CN113150000A - Multichannel tunable weak light up-conversion light-emitting system and application thereof - Google Patents
Multichannel tunable weak light up-conversion light-emitting system and application thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 102
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 230000005284 excitation Effects 0.000 claims abstract description 58
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- HCIIFBHDBOCSAF-UHFFFAOYSA-N octaethylporphyrin Chemical compound N1C(C=C2C(=C(CC)C(C=C3C(=C(CC)C(=C4)N3)CC)=N2)CC)=C(CC)C(CC)=C1C=C1C(CC)=C(CC)C4=N1 HCIIFBHDBOCSAF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000001454 anthracenes Chemical class 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 8
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical group C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 108
- 239000000243 solution Substances 0.000 description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000003504 photosensitizing agent Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 238000004020 luminiscence type Methods 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- 238000001831 conversion spectrum Methods 0.000 description 4
- 239000000891 luminescent agent Substances 0.000 description 4
- 229950000688 phenothiazine Drugs 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 2
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- 238000001748 luminescence spectrum Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
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- 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
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- 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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
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- 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
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- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Abstract
The invention discloses a multi-channel tunable weak light up-conversion luminescent system and application thereof, wherein the weak light up-conversion two-component system consists of octaethylporphyrin palladium, an anthracene derivative and a solvent; the weak light up-conversion single-component system consists of octaethylporphyrin palladium and a solvent. And irradiating the weak light up-conversion two-component system or the weak light up-conversion single-component system by using red light to obtain yellow light or blue light, and realizing red light up-conversion. The invention discloses an octaethylporphyrin palladium system for realizing red light excitation upconversion material for the first time, and overcomes the technical prejudice that octaethylporphyrin palladium is a green light excitation upconversion material in the prior art.
Description
Technical Field
The invention relates to the field of weak light up-conversion, in particular to a multichannel tunable weak light up-conversion light-emitting system and application thereof.
Background
Up-conversion means that light of a short wavelength (light of high energy) is obtained under excitation by light of a long wavelength (light of low energy). There are currently three classes of upconversion based on organic materials: strong two-photon absorption upconversion (TPA-UC), triplet-triplet annihilation upconversion (TTA-UC), and single-photon absorption upconversion (OPA-UC). TPA-UC requires intense light at megawatts per square centimeter>MW×cm-2) Obtained under excitation, so it is called strong light up-conversion; TTA-UC and OPA-UC require weak light (mW x cm) in milliwatt/square centimeter-2) Obtained under excitation, and is called weak light up-conversion. Obviously, the weak light up-conversion has greater application value in the fields of solar photovoltaic, photocatalysis, biomedicine, light control illumination, environmental detection and the like.
TTA-UC and OPA-UC are related to different materials. The TTA-UC material is a two-component system, while the OPA-UC material is a single-component system. TTA-UC requires the co-participation of two components of a photosensitizer and an annihilator (the medium is usually a solvent). The microscopic mechanism is as follows: the photosensitizer first harvests low-energy excitation light, and then intersystem crossing (ISC); the photosensitizer then transfers triplet energy to the annihilator; the last two excited triplet annihilator molecules undergo an electron spin conversion process, emitting high-energy photons that are upconverted relative to low-energy excitation light. The OPA-UC only relates to the luminescent agent (namely, the single component) and has the following mechanism: the luminescent agent molecules have tropical absorption properties: i.e. from the ground state (S)0) Higher vibration level (tropical) (S)t) Transition to excited singlet state (S)1) Excitation followed by emission of a photon of higher energy than the absorbed photon. From the above, TTA-UC and OPA-UC can be classified into two unrelated luminescence mechanisms andand (4) preparing the system.
The prior art has the problems that the material is suitable for up-conversion luminescence of a two-component system and a single-component system at the same time, but the anti-Stokes displacement is small, and the exciting light of the two-component system is different from that of the single-component system.
Disclosure of Invention
The invention discloses a palladium octaethylporphyrin (PdOEP) single-photon solution for the first time, and red-to-yellow up-conversion emission is obtained; further, PdOEP and annihilator 9, 10-Diphenylanthracene (DPA) are prepared into a mixed solution to emit red-to-blue up-conversion emission. Therefore, the tunable up-conversion luminescent system can be obtained under the excitation of different wavelengths of light, and the tunable up-conversion luminescent system has application value in the fields of anti-counterfeiting and biological detection.
The invention adopts the following technical scheme:
a multi-channel tunable weak light up-conversion two-component system, which comprises octaethylporphyrin palladium, an anthracene derivative and a solvent; preferably, the weak light up-conversion two-component system consists of octaethylporphyrin palladium, an anthracene derivative and a solvent.
The multichannel tunable weak light upconversion single-component system comprises octaethylporphyrin palladium and a solvent; preferably, the weak light upconversion two-component system consists of octaethylporphyrin palladium and a solvent.
The invention discloses an application of the multichannel tunable weak light up-conversion two-component system in preparation of a red-to-blue up-conversion material or a red-to-yellow up-conversion material, or an application of the multichannel tunable weak light up-conversion two-component system as the red-to-blue up-conversion material or the red-to-yellow up-conversion material.
The invention discloses an application of the multichannel tunable weak light up-conversion single-component system in preparation of a red-to-yellow up-conversion material, or an application of the multichannel tunable weak light up-conversion single-component system as the red-to-yellow up-conversion material.
The invention discloses an octaethylporphyrin palladium system for realizing red light excitation upconversion material for the first time, and overcomes the technical prejudice that octaethylporphyrin palladium is a green light excitation upconversion material in the prior art.
The invention discloses a red light up-conversion method, which comprises the following steps of irradiating a weak light up-conversion two-component system or a weak light up-conversion single-component system by using red light to obtain yellow light or blue light, and realizing red light up-conversion; the weak light up-conversion two-component system consists of octaethylporphyrin palladium, an anthracene derivative and a solvent; the weak light up-conversion single-component system consists of octaethyl porphyrin palladium and a solvent. The red light up-conversion disclosed by the invention can obtain blue light and also can obtain yellow light.
The two-component system prepared by the invention comprises octaethylporphyrin palladium (PdOEP which can be used as a photosensitizer and a luminescent agent) and 9, 10-diphenylanthracene (DPA which is used as an annihilator), and a solvent is DMF (N, N-dimethylformamide). The double-component system is put into a cuvette and can obtain red-to-blue up-conversion emission under the irradiation of 655nm exciting light (oxygen isolation), the anti-Stokes shift is 0.99 eV, and the maximum red-to-blue up-conversion efficiency is 1.23%. Under 655nm exciting light irradiation (without oxygen isolation), red-to-yellow up-conversion emission can be obtained, the anti-Stokes shift is 0.26 eV, and the maximum red-to-blue up-conversion efficiency is 0.38%. In the prior art, aiming at octaethylporphyrin palladium, green-to-blue up-conversion emission is obtained under the irradiation of 532nm exciting light (oxygen isolation), and no report of irradiation with other wavelengths is found.
The exciting light of the weak light up-conversion two-component system or the weak light up-conversion single-component system is taken as a light source by a conventional semiconductor laser, and the intensity of the exciting light is 0.5-2W/cm2。
In the invention, the palladium octaethylporphyrin (PdOEP) can be used as a photosensitizer and a luminescent agent, and has the following chemical structural formula:
the chemical structural formula of the 9, 10-diphenyl anthracene (DPA) is as follows:
in the invention, in a weak light up-conversion two-component system, the molar ratio of the octaethylporphyrin palladium to the anthracene derivative is 1: 5-30, preferably 1: 25; the concentration of palladium octaethylporphyrin is 50mM to 125mM, preferably 100 mM.
In the present invention, the concentration of octaethylporphyrin palladium in the weak light upconversion single-component system is 80 mM-120 mM, preferably 100 mM.
Under the excitation of 655nm (oxygen is isolated), the DMF solution of PdOEP/DPA emits 430nm blue upconversion, the upconversion is red-to-blue luminescence, and the maximum anti-Stokes shift of the red-to-blue upconversion is 0.99 eV. An octaethylporphyrin palladium (PdOEP) red light excitation up-conversion system is disclosed for the first time.
