CN104744481A - Sandwich-type phthalocyanine metal complex with red-to-yellow weak light upconversion characteristics - Google Patents
Sandwich-type phthalocyanine metal complex with red-to-yellow weak light upconversion characteristics Download PDFInfo
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Abstract
The invention relates to the field of triplet annihilation upconversion, and specifically relates to a sandwich-type phthalocyanine metal complex with red-to-yellow weak light upconversion characteristics. According to the invention, the solubility of metal phthalocyanine is effectively improved. The first layer and third layer of the sandwich-type phthalocyanine metal complex provided by the invention are a phthalocyanine macrocycle, and the second layer comprises central metal atoms Pd/Pt, and the first layer, the second layer and the third layer are directly connected with a coordination bond manner. The three planes form a three-dimensional molecular in space. The sandwich-type phthalocyanine metal complex provided by the invention has relatively long triplet lifetime, and has relatively strong absorption capacity upon visible lights and near-infrared light. When the metal complex is used as a sensitizing agent in a triplet annihilation upconversion material, the utilization of the upconversion material upon weak lights and especially sunlight can be facilitated. The pump light source intensity of a bimolecular triplet annihilation upconversion system with the metal complex as the sensitizing agent is lower than 50 mW*cm<-2>. Upconversion fluorescence can be obtained under the excitation of a common laser pen or even sunlight, such that the application of the triplet annihilation upconversion system is expanded.
Description
Technical field
The invention belongs to triplet state and bury in oblivion upper conversion art, be specifically related to a class sandwich type phthalocyanine metal complex and bury in oblivion the application of sensitizing agent material in upper conversion bicomponent system as triplet state.
Background technology
Triplet state-triplet state annihilation being changed (TTA-UC) is a Multiple-quantum process, usually need sensitizing agent and luminous agent to be mixed formation triplet state and bury in oblivion upper conversion bicomponent system, producing based on Triplet Sensitizers and the interphase interaction of triplet emission agent molecule, is the process that low-yield (wavelength is a long) light is converted to high-energy (wavelength is short) light.Its process is exactly: i), and first sensitizing agent absorbs after a photon arrives excited state and arrive its triplet state by intersystem crossing (ISC); Ii), then by triplet state-triplet state energy trasfer (TTT) occurs sensitizing agent to luminous agent; Iii), two are in triplet emission agent generation triplet state-triplet state annihilation (TTA) and launch up-conversion fluorescence.On whole TTA, switching process is exactly: sensitizing agent photon is when ground state, absorb energy, be excited and come singlet excited state, it passes through intersystem crossing, arrive Triplet Excited State, again by San Xian Tai – Triplet energy transfer, transmission ofenergy now to acceptor (luminous agent) photon (the collision transferring energy of sensitizing agent photon needs and luminous agent), it is made to arrive Triplet Excited State, when the luminous agent photon being in Triplet Excited State reaches finite concentration, two luminous agent photons being in Triplet Excited State are by triplet state-triplet state annihilation (mutually colliding), on certain probability, generation one is in the luminous agent photon of singlet excited state, another then gets back to ground state, the luminous agent photo emissions being now in singlet excited goes out fluorescence and gets back to ground state.
Triplet state-triplet state annihilation is changed (TTA-UC) and show a lot of advantages, be first that the exciting power density that on TTA, conversion needs is quite low, usually use mW/cm
2order of magnitude optical intensity density excites, and sunlight can be used as the excitation light source of conversion on TTA; In addition, the excitation wavelength of the upper conversion of TTA and emission wavelength tuning easily.Therefore, the upper conversion of TTA has tempting application future in Solar use (as photovoltaic, photochemical catalysis synthesis and photodegradation etc.).
The Baluschev reported first of German Ma Pu institute in 2006, utilizes the metastable triplet state of dye molecule, achieves incoherent light (< 10 W × cm
-2) frequency upooaversion (external quantum efficiency is greater than 1%), sunlight medium and low frequency ripple can be converted to the light wave of high frequency by this achievement in research, a brand-new step is stepped for sunlight utilizes, as this sunlight " is above changed " the words that system and solar cell combine, then can store more sun power, organic photovoltaic solar panel can be made to be benefited (see S. T. Baluschev, V Miteva, G. Yakutkin, et al, Physical Review Lett., 2006,6:143903); German horse in 2008 general Michael report near infrared light excite two Component Systems of metalloporphyrin/anthracene derivant to obtain the upper conversion that external quantum efficiencys reach 3.2%; The same year U.S. Currie group Miteva by guide technology in the Two-Component Mixed System of platinum porphyrins/pyran derivate, obtain the upper efficiency of conversion of 6.8%; 2009, the Chen of Chow research group of Cambridge University laser irradiation fluorone derivative/9 of wavelength 532 nm, the Two-Component Mixed System of 10-diphenylanthrancene, obtain efficiency and reach the up-conversion fluorescence of 1% (see M. J. Michael, J. K. M. Mapel, T. D. Heidel et al, Science, 2008,321:226; T. Miteva, V. Yakutkin, G. Nelles, S. Baluschev, New Journal of Physics, 2008,10:103002; H. C. Chen, C-Y. Hung, K-H Wang, et al, Chem. Commun., 2009,4064).
The wave band that solar spectrum covers is very wide, and in its electromagnetic radiation, the energy of 99% all concentrates on infrared region and visible region.The former accounts for about 50% of solar radiation total energy, and the latter accounts for about 43%, and the near-infrared band made full use of in sun power is extremely important as the efficient light sources that the low light level is changed.Phthalocyanine complex is because of its special structure, so have good catalytic activity, have following characteristic from structure: aromatic series π-electron is conjugation on whole tetraazatetradecane porphyrin ring, the cavity energy being positioned at ring center holds Determination of multiple metal elements, and metallic element can form title complex with phthalocyanine; LARGE CONJUGATE MOLECULES presents the planarity of height, and catalyzed reaction can occur at the axial location of this plane.Along with the development of science and technology, metal phthalocyanine complex is synthesized gradually, and has evoked the research enthusiasm of people in electrochromism and semi-conductor conductance field.But the solvability of existing phthalocyanine and metal phthalocyanine is all very poor, this greatly limits its application.
At present, yet there are no the report of palladium/platinum three-dimensional structure phthalocyanines title complex, more not about the application report of palladium/platinum three-dimensional structure phthalocyanines title complex conversion art on triplet state is buried in oblivion.
Summary of the invention
The object of this invention is to provide the palladium/platinum phthalocyanine complex of two kinds of three-dimensional structures, solve the difficult problem that metal phthalocyanine is poorly soluble, remain the triplet state characteristic that heavy metal phthalocyanine is fabulous simultaneously; Make public for the first time this metal complexes and bury in oblivion sensitizing agent in up-conversion for triplet state.Utilize the palladium of three-dimensional structure/platinum phthalocyanine complex as triplet state prepared by sensitizing agent bury in oblivion up-conversion achieve red-turn-the yellow low light level on change, in field of solar energy utilization, there is potential application prospect.
To achieve the above object of the invention, the technical solution used in the present invention is:
A kind of sandwich type phthalocyanine metal complex, its general structure is as follows:
Wherein R is selected from hydrogen, nitro, methyl, carboxyl or chlorine; M is atoms metal, is selected from palladium or platinum.
In the present invention, sandwich type phthalocyanine metal complex is space three-dimensional structure, roughly can be divided into three plane layers, the first layer and third layer are a large ring of phthalocyanine, atoms metal Pd/Pt centered by the second layer, they are directly interconnected in the mode of coordinate bond, these three planes constitute a three-dimensional molecular spatially, i.e. sandwich type phthalocyanine metal complex.
The preparation method of above-mentioned sandwich type phthalocyanine metal complex is: in nitrogen atmosphere, under the effect of catalyzer, in organic solvent, is reacted by phthalonitrile analog derivative metallizing thing, obtains sandwich type phthalocyanine metal complex;
Described metallic compound is: palladium acetylacetonate, potassium platinichloride;
Described catalyzer is: 1,8-diazabicylo 11 carbon-7-alkene;
The boiling point of described organic solvent is 130 DEG C ~ 150 DEG C;
The structural formula of described phthalonitrile analog derivative is:
.
In above-mentioned preparation method, described reaction conditions is: in nitrogen atmosphere, with phthalonitrile analog derivative for raw material, at catalyzer 1, under the effect of 8-diazabicylo 11 carbon-7-alkene (DBU), respectively with palladium acetylacetonate or potassium platinichloride, back flow reaction obtains three-dimensional structure metal phthalocyanine class title complex for 24 hours in organic solvent.The solvability of the sandwich type phthalocyanine Pd/Pt title complex of preparation is improved greatly than individual layer phthalocyanine metal complex solvability.
Described organic solvent is Pentyl alcohol.
Sandwich type phthalocyanine metal complex can realize triplet state and bury in oblivion in upper conversion ruddiness (long wavelength) to the conversion of gold-tinted (short wavelength), therefore the invention also discloses above-mentioned sandwich type phthalocyanine metal complex and buries in oblivion application in up-conversion in preparation triplet state.It is that triplet state ruddiness being converted to gold-tinted buries in oblivion up-conversion that described triplet state buries in oblivion up-conversion.
The present invention further discloses a kind of triplet state and bury in oblivion the two Component System of upper conversion, comprise sensitizing agent and luminous agent, described sensitizing agent is above-mentioned sandwich type phthalocyanine metal complex.
Described luminous agent is not particularly limited, and those skilled in the art can select as required voluntarily, and can be rubrene, its structural formula be as follows:
Can also be anthracene-boron fluoride, its structural formula:
In technique scheme, the mol ratio of described luminous agent, sensitizing agent is 1: 250 ~ 2500.
Triplet state of the present invention is buried in oblivion in the two Component System of upper conversion, shifted by triplet state between sensitizing agent and luminous agent molecule, the light of long wavelength is converted to the light of short wavelength, this process is called frequency upooaversion (burying in oblivion upper conversion also known as triplet state), and this process only need by low light level field (< 100 mW × cm
-2) excite and just can realize being converted into high frequency gold-tinted by low frequency ruddiness.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. sandwich type phthalocyanine metal complex disclosed by the invention, there is longer triplet lifetime, to visible ray and near infrared light, there is stronger receptivity, the sensitizing agent in up-conversion is buried in oblivion as triplet state, can realize red-turn-the yellow low light level on change, be conducive to up-conversion to the low light level, particularly the utilization of sunlight.
2. the light intensity that sandwich type phthalocyanine metal complex disclosed by the invention buries in oblivion the pump light source of upper converting system as the bimolecular triplet state of sensitizing agent is less than 100 mW × cm
-2, greatly extend the application that triplet state buries in oblivion upper converting system.
3. sandwich type phthalocyanine metal complex solvability of the present invention is good, and the actual concentrations of obtain solution can reach 1 × 10
-3mol/L; Overcome the shortcoming of phthalocyanine metal complex indissoluble in prior art; Improve the transmission ofenergy between luminous agent and sensitizing agent, increase the upper efficiency of conversion that triplet state buries in oblivion upper converting system further.
4. the cheaper starting materials such as reactant that the present invention uses is easy to get, and non-pollutant discharge, meets requirement and the direction of contemporary green chemistry, and preparation technology is simple, is suitable for industrial production.
Accompanying drawing explanation
Fig. 1 is the MALDI-TOF mass spectrum of sandwich type phthalocyanine metal complex in embodiment one;
Fig. 2 is the MALDI-TOF mass spectrum of sandwich type phthalocyanine metal complex in embodiment two;
Fig. 3 is the thermogravimetric curve figure of sandwich type phthalocyanine metal complex in embodiment;
Fig. 4 is the infrared spectrum of sandwich type phthalocyanine metal complex in embodiment;
Fig. 5 is normalization method absorption and the utilizing emitted light spectrogram of sandwich type phthalocyanine metal complex in embodiment;
Fig. 6 is the double exponential fitting sensitizing agent phosphor-decay curve of sandwich type phthalocyanine metal complex in embodiment;
Fig. 7 is sandwich type phthalocyanine metal complex solvability performance exploded view in embodiment;
Fig. 8 is PdPc in embodiment three
2the upper conversion testing realistic picture of/Rubrene bicomponent system;
Fig. 9 is PdPc in embodiment three
2the upconversion emission of/Rubrene bicomponent system is with luminous agent change in concentration spectrogram;
Figure 10 is PdPc in embodiment three
2the upconversion emission of/Rubrene bicomponent system is with excitation light source power density change spectrogram;
Figure 11 is PtPc in embodiