up-conversion two-component system, including octaethyl porphyrin palladium, anthracene derivatives and a solvent; preferably, the weak light up-conversion two-component system is composed of octaethyl porphyrin Palladium, anthracene derivatives and solvent composition.
多通道可调谐弱光上转换单组份体系，包括八乙基卟啉钯与溶剂；优选的，弱光上转换双组份体系由八乙基卟啉钯与溶剂组成。The multi-channel tunable weak light up-conversion one-component system includes octaethyl porphyrin palladium and a solvent; preferably, the weak light up-conversion two-component system is composed of octaethyl porphyrin palladium and a solvent.
本发明公开了上述多通道可调谐弱光上转换双组份体系在制备红-转-蓝上转换材料或者红-转-黄上转换材料中的应用，或者上述多通道可调谐弱光上转换双组份体系作为红-转-蓝上转换材料或者红-转-黄上转换材料的应用。The invention discloses the application of the above-mentioned multi-channel tunable weak light up-conversion two-component system in preparing red-to-blue up-conversion material or red-to-yellow up-conversion material, or the above-mentioned multi-channel tunable weak light up-conversion Application of two-component system as red-to-blue upconversion material or red-to-yellow upconversion material.
本发明公开了上述多通道可调谐弱光上转换单组份体系在制备红-转-黄上转换材料中的应用，或者上述多通道可调谐弱光上转换单组份体系作为红-转-黄上转换材料的应用。The invention discloses the application of the above-mentioned multi-channel tunable weak light up-conversion one-component system in the preparation of red-to-yellow up-conversion materials, or the above-mentioned multi-channel tunable weak light up-conversion one-component system as a red-to-yellow up-conversion one-component system. Application of yellow up-conversion materials.
本发明的创造性在于首次公开了八乙基卟啉钯体系实现红光激发上转换材料，克服了现有技术认为八乙基卟啉钯都是绿光激发上转换材料的技术偏见。The creativity of the present invention lies in that the octaethyl porphyrin palladium system is disclosed for the first time to realize the red light excited up-conversion material, which overcomes the technical prejudice that the octaethyl porphyrin palladium is the green light excited up-conversion material in the prior art.
本发明公开了一种红光上转换的方法，具体为，利用红光照射弱光上转换双组份体系或者弱光上转换单组份体系，得到黄光或者蓝光，实现红光上转换；所述弱光上转换双组份体系由八乙基卟啉钯、蒽衍生物与溶剂组成；所述弱光上转换单组份体系由八乙基卟啉钯与溶剂组成。本发明公开的红光上转换可以得到蓝光，也可以得到黄光。The invention discloses a method for up-conversion of red light. Specifically, the red light is used to irradiate a weak-light up-conversion two-component system or a weak-light up-conversion single-component system to obtain yellow light or blue light, and realize the red light up-conversion; The weak light up-conversion two-component system is composed of octaethyl porphyrin palladium, an anthracene derivative and a solvent; the weak light up-conversion one-component system is composed of octaethyl porphyrin palladium and a solvent. The red light up-conversion disclosed in the present invention can obtain blue light and yellow light.
本发明制备的双组份体系包含八乙基卟啉钯（PdOEP，其即可作为光敏剂又可作为发光剂）和9,10-二苯基蒽（DPA，其作为湮灭剂），溶剂为DMF（N,N-二甲基甲酰胺）。将上述双组分体系装入比色皿中，在655 nm激发光照射下（隔氧），可得到红-转-蓝上转换发射，反斯托克斯位移为0.99 eV，最大红-转-蓝上转换效率为1.23%。在655 nm激发光照射下（不隔氧），则可得到红-转-黄上转换发射，反斯托克斯位移为0.26 eV，最大红-转-蓝上转换效率为0.38%。现有技术针对八乙基卟啉钯，都是在532 nm激发光照射下（隔氧），得到绿-转-蓝上转换发射，未见采用其他波长光照射的报道。The two-component system prepared by the present invention comprises palladium octaethylporphyrin (PdOEP, which can be used as both a photosensitizer and a luminescent agent) and 9,10-diphenylanthracene (DPA, which is used as an annihilating agent), and the solvent is DMF (N,N-dimethylformamide). Load the above two-component system into a cuvette, at 655 Under the irradiation of nm excitation light (oxygen barrier), red-to-blue upconversion emission can be obtained, the anti-Stokes shift is 0.99 eV, and the maximum red-to-blue upconversion efficiency is 1.23%. Under the irradiation of 655 nm excitation light (without oxygen barrier), red-to-yellow upconversion emission can be obtained, the anti-Stokes shift is 0.26 eV, and the maximum red-to-blue upconversion efficiency is 0.38%. Prior art for octaethyl porphyrin palladium, all at 532 Under the irradiation of nm excitation light (oxygen barrier), green-to-blue up-conversion emission is obtained, and there is no report of using other wavelengths of light.
本发明弱光上转换双组份体系或者弱光上转换单组份体系的激发光由常规半导体激光器作为光源，激发光强度在0.5~2 W/cm 2。 The excitation light of the weak light up-conversion two-component system or the weak light up-conversion single-component system of the present invention uses a conventional semiconductor laser as a light source, and the excitation light intensity is 0.5-2 W/cm 2 .
本发明中，所述八乙基卟啉钯(PdOEP)即可作为光敏剂又可作为发光剂，其化学结构式如下：
Figure 653256dest_path_image001
。 In the present invention, the octaethylporphyrin palladium (PdOEP) can be used as both a photosensitizer and a luminescent agent, and its chemical structural formula is as follows:
Figure 653256dest_path_image001
.
所述9,10-二苯基蒽(DPA)的化学结构式如下：
Figure 56555dest_path_image002
。 The chemical structural formula of the 9,10-diphenylanthracene (DPA) is as follows:
Figure 56555dest_path_image002
.
本发明中，弱光上转换双组份体系中，八乙基卟啉钯、蒽衍生物的摩尔比为1∶（5～30），优选为1∶25；八乙基卟啉钯的浓度为50mM～125mM，优选为100mM。In the present invention, in the weak light up-conversion two-component system, the molar ratio of octaethyl porphyrin palladium and anthracene derivatives is 1: (5-30), preferably 1: 25; the concentration of octaethyl porphyrin palladium It is 50 mM to 125 mM, preferably 100 mM.
本发明中，弱光上转换单组份体系中，八乙基卟啉钯的浓度为80mM～120mM，优选为100mM。In the present invention, in the weak light up-conversion one-component system, the concentration of octaethylporphyrin palladium is 80mM-120mM, preferably 100mM.
本发明在655 nm激发下（隔绝氧气），PdOEP/DPA的DMF溶液发出430nm的蓝色上转换，此上转换为红-转-蓝发光，红-转-蓝上转换的最大反斯托克斯位移为0.99 eV。首次公开了八乙基卟啉钯(PdOEP)红光激发上转换体系。In the present invention, under the excitation of 655 nm (isolated from oxygen), the DMF solution of PdOEP/DPA emits blue up-conversion at 430 nm, and this up-conversion is red-to-blue luminescence, and the maximum anti-Stokes of red-to-blue up-conversion The Sterling shift is 0.99 eV. The red light excited upconversion system of octaethylporphyrin palladium (PdOEP) was disclosed for the first time.
附图说明Description of drawings
图 1为PdOEP(100 mM)和DPA(10 mM)的吸收光谱和荧光光谱（溶剂：DMF）。Figure 1 shows the absorption and fluorescence spectra of PdOEP (100 mM) and DPA (10 mM) (solvent: DMF).
图 2为在532 nm激发下，PdOEP/DPA溶液（脱气的DMF）二元体系上转换光谱强度与激发光功率密度之间关系（上）和相应的上转换积分对数与功率密度对数作图（下）（PdOEP/DPA浓度为10 µM/1 mM）。Figure 2 shows the relationship between the upconversion spectral intensity and the excitation light power density of the PdOEP/DPA solution (degassed DMF) binary system under excitation at 532 nm (top) and the corresponding upconversion integral logarithm and power density logarithm Plot (bottom) (PdOEP/DPA at 10 µM/1 mM).
图 3为在655 nm激发下，PdOEP溶液（100 mM，无脱气DMF溶液）发出黄色上转换光谱强度与激发光功率密度之间关系（上，插图为上转换光谱的寿命）和相应的上转换积分对数与功率密度对数作图（下）。Figure 3 shows the relationship between the intensity of the yellow upconversion spectrum emitted by PdOEP solution (100 mM, no degassed DMF solution) and the excitation light power density under excitation at 655 nm (upper, the inset is the lifetime of the upconversion spectrum) and the corresponding upper The logarithm of the transformation integral is plotted against the logarithm of the power density (bottom).
图 4 为在655 nm 激发下，PdOEP （100 mM，无脱气DMF溶液）随温度变化的上转换光谱（其中，a:195 K; b:226 K; c:232 K; d:244 K；e:263 K; f:286 K）。Figure 4 shows the temperature-dependent upconversion spectra of PdOEP (100 mM, without degassing DMF solution) under excitation at 655 nm (where a:195 K; b: 226 K; c: 232 K; d: 244 K; e: 263 K; f: 286 K).
图 5为在655 nm激发下（隔绝氧气），PdOEP/DPA溶液上转换光谱强度与湮灭剂浓度之间的关系（脱气DMF，光敏剂浓度固定为100 µM）。Figure 5 shows the relationship between the upconversion spectral intensity of PdOEP/DPA solution and the concentration of annihilating agent (degassed DMF, with a fixed photosensitizer concentration of 100 µM) under excitation at 655 nm (with oxygen exclusion).
图 6为在655 nm激发下（隔绝氧气），PdOEP/DPA溶液上转换光谱强度与光敏剂浓度之间的关系（脱气DMF，湮灭剂浓度固定为2.5 mM）。Figure 6 shows the relationship between the upconversion spectral intensity of PdOEP/DPA solution and the concentration of photosensitizer under excitation at 655 nm (isolated from oxygen) (degassed DMF, and the concentration of annihilation agent was fixed at 2.5 mM).
图 7为在655 nm激发下（隔绝氧气），PdOEP/DPA（100 µM/2.5 mM）上转换光谱溶剂效应。Figure 7 shows the PdOEP/DPA (100 µM/2.5 mM) upconversion spectral solvent effects.
图 8为在655 nm激发下（隔绝氧气），PdOEP/DPA（100 µM/2.5 mM）溶液发出430nm的蓝色上转换和575nm的黄色上转换，其上转换光谱强度与激发光功率密度之间关系。Figure 8 shows the PdOEP/DPA (100 µM/2.5 mM) solution emits blue upconversion at 430 nm and yellow upconversion at 575 nm, and the relationship between the upconversion spectral intensity and the excitation light power density.
图 9为在655 nm激发下（隔绝氧气），PdOEP/DPA（100 µM/2.5 mM）溶液发出430 nm的蓝色上转换强度积分对数与功率密度对数作图。Figure 9 shows the PdOEP/DPA (100 μM/2.5 mM) solution emits a blue upconversion intensity at 430 nm plotted against the logarithm of the logarithm of the power density.
图 10为在655 nm激发下（隔绝氧气），PdOEP/DPA（100 µM/2.5 mM）溶液发出575 nm的黄色上转换强度积分对数与功率密度对数作图。Figure 10 shows the PdOEP/DPA (100 µM/2.5 mM) solution emits a yellow upconversion intensity at 575 nm plotted against the logarithm of the logarithm of the power density.
图 11为PdOEP溶液（100mM，DMF溶剂)和参比ZnPc溶液（0.5mM，DMSO溶剂)的激发光谱，其中，ZnPc强度比实测数据缩小了50倍（发射波长固定在575 nm）。Figure 11 shows the excitation spectra of the PdOEP solution (100 mM, DMF solvent) and the reference ZnPc solution (0.5 mM, DMSO solvent), where the ZnPc intensity is 50 times smaller than the measured data (the emission wavelength is fixed at 575 nm).
图 12为在655 nm激发下，PdOEP溶液(100mM，DMF溶剂，无需除氧)的红-转-黄上转换光谱(a)和ZnPc溶液（0.5mM，DMSO溶剂)的荧光光谱(b)，其中，ZnPc强度比实测数据缩小了100倍。Figure 12 shows the red-to-yellow upconversion spectrum (a) of PdOEP solution (100mM, DMF solvent, without oxygen removal) and the fluorescence spectrum (b) of ZnPc solution (0.5mM, DMSO solvent) under excitation at 655 nm, Among them, the intensity of ZnPc is 100 times smaller than the measured data.
图 13为在655 nm激发下， DPA/PdOEP溶液 (2.5 mM/100 mM，脱气的DMF)的红转蓝上转换光谱(a)和ZnPc溶液（0.5mM，DMSO溶剂)的荧光光谱(b)，其中，ZnPc强度比实测数据缩小了100倍。Figure 13 shows the DPA/PdOEP solution (2.5 mM/100 mM, degassed DMF) red-to-blue upconversion spectrum (a) and fluorescence spectrum (b) of ZnPc solution (0.5 mM, DMSO solvent), where the ZnPc intensity is 100-fold smaller than the observed data.
本发明的实施方式Embodiments of the present invention
下面结合附图以及实施例对本发明作进一步描述：本实施例中，紫外-可见吸收光谱的测定是在SHIMADZU UV2600型紫外分光光度计上进行的；荧光光谱与上转换寿命是在Edinburgh FLS-920型荧光光谱仪上进行测定的。上转换光谱测试是分别在532nm和655 nm的半导体激光器作为光源（激发光强度为0.5~2W/cm 2，如无特殊说明，选择1718.9mW/cm 2）测试的（溶剂为DMF），用PR655光谱仪记录光谱。本发明的原料都是常规市售产品，具体制备方法以及测试方法都为常规技术；如无特殊说明，所有操作都在室温进行。 Below in conjunction with accompanying drawing and embodiment, the present invention is further described: in the present embodiment, the determination of ultraviolet-visible absorption spectrum is carried out on SHIMADZU UV2600 type ultraviolet spectrophotometer; measured on a fluorescence spectrometer. The up-conversion spectrum test is performed with semiconductor lasers at 532 nm and 655 nm as the light source (the excitation light intensity is 0.5~2W/cm 2 , if there is no special instruction, choose 1718.9mW/cm 2 ) (the solvent is DMF), using PR655 The spectrometer records the spectrum. The raw materials of the present invention are all conventional commercial products, and the specific preparation methods and testing methods are conventional techniques; unless otherwise specified, all operations are performed at room temperature.
溶液制备：弱光上转换双组份体系（光敏剂/湮灭剂）的制备方法如下：按照光敏剂/湮灭剂摩尔数配比为1: 25配制，配制光敏剂浓度为100 mM，湮灭剂浓度为2.5 mM的上转换双组份溶液进行测试（溶剂：DMF）；将光敏剂、湮灭剂加入DMF中，得到弱光上转换双组份体系。 Solution preparation: The preparation method of the weak light up-conversion two-component system (photosensitizer/annihilation agent) is as follows: according to the mole ratio of photosensitizer/annihilation agent is 1:25, the concentration of photosensitizer is 100 mM, and the concentration of annihilating agent is 100 mM. The test was performed on a 2.5 mM upconversion two-component solution (solvent: DMF); the photosensitizer and annihilation agent were added to DMF to obtain a weak light upconversion two-component system.
弱光上转换单组份体系制备方法如下：配制光敏剂浓度为100 mM单组份溶液进行测试（溶剂：DMF）；将光敏剂加入DMF中，得到弱光上转换单组份体系。The preparation method of the weak light up-conversion one-component system is as follows: prepare a single-component solution with a concentration of 100 mM photosensitizer for testing (solvent: DMF); add the photosensitizer to DMF to obtain a weak light up-conversion one-component system.
光敏剂八乙基卟啉钯(PdOEP)的化学结构式如下：
Figure 784340dest_path_image003
。 The chemical structural formula of the photosensitizer octaethylporphyrin palladium (PdOEP) is as follows:
Figure 784340dest_path_image003
.
湮灭剂9,10-二苯基蒽(DPA)的化学结构式如下：
Figure 7511dest_path_image004
。 The chemical structural formula of the annihilation agent 9,10-diphenylanthracene (DPA) is as follows:
Figure 7511dest_path_image004
.
光谱测试：光敏剂PdOEP（100 mM）与湮灭剂DPA（10 mM）的吸收光谱与荧光光谱如图1所示，可见，PdOEP的Soret带在391 nm，Q带吸收峰位分别在511nm和544 nm；在544 nm激发下记录到的559 nm和598 nm双发光带为荧光发射（见图1画圈处），在665 nm的发光和肩峰734 nm处的发光均为磷光发射。湮灭剂DPA的吸收峰位在356 nm，375 nm和395 nm，荧光峰位在411 nm和434 nm。 Spectral test: The absorption and fluorescence spectra of the photosensitizer PdOEP (100 mM) and the annihilation agent DPA (10 mM) are shown in Figure 1. It can be seen that the Soret band of PdOEP is at 391 nm, and the Q-band absorption peaks are at 511 nm and 544, respectively. nm; the double emission bands at 559 nm and 598 nm recorded under excitation at 544 nm are fluorescence emission (see the circle in Figure 1), and the emission at 665 nm and the shoulder at 734 nm are both phosphorescence emission. The absorption peaks of the annihilating agent DPA are at 356 nm, 375 nm and 395 nm, and the fluorescence peaks are at 411 nm and 434 nm.
绿 - 转 - 蓝光谱测试具体操作如下：将弱光上转换双组份体系加入到石英比色皿中，通入氮气15min以除去氧气，然后拧紧比色皿帽盖，得到双组份体系。放置到光学平台上，然后用532nm半导体激光器照射该双组份体系，即可记录得到图2。图2是在532 nm激发下，PdOEP/DPA（10 µM/1 mM，脱气，DMF）二元体系的蓝色上转换光谱图（峰位430 nm），其中上图为上转换光谱强度与激发光功率密度之间关系图，下图为相应的上转换积分对数与功率密度（激发光强度）对数作图。可见，随着激发光强度的增大，蓝色上转换强度也在增大，将上转换强度的对数值与激发光的功率密度对数值作图（下图），得出一条斜率值为~2的曲线。由于使用的激发光源为532nm绿光光源，此上转换为绿-转-蓝发光，绿-转-蓝上转换的反斯托克斯位移为0.55 eV。 The specific operation of the green - to - blue spectral test is as follows : add the low-light up-conversion two-component system into a quartz cuvette, pass nitrogen for 15 minutes to remove oxygen, and then tighten the cap of the cuvette to obtain a two-component system. Placed on an optical table, and then irradiated the two-component system with a 532nm semiconductor laser, Figure 2 can be recorded. Figure 2 is the blue upconversion spectrum (peak at 430 nm) of the PdOEP/DPA (10 µM/1 mM, degassed, DMF) binary system under excitation at 532 nm. The relationship between the excitation light power density, the lower figure is the corresponding logarithm of the upconversion integral and the logarithm of the power density (excitation light intensity). It can be seen that with the increase of the excitation light intensity, the blue up-conversion intensity also increases. The log value of the up-conversion intensity and the log value of the power density of the excitation light are plotted (below), and a slope value is obtained. ~ 2 curves. Since the excitation light source used is a 532 nm green light source, this upconversion is green-to-blue emission, and the anti-Stokes shift of green-to-blue upconversion is 0.55 eV.
红 - 转 - 黄发光测试具体操作如下：将PdOEP加入DMF中，配制出PdOEP（100mM）DMF溶液，加入到石英比色皿中，拧紧比色皿帽盖（无需除氧），得到单组份体系。放置到光学平台上，直接用655nm半导体激光器照射，即可记录出图3。图3记录的是通过热振动能级激发的单光子吸收上转换光谱。上图为上转换光谱强度与激发光功率密度之间关系，下图为相应的上转换积分对数与功率密度对数作图，得出斜率（slope）=1.0，说明该红-转-黄上转换经历了单光子吸收过程。由于使用的激发光源为655nm红光光源，此上转换为红-转-黄发光，红-转-黄上转换的最大反斯托克斯位移为0.26 eV。 The specific operation of the red - to - yellow luminescence test is as follows: add PdOEP to DMF to prepare a PdOEP (100mM) DMF solution, add it to a quartz cuvette, tighten the cap of the cuvette (no oxygen removal is required), and obtain a single-component system. Place it on an optical table and directly irradiate it with a 655nm semiconductor laser to record Figure 3. Figure 3 records single-photon absorption upconversion spectra excited by thermal vibrational levels. The upper figure is the relationship between the up-conversion spectral intensity and the excitation light power density, and the lower figure is the corresponding up-conversion integral logarithm and the power density logarithm plot, and the slope (slope) = 1.0, indicating that the red-to-yellow The upconversion undergoes a single-photon absorption process. Since the excitation light source used is a 655 nm red light source, this upconversion is red-to-yellow emission, and the maximum anti-Stokes shift of red-to-yellow upconversion is 0.26 eV.
进一步测试了在655 nm激光器的激发下的低温上转换光谱，如图4所示，其中，a:195 K、b:226 K、c:232 K、d:244 K、e:263 K、f:286 K。可见，当温度为195 K时，PdOEP在575 nm处没有出现光谱；当温度升高为226 K时，575 nm处出现了明显上转换发射光谱，需要指出的是，位于626 nm的峰不是PdOEP的上转换发光，而是来自激光器的杂峰（见图4插图）。当温度继续升高，由232 K到286 K时，位于575 nm和~617 nm的上转换光谱越来越强，此为PdOEP典型的发光光谱的形状。The low-temperature upconversion spectra under the excitation of 655 nm laser were further tested, as shown in Fig. 4, where a: 195 K, b: 226 K, c: 232 K, d: 244 K, e: 263 K, f :286K. It can be seen that when the temperature is 195 K, PdOEP has no spectrum at 575 nm; when the temperature is increased to 226 K, there is an obvious up-conversion emission spectrum at 575 nm. It should be pointed out that at 626 The peak at nm is not the upconversion luminescence of PdOEP, but the spurious peak from the laser (see inset of Fig. 4). When the temperature continued to increase, from 232 K to 286 K, the upconversion spectra at 575 nm and ~617 nm became stronger and stronger, which is the typical shape of the luminescence spectrum of PdOEP.
通过以上这些实验数据，证实本发明首次公开的PdOEP/DMF溶液实现了单光子吸收（OPA）红-转-黄上转换。Through the above experimental data, it is confirmed that the PdOEP/DMF solution disclosed for the first time in the present invention realizes one-photon absorption (OPA) red-to-yellow up-conversion.
红 - 转 - 蓝发光测试具体操作如下：将弱光上转换双组份体系加入到石英比色皿中，通入氮气15min以除去氧气，然后拧紧比色皿帽盖，得到双组份体系。放置到光学平台上，然后用655nm半导体激光器照射该双组份体系，即可记录得到如下图谱。 The specific operation of the red - to - blue luminescence test is as follows: add the low-light up-conversion two-component system into a quartz cuvette, pass nitrogen for 15 minutes to remove oxygen, and then tighten the cap of the cuvette to obtain a two-component system. Place it on an optical table, and then irradiate the two-component system with a 655nm semiconductor laser, and the following spectrum can be recorded.
图5是在655 nm激发下，PdOEP/DPA的上转换强度与DPA浓度之间的关系（脱氧气，DMF，光敏剂浓度固定为100 µM）；可见，当DPA的浓度为2.5 mM时，上转换强度最大。Figure 5 is the relationship between the upconversion intensity of PdOEP/DPA and DPA concentration under excitation at 655 nm (deoxygenation, DMF, photosensitizer concentration fixed at 100 µM); it can be seen that when the concentration of DPA is 2.5 mM, the Conversion intensity is maximum.
图6是在655 nm激发下，PdOEP/DPA上转换强度与PdOEP浓度之间的关系（脱氧气，DMF，湮灭剂浓度固定为2.5 mM）；可见，当PdOEP的浓度为100 mM时，上转换强度最大。Figure 6 is the relationship between the upconversion intensity of PdOEP/DPA and the concentration of PdOEP under excitation at 655 nm (deoxygenation, DMF, and the annihilating agent concentration was fixed at 2.5 mM); it can be seen that when the concentration of PdOEP is 100 mM, the upconversion maximum strength.
图7是在655 nm激发下（隔绝氧气），固定PdOEP/DPA的浓度为100 µM/2.5 mM，在不同溶剂（乙酸乙酯、甲苯、二氯甲烷、N,N-二甲基甲酰胺和正丙醇）中，其上转换光谱强度与溶剂种类之间的关系；可见，当溶剂为DMF时，上转换强度最大。Figure 7 shows the concentration of immobilized PdOEP/DPA at 100 under excitation at 655 nm (isolated from oxygen). µM/2.5 mM, in different solvents (ethyl acetate, toluene, dichloromethane, N,N-dimethylformamide, and n-propanol), the relationship between the upconversion spectral intensity and solvent species; it can be seen that when The upconversion intensity is the largest when the solvent is DMF.
图 8 在655 nm激发下（隔绝氧气），PdOEP/DPA（100 µM/2.5 mM，DMF）溶液发出430nm的蓝色上转换和575nm的黄色上转换，其上转换光谱强度随着激发光功率密度提高而增强。由于使用的激发光源为655nm红光光源，在430 nm处的光谱为红-转-蓝发光，红-转-蓝上转换的最大反斯托克斯位移为0.99 eV。在~575 nm处的光谱为红-转-黄上转换发光，蓝光最高强度在4.4×10 -5，黄光最高强度在6×10 -6，前者强度是后者强度的7.3倍。 Fig.8 Under excitation at 655 nm (isolated from oxygen), PdOEP/DPA (100 µM/2.5 mM, DMF) solution emits blue upconversion at 430 nm and yellow upconversion at 575 nm, and the upconversion spectral intensity varies with the excitation light power density enhance and enhance. Since the excitation light source used is a 655 nm red light source, the spectrum at 430 nm is red-to-blue emission, and the maximum anti-Stokes shift of red-to-blue up-conversion is 0.99 eV. The spectrum at ~575 nm is red-to-yellow up-conversion luminescence, the highest intensity of blue light is 4.4×10 -5 , and the highest intensity of yellow light is 6×10 -6 . The intensity of the former is 7.3 times that of the latter.
图 9为在655 nm激发下（隔绝氧气），PdOEP/DPA（100 µM/2.5 mM，DMF）溶液发出430nm的蓝色上转换强度积分对数与功率密度对数图，可见其斜率（slope）=2.7，接近3。Figure 9 shows the PdOEP/DPA (100 μM/2.5 mM, DMF) solution emits a blue up-conversion intensity logarithm and power density logarithm plot at 430 nm, and its slope (slope) = 2.7, close to 3.
图10为在655 nm激发下（隔绝氧气），PdOEP/DPA（100 µM/2.5 mM，DMF）溶液发出570nm的黄色上转换强度积分对数与功率密度对数作图，其斜率（slope）=0.8（接近1）。Figure 10 shows the PdOEP/DPA (100 µM/2.5 mM, DMF) solution emits yellow at 570 nm. The integrated logarithm of the upconversion intensity is plotted against the logarithm of the power density, with slope = 0.8 (close to 1).
红 - 转 - 黄上转换效率：对于单光子吸收上转换(OPA-UC)的测量，制备不脱气DMF的PdOEP溶液（100mM）。用半导体固态激光器(655 nm)。用位于滤光片背面的PR655光谱扫描仪(655 nm)记录OPA-UC光谱，根据式（2）计算相对于ZnPc的红转黄净上转换效（F OPA-UC）。 Red - to - yellow upconversion efficiency: For the measurement of one-photon absorption upconversion (OPA-UC), a PdOEP solution (100 mM) without degassing DMF was prepared. A semiconductor solid-state laser (655 nm) was used. The OPA-UC spectrum was recorded with a PR655 spectral scanner (655 nm) located on the back of the filter, and the net red-to-yellow upconversion efficiency (F OPA-UC ) relative to ZnPc was calculated according to equation (2).
Figure 478944dest_path_image005
 。
Figure 478944dest_path_image005
.
式中，F r为ZnPc的荧光量子产率，以其为参考标准(F r=20%，在DMSO中为0.5 mM)。F s和F r分别是PdOEP和ZnPc在655 nm激发波长下的积分发射。I s(655)和I r(655)分别为PdOEP和ZnPc在655 nm波长处的激发强度。这里利用的是激发强度(I ex)，而不是通常使用的吸光度(A)。这是因为无法得到PdOEP在655 nm处的吸光度(A)，而PdOEP在655 nm处的激发强度则可得到（图11）。n s和n r分别是样品溶液和参比溶液的折射率。详细数据见图11和图12。由此计算出红-转-黄上转换效率为0.38%。 In the formula, F r is the fluorescence quantum yield of ZnPc, which is used as the reference standard (F r =20%, 0.5 mM in DMSO). Fs and Fr are the integrated emission of PdOEP and ZnPc at the excitation wavelength of 655 nm, respectively. Is (655) and Ir(655) are the excitation intensities of PdOEP and ZnPc at the wavelength of 655 nm, respectively. The excitation intensity (I ex ) is used here, rather than the absorbance (A) commonly used. This is because the absorbance (A) of PdOEP at 655 nm is not available, while the excitation intensity of PdOEP at 655 nm is available (Figure 11). n s and n r are the refractive indices of the sample solution and the reference solution, respectively. See Figure 11 and Figure 12 for detailed data. From this, the red-to-yellow up-conversion efficiency was calculated to be 0.38%.
为了获得红转蓝上转换效率，在DMF中配制了DPA/PdOEP双组分溶液（100 µM/2.5 mM，DMF），氮气脱气约15 min。用半导体固态激光器(655 nm)激发。用位于滤光片背面的PR655光谱扫描仪（655 nm）记录OPA-TTA-UC光谱，根据式（2）计算相对于ZnPc的红-转-蓝净上转换效率 (F OPA-TTA-UC)。式(2)中，F r为ZnPc的荧光量子子产率(F r = 20%)。F s和F r分别为DPA和参比ZnPc在655 nm激发波长下的积分发射。I s(655)、I r(655)、n s和n r等参数与红转黄效率的计算相同。详细数据见图11和图13。由此计算出红-转-蓝上转换效率为1.23%。 To obtain the red-to-blue upconversion efficiency, a two-component solution of DPA/PdOEP (100 µM/2.5 mM, DMF) was prepared in DMF and degassed with nitrogen for about 15 min. Excitation with a semiconductor solid-state laser (655 nm). The OPA-TTA-UC spectrum was recorded with a PR655 spectral scanner (655 nm) located on the back of the filter, and the red-to-blue upconversion efficiency (F OPA-TTA-UC ) relative to ZnPc was calculated according to equation (2). . In formula (2), F r is the fluorescence quantum quantum yield of ZnPc (F r = 20%). F s and F r are the integrated emission of DPA and reference ZnPc at excitation wavelength of 655 nm, respectively. Parameters such as I s(655) , I r(655) , ns and n r are the same as the calculation of the red-to-yellow efficiency. See Figure 11 and Figure 13 for detailed data. From this, the red-to-blue up-conversion efficiency was calculated to be 1.23%.
注意，以上所有上转换效率均为净效率，F OPA-TTA-UC 也没有乘以OPA和TTA机制中的3倍。此外，为了简单起见，在计算中使用溶剂的折射率而不是溶液的折射率。 Note that all the above upconversion efficiencies are net efficiencies, and the F OPA-TTA-UC is also not multiplied by a factor of 3 in the OPA and TTA mechanisms. Also, for simplicity, the refractive index of the solvent is used in the calculations instead of the refractive index of the solution.
对比例：将四苯基卟啉钯（PdTPP）加入DMF中，配制出PdTPP（100mM）DMF溶液，加入到石英比色皿中，拧紧比色皿帽盖（无需除氧），得到单组份体系；放置到光学平台上，直接用655nm半导体激光器照射，无发射光，即不发生上转换。 Comparative example: Add tetraphenylporphyrin palladium (PdTPP) to DMF to prepare a PdTPP (100mM) DMF solution, add it to a quartz cuvette, tighten the cap of the cuvette (without deoxygenation), and obtain a single component system; placed on the optical platform, directly irradiated with a 655nm semiconductor laser, no emission light, that is, no up-conversion occurs.
将四苯基卟啉钯（PdTPP）、9,10-二苯基蒽(DPA)加入DMF中，配制出PdTPP/DPA（100 µM/2.5 mM，DMF）溶液，加入到石英比色皿中，拧紧比色皿帽盖（除氧），得到单组份体系；放置到光学平台上，直接用655nm半导体激光器照射，无发射光，即不发生上转换。但是用532nm半导体激光器照射该双组份体系，即可实现蓝色上转换。Tetraphenylporphyrin palladium (PdTPP) and 9,10-diphenylanthracene (DPA) were added to DMF to prepare a PdTPP/DPA (100 µM/2.5 mM, DMF) solution, which was added to a quartz cuvette, Tighten the cap of the cuvette (deoxygenation) to obtain a one-component system; place it on the optical platform and directly irradiate it with a 655nm semiconductor laser, no emission light, that is, no up-conversion occurs. But irradiating the two-component system with a 532nm semiconductor laser can achieve blue up-conversion.
将吩噻嗪加入DMF中，配制出吩噻嗪（100mM）DMF溶液，加入到石英比色皿中，拧紧比色皿帽盖（无需除氧），得到单组份体系；放置到光学平台上，直接用655nm半导体激光器照射，无发射光，即不发生上转换。Add phenothiazine to DMF to prepare a phenothiazine (100mM) DMF solution, add it to a quartz cuvette, tighten the cap of the cuvette (without deoxygenation) to obtain a one-component system; place it on an optical table , directly irradiated with a 655nm semiconductor laser, no emission light, that is, no up-conversion occurs.
吩噻嗪结构式如下：
Figure 736750dest_path_image006
 。 The structural formula of phenothiazine is as follows:
Figure 736750dest_path_image006
.
以氮杂蒽衍生物PSF作为光敏剂（浓度为10 μM），与发光剂DPA（浓度为1 mM）复配进行三线态-三线态湮灭上转换测试，测试溶剂为二氯甲烷/正丙醇=1/1（v/v）。结果发现，以532 nm 波长的光作为激发，PSF能与DPA复配产生明显的上转换；但是以655 nm波长的光作为激发，未出现上转换现象。进一步的，以655 nm波长的光作为激发，单组份PSF的DMSO溶液出现单光子上转换，肉眼观察红-转-黄的变化；但是以532 nm 波长的光作为激发，未出现上转换现象。The triplet-triplet annihilation upconversion test was performed using the azaanthene derivative PSF as a photosensitizer (concentration of 10 μM) and luminescent agent DPA (concentration of 1 mM). The test solvent was dichloromethane/n-propanol =1/1(v/v). The results showed that when the light of 532 nm wavelength was used as excitation, PSF could be combined with DPA to produce obvious up-conversion; but when the light of 655 nm wavelength was used as excitation, no up-conversion phenomenon occurred. Further, to 655 With the light of nm wavelength as excitation, the DMSO solution of one-component PSF showed single-photon up-conversion, and the change of red-to-yellow was observed with the naked eye; however, when the light of 532 nm wavelength was used as the excitation, no up-conversion phenomenon occurred.
氮杂蒽衍生物PSF结构式如下：
Figure 901015dest_path_image007
。 The structural formula of the azaanthene derivative PSF is as follows:
Figure 901015dest_path_image007
.
本发明通过多种激发机制实现在不同波长光激发下，获得可调谐上转换发光，创造性公开了八乙基卟啉钯(PdOEP)单光子发光体系，获得红-转-黄上转换发射；八乙基卟啉钯(PdOEP)双光子发光体系，获得红-转-蓝上转换发射；克服了现有技术认为八乙基卟啉钯(PdOEP)仅能实现绿转蓝上转换的技术偏见；在防伪和生物探测领域具有应用价值。The invention achieves tunable up-conversion luminescence under excitation of different wavelengths of light through various excitation mechanisms, and creatively discloses a single-photon luminescence system of palladium octaethylporphyrin (PdOEP) to obtain red-to-yellow up-conversion emission; Palladium ethyl porphyrin (PdOEP) two-photon luminescence system to obtain red-to-blue up-conversion emission; overcome the technical prejudice that octaethyl porphyrin palladium (PdOEP) can only achieve green-to-blue up-conversion in the prior art; It has application value in the field of anti-counterfeiting and biological detection.

Claims (10)

  1. 一种多通道可调谐弱光上转换双组份体系，其特征在于，包括八乙基卟啉钯、蒽衍生物与溶剂。A multi-channel tunable weak light up-conversion two-component system is characterized in that it comprises octaethylporphyrin palladium, an anthracene derivative and a solvent.
  2. 根据权利要求1所述多通道可调谐弱光上转换双组份体系，其特征在于，蒽衍生物为9,10-二苯基蒽；溶剂为DMF；八乙基卟啉钯、蒽衍生物的摩尔比为1∶（5～30）；八乙基卟啉钯的浓度为50mM～125mM。The multi-channel tunable weak light up-conversion two-component system according to claim 1, wherein the anthracene derivative is 9,10-diphenylanthracene; the solvent is DMF; octaethylporphyrin palladium, anthracene derivatives The molar ratio is 1: (5～30); the concentration of octaethylporphyrin palladium is 50mM～125mM.
  3. 一种多通道可调谐弱光上转换单组份体系，包括八乙基卟啉钯与溶剂。A multi-channel tunable weak light up-conversion one-component system comprises octaethyl porphyrin palladium and a solvent.
  4. 根据权利要求3所述多通道可调谐弱光上转换单组份体系，其特征在于，溶剂为DMF；八乙基卟啉钯的浓度为80mM～120mM。The multi-channel tunable weak light up-conversion one-component system according to claim 3, wherein the solvent is DMF; the concentration of octaethylporphyrin palladium is 80mM-120mM.
  5. 权利要求1所述多通道可调谐弱光上转换双组份体系在制备红-转-蓝上转换材料或者红-转-黄上转换材料中的应用，或者作为红-转-蓝上转换材料或者红-转-黄上转换材料的应用。Application of the multi-channel tunable weak light up-conversion two-component system of claim 1 in the preparation of a red-to-blue up-conversion material or a red-to-yellow up-conversion material, or as a red-to-blue up-conversion material Or the application of red-to-yellow upconversion materials.
  6. 权利要求3所述多通道可调谐弱光上转换单组份体系在制备红-转-黄上转换材料中的应用，或者作为红-转-黄上转换材料的应用。The application of the multi-channel tunable weak light up-conversion one-component system of claim 3 in the preparation of red-to-yellow up-conversion materials, or as the application of red-to-yellow up-conversion materials.
  7. 八乙基卟啉钯在制备红光激发上转换体系中的应用。Application of octaethylporphyrin palladium in the preparation of red light-excited upconversion systems.
  8. 一种红光上转换的方法，其特征在于，利用红光照射弱光上转换双组份体系或者弱光上转换单组份体系，得到黄光或者蓝光，实现红光上转换；所述弱光上转换双组份体系由八乙基卟啉钯、蒽衍生物与溶剂组成；所述弱光上转换单组份体系由八乙基卟啉钯与溶剂组成。A method for red light up-conversion, characterized in that, using red light to irradiate a weak light up-conversion two-component system or a weak light up-conversion single-component system to obtain yellow light or blue light to realize red light up-conversion; The light up-conversion two-component system is composed of octaethyl porphyrin palladium, an anthracene derivative and a solvent; the weak light up-conversion one-component system is composed of octaethyl porphyrin palladium and a solvent.
  9. 根据权利要求8所述红光上转换的方法，其特征在于，红光照射的强度为0.5~2 W/cm 2。 The method for red light up-conversion according to claim 8, wherein the intensity of the red light irradiation is 0.5-2 W/cm 2 .
  10. 根据权利要求8所述红光上转换的方法，其特征在于，溶剂为DMF。The method for red light up-conversion according to claim 8, wherein the solvent is DMF.
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