Drawings
FIG. 1 shows absorption and fluorescence spectra of PdOEP (100 mM) and DPA (10 mM) (solvent: DMF);
FIG. 2 is a graph of the relationship between upconversion spectral intensity and excitation light power density for a binary system of PdOEP/DPA solution (degassed DMF) at 532nm excitation (up) and the corresponding logarithm of the integrated upconversion versus logarithm of the power density (down) (concentration of PdOEP/DPA 10. mu.M/1 mM);
FIG. 3 is a plot of the intensity of the yellow upconversion spectrum emitted by PdOEP solutions (100mM, without degassed DMF solution) versus the excitation light power density (upper, inset is lifetime of the upconversion spectrum) and the corresponding logarithm of the upconversion integral versus the logarithm of the power density (lower) at 655nm excitation;
FIG. 4 is an upconversion spectrum of PdOEP (100mM, in non-degassed DMF) with temperature under 655nm excitation (where a: 195K; b: 226K; c: 232K; d: 244K; e: 263K; f: 286K);
FIG. 5 is a plot of the relationship between the upconversion spectral intensity of PdOEP/DPA solution and the concentration of the annihilator under 655nm excitation (with degassed DMF, fixed photosensitizer concentration at 100 μ M);
FIG. 6 is the relationship between the converted spectral intensity on PdOEP/DPA solution and photosensitizer concentration under 655nm excitation (oxygen excluded) (degassed DMF, fixed concentration of annihilator at 2.5 mM);
FIG. 7 is a conversion spectrum solvent effect on PdOEP/DPA (100 μ M/2.5 mM) under 655nm excitation (with oxygen excluded);
FIG. 8 is a graph of the relationship between upconversion spectral intensity and excitation light power density for a blue upconversion at 430nm and a yellow upconversion at 575nm emitted from a PdOEP/DPA (100 μ M/2.5 mM) solution under 655nm excitation (with oxygen excluded);
FIG. 9 is a plot of logarithm of integrated blue upconversion intensity at 430nm emitted by PdOEP/DPA (100 μ M/2.5 mM) solution under 655nm excitation (with oxygen excluded) versus logarithm of power density;
FIG. 10 is a plot of the integrated logarithm of yellow upconversion intensity at 575nm emitted by PdOEP/DPA (100 μ M/2.5 mM) solution under 655nm excitation (with oxygen excluded) versus the logarithm of power density;
FIG. 11 shows excitation spectra of PdOEP solution (100mM, DMF solvent) and reference ZnPc solution (0.5 mM, DMSO solvent), in which the ZnPc intensity is reduced by a factor of 50 (emission wavelength fixed at 575 nm) from the measured data;
FIG. 12 is a plot of the red-to-yellow upconversion spectrum (a) of PdOEP solution (100mM, DMF solvent, without oxygen removal) and the fluorescence spectrum (b) of ZnPc solution (0.5 mM, DMSO solvent) at 655nm excitation, where the ZnPc intensity is 100-fold less than the observed data;
FIG. 13 shows the red-to-blue up-conversion spectrum (a) of a DPA/PdOEP solution (2.5 mM/100 mM, degassed DMF) and the fluorescence spectrum (b) of a ZnPc solution (0.5 mM, DMSO solvent) under 655nm excitation, where the ZnPc intensity is 100-fold less than the observed data.
Detailed Description
The invention is further described with reference to the following figures and examples:
in this example, the measurement of the UV-vis absorption spectrum was performed on a SHIMADZU UV2600 type UV spectrophotometer; fluorescence spectra and upconversion lifetimes were determined on an Edinburgh FLS-920 type fluorescence spectrometer. The up-conversion spectrum test is that semiconductor lasers with the wavelengths of 532nm and 655nm are respectively used as light sources (the excitation light intensity is 0.5-2W/cm)2If not otherwise specified, 1718.9mW/cm was selected2) Tested (solvent DMF), irradiated with PR655The spectrometer records the spectrum. The raw materials of the invention are conventional products sold on the market, and the specific preparation method and the test method are conventional technologies; all operations were carried out at room temperature unless otherwise specified.
Solution preparation:
the preparation method of the weak light up-conversion two-component system (photosensitizer/annihilator) comprises the following steps: preparing an up-conversion two-component solution with the photosensitizer concentration of 100mM and the annihilator concentration of 2.5 mM according to the molar ratio of the photosensitizer to the annihilator of 1: 25 for testing (solvent: DMF); adding a photosensitizer and an annihilating agent into DMF to obtain a weak light up-conversion two-component system.
The preparation method of the weak light up-conversion single-component system comprises the following steps: preparing a single-component solution with 100mM of photosensitizer concentration for testing (solvent: DMF); and adding a photosensitizer into DMF to obtain a weak light upconversion single-component system.
The chemical structural formula of the photosensitizer palladium octaethylporphyrin (PdOEP) is as follows:
the chemical structural formula of the annihilator 9, 10-Diphenylanthracene (DPA) is as follows:
and (3) spectrum testing:
the absorption spectrum and fluorescence spectrum of the photosensitizer PdOEP (100 mM) and the annihilator DPA (10 mM) are shown in figure 1, and the Soret band of the PdOEP is 391 nm, and the Q band absorption peak positions are 511nm and 544 nm respectively; the double emission bands of 559 nm and 598 nm recorded under 544 nm excitation are fluorescent emissions (see circled FIG. 1), and the emission at 665 nm and the emission at 734 nm shoulder are phosphorescent emissions. The absorption peak positions of the annihilator DPA are 356 nm, 375 nm and 395 nm, and the fluorescence peak positions are 411 nm and 434 nm.
The green-to-blue spectrum test specifically operates as follows:
and adding the low-light up-conversion two-component system into a quartz cuvette, introducing nitrogen for 15min to remove oxygen, and screwing a cuvette cap to obtain the two-component system. Placing the two-component system on an optical platform, and then irradiating the two-component system by using a 532nm semiconductor laser to obtain the graph 2 through recording. FIG. 2 is a blue upconversion spectrum (peak position 430 nm) of a PdOEP/DPA (10 μ M/1 mM, degassing, DMF) binary system under excitation of 532nm, wherein the upper graph is a graph of the upconversion spectrum intensity and the excitation light power density, and the lower graph is a graph of the corresponding logarithm of integration of upconversion and the logarithm of power density (excitation light intensity). It can be seen that as the intensity of the excitation light increases, the up-conversion intensity of blue light also increases, and the logarithm of the up-conversion intensity is plotted against the logarithm of the power density of the excitation light (lower graph), resulting in a curve with a slope value of 2. Since the excitation light source used was a 532nm green light source, this up-conversion was green-to-blue luminescence, and the anti-stokes shift of the green-to-blue up-conversion was 0.55 eV.
The red-turn-yellow luminescence test is specifically performed as follows:
adding PdOEP into DMF to prepare a PdOEP (100 mM) DMF solution, adding the solution into a quartz cuvette, and screwing a cuvette cap (without removing oxygen) to obtain a single-component system. The image can be recorded by placing the film on an optical platform and directly irradiating the film by a 655nm semiconductor laser. Figure 3 records a single photon absorption upconversion spectrum excited by thermal vibrational levels. The upper graph is the relationship between the upconversion spectral intensity and the excitation light power density, and the lower graph is the corresponding logarithm of the upconversion integral and the logarithm of the power density, so that the slope (slope) =1.0 is obtained, and the red-to-yellow upconversion is illustrated to undergo the single photon absorption process. Since the excitation light source used is a 655nm red light source, this up-conversion is red-to-yellow luminescence, and the maximum anti-stokes shift for red-to-yellow up-conversion is 0.26 eV.
The low temperature upconversion spectrum under excitation with a 655nm laser was further tested as shown in fig. 4, where a: 195K, b: 226K, c: 232K, d: 244K, e: 263K, f: 286K. It can be seen that PdOEP shows no spectrum at 575nm when the temperature is 195K; when the temperature was raised to 226K, a significant up-conversion emission spectrum appeared at 575nm, noting that the peak at 626 nm was not the up-conversion luminescence of PdOEP, but rather a stray peak from the laser (see inset FIG. 4). When the temperature is increased from 232K to 286K, the up-conversion spectra at 575nm and 617 nm are increasingly stronger, which is the shape of the typical luminescence spectrum of PdOEP.
From the above experimental data, it is confirmed that the PdOEP/DMF solution disclosed for the first time in the present invention realizes single photon absorption (OPA) red-to-yellow up-conversion.
The red-to-blue luminescence test operates specifically as follows:
and adding the low-light up-conversion two-component system into a quartz cuvette, introducing nitrogen for 15min to remove oxygen, and screwing a cuvette cap to obtain the two-component system. Placing the two-component system on an optical platform, and then irradiating the two-component system by using a 655nm semiconductor laser, so as to record and obtain the following atlas.
FIG. 5 is the relationship between the upconversion intensity of PdOEP/DPA and the DPA concentration under 655nm excitation (deoxygenated gas, DMF, photosensitizer concentration fixed at 100 μ M); it can be seen that the up-conversion intensity is maximal at a concentration of 2.5 mM of DPA.
FIG. 6 is the relationship between PdOEP/DPA up-conversion intensity and PdOEP concentration at 655nm excitation (deoxygenated gas, DMF, fixed concentration of annihilator at 2.5 mM); it can be seen that the up-conversion intensity is maximal at a concentration of 100mM PdOEP.
FIG. 7 is a graph of the relationship between upconversion spectral intensity and solvent type in different solvents (ethyl acetate, toluene, dichloromethane, N-dimethylformamide and N-propanol) with excitation at 655nm (oxygen excluded) and fixed concentration of PdOEP/DPA at 100 μ M/2.5 mM; it can be seen that the upconversion intensity is maximal when the solvent is DMF.
FIG. 8 under 655nm excitation (oxygen excluded), PdOEP/DPA (100. mu.M/2.5 mM, DMF) solution emits a blue upconversion at 430nm and a yellow upconversion at 575nm with the upconversion spectral intensity increasing with increasing excitation light power density. Since the excitation light source used is a 655nm red light source, the spectrum at 430nm is red-to-blue luminescence, and the maximum anti-stokes shift for red-to-blue up-conversion is 0.99 eV. The spectrum at-575 nm is red-convertedYellow up-conversion luminescence with a maximum intensity of blue light of 4.4X 10-5The highest intensity of yellow light is 6X 10-6The former intensity is 7.3 times higher than the latter intensity.
FIG. 9 is a graph of integrated logarithm of blue upconversion intensity at 430nm emitted from PdOEP/DPA (100. mu.M/2.5 mM, DMF) solution under 655nm excitation (with oxygen excluded) versus logarithm of power density, with a slope (slope) =2.7, close to 3, as can be seen.
FIG. 10 is a plot of the integrated logarithm of the yellow upconversion intensity at 570nm emitted by a solution of PdOEP/DPA (100. mu.M/2.5 mM, DMF) under 655nm excitation (with exclusion of oxygen) plotted against the logarithm of the power density with a slope (slope) =0.8 (close to 1).
Red-to-yellow conversion efficiency:
for the measurement of single photon absorption upconversion (OPA-UC), a solution of PdOEP (100 mM) in non-degassed DMF was prepared. Using a semiconductor solid-state laser (655 nm). OPA-UC spectra were recorded with a PR655 spectroscanner (655 nm) located on the back of the filter, and the red to yellow net up-conversion efficiency (F) relative to ZnPc was calculated according to equation (2)OPA-UC）。
In the formula, FrIs the fluorescence quantum yield of ZnPc, using it as reference standard (F)r=20%, 0.5mM in DMSO). FsAnd FrThe integrated emissions of PdOEP and ZnPc at an excitation wavelength of 655nm, respectively. I iss(655)And Ir(655)The excitation intensities at 655nm wavelength of PdOEP and ZnPc, respectively. Here, the excitation intensity (I) is usedex) Rather than the absorbance (a) normally used. This is because the absorbance (A) of PdOEP at 655nm could not be obtained, while the excitation intensity of PdOEP at 655nm could be obtained (FIG. 11). n issAnd nrThe refractive indices of the sample solution and the reference solution, respectively. See figures 11 and 12 for detailed data. From this, the red-to-yellow conversion efficiency was calculated to be 0.38%.
In order to obtain the conversion efficiency from red to blue, a DPA/PdOEP two-component solution is prepared in DMF(100. mu.M/2.5 mM, DMF), nitrogen degassing for about 15 min. Excited with a semiconductor solid-state laser (655 nm). OPA-TTA-UC spectra were recorded with a PR655 spectroscanner (655 nm) located on the back of the filter, and the red-to-blue net up-conversion efficiency (F) relative to ZnPc was calculated according to equation (2)OPA-TTA-UC). In the formula (2), FrFluorescent Quantum yield (F) of ZnPcr = 20%)。FsAnd FrThe integrated emission of DPA and reference ZnPc at an excitation wavelength of 655nm, respectively. I iss(655)、Ir(655)、nsAnd nrThe isoparametric is the same as the calculation of the red to yellow efficiency. See fig. 11 and 13 for detailed data. From this, the red-to-blue upconversion efficiency was calculated to be 1.23%.
Note that all the above upconversion efficiencies are net efficiencies, FOPA-TTA-UC is also disclosedNot multiplied by a factor of 3 in the OPA and TTA mechanisms. Furthermore, for simplicity, the refractive index of the solvent is used in the calculation instead of the refractive index of the solution.
Comparative example
Adding palladium tetraphenylporphyrin (PdTPP) into DMF (dimethyl formamide), preparing a PdTPP (100 mM) DMF solution, adding the solution into a quartz cuvette, and screwing a cuvette cap (without deoxidization) to obtain a single-component system; placed on an optical platform and directly irradiated with a 655nm semiconductor laser without emitting light, i.e. without up-conversion.
Adding palladium tetraphenylporphyrin (PdTPP) and 9, 10-Diphenylanthracene (DPA) into DMF (dimethyl formamide), preparing a PdTPP/DPA (100 mu M/2.5 mM, DMF) solution, adding the solution into a quartz cuvette, and screwing a cuvette cap (removing oxygen) to obtain a single-component system; placed on an optical platform and directly irradiated with a 655nm semiconductor laser without emitting light, i.e. without up-conversion. However, the two-component system is irradiated by a 532nm semiconductor laser, so that blue up-conversion can be realized.
Adding phenothiazine into DMF to prepare a phenothiazine (100 mM) DMF solution, adding the phenothiazine DMF solution into a quartz cuvette, and screwing a cuvette cap (without oxygen removal) to obtain a single-component system; placed on an optical platform and directly irradiated with a 655nm semiconductor laser without emitting light, i.e. without up-conversion.
The structural formula of phenothiazine is as follows:
the azaanthracene derivative PSF was used as a photosensitizer (concentration of 10 μ M) in combination with a luminophore DPA (concentration of 1 mM) for triplet-triplet annihilation up-conversion testing in dichloromethane/n-propanol =1/1 (v/v). The result shows that the PSF can be compounded with the DPA to generate obvious up-conversion by taking light with the wavelength of 532nm as excitation; but light with a wavelength of 655nm is used as excitation, and an up-conversion phenomenon does not occur. Further, light with the wavelength of 655nm is used as excitation, single photon up-conversion occurs in a DMSO solution of the single-component PSF, and the change of red-conversion-yellow is observed by naked eyes; however, light with a wavelength of 532nm was used as excitation, and no upconversion phenomenon occurred.
The azaanthracene derivative PSF has the following structural formula:
the invention realizes tunable up-conversion luminescence under the excitation of different wavelengths of light through a plurality of excitation mechanisms, creatively discloses a palladium octaethylporphyrin (PdOEP) single photon luminescence system, and obtains red-to-yellow up-conversion emission; octaethylporphyrin palladium (PdOEP) two-photon luminescence system to obtain red-to-blue up-conversion emission; the technical prejudice that the octaethylporphyrin palladium (PdOEP) can only realize green-to-blue up-conversion in the prior art is overcome; has application value in the fields of anti-counterfeiting and biological detection.
Claims (10)
1. A multichannel tunable weak light upconversion two-component system is characterized by comprising octaethylporphyrin palladium, an anthracene derivative and a solvent.
2. 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; the molar ratio of the octaethylporphyrin palladium to the anthracene derivative is 1: 5-30; the concentration of the octaethylporphyrin palladium is 50 mM-125 mM.
3. A multi-channel tunable weak light upconversion single-component system comprises octaethylporphyrin palladium and a solvent.
4. The multi-channel tunable weak-light upconversion single-component system according to claim 3, wherein the solvent is DMF; the concentration of the octaethylporphyrin palladium is 80 mM-120 mM.
5. The use of the multichannel tunable weak light up-conversion two-component system according to claim 1 for preparing red-to-blue up-conversion materials or red-to-yellow up-conversion materials, or as red-to-blue up-conversion materials or red-to-yellow up-conversion materials.
6. The use of the multi-channel tunable weak light up-conversion single-component system of claim 3 in the preparation of red-to-yellow up-conversion materials or as red-to-yellow up-conversion materials.
7. Application of octaethylporphyrin palladium in preparation of red light excitation up-conversion system.
8. A red light up-conversion method is characterized in that red light is used for irradiating 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 red light up-conversion is realized; the weak light up-conversion two-component system consists of octaethylporphyrin palladium, an anthracene derivative and a solvent; the weak light up-conversion single-component system consists of octaethyl porphyrin palladium and a solvent.
9. The method for red light upconversion according to claim 8, wherein an intensity of the red light irradiation is 0.5-2W/cm2。
10. The method of red light up-conversion according to claim 8, wherein the solvent is DMF.
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| CN103320123A (en) * | 2013-07-11 | 2013-09-25 | 苏州科技学院 | Weak light frequency up-conversion ternary supramolecular composite system |
| CN104212087A (en) * | 2014-09-19 | 2014-12-17 | 哈尔滨工业大学 | Preparation method of monodisperse fluorescent microspheres |
| CN109180692A (en) * | 2018-08-26 | 2019-01-11 | 苏州科技大学 | Converting system and preparation method thereof and the application in preparation temperature sensor on Thermo-sensitive |
| JP2019168337A (en) * | 2018-03-23 | 2019-10-03 | 和歌山県 | Vibration visualization sensor |
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| CN103320123A (en) * | 2013-07-11 | 2013-09-25 | 苏州科技学院 | Weak light frequency up-conversion ternary supramolecular composite system |
| CN104212087A (en) * | 2014-09-19 | 2014-12-17 | 哈尔滨工业大学 | Preparation method of monodisperse fluorescent microspheres |
| JP2019168337A (en) * | 2018-03-23 | 2019-10-03 | 和歌山県 | Vibration visualization sensor |
| CN109180692A (en) * | 2018-08-26 | 2019-01-11 | 苏州科技大学 | Converting system and preparation method thereof and the application in preparation temperature sensor on Thermo-sensitive |
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| BAO WANG 等: "Efficient Triplet Sensitizers of Palladium(II) Tetraphenylporphyrins for Upconversion-Powered Photoelectrochemistry", 《J. PHYS. CHEM. C》 * |
| MARTA PENCONI 等: "New molecular pairs for low power non-coherent triplet–triplet annihilation based upconversion: dependence on the triplet energies of sensitizer and emitter", 《JOURNAL OF LUMINESCENCE》 * |
| RADIY R. ISLANGULOV 等: "Noncoherent Low-Power Upconversion in Solid Polymer Films", 《J. AM. CHEM. SOC.》 * |
| 汪彩虹: "复合荧光探针的构建及在多底物检测中的应用", 《工程科技Ⅰ辑》 * |
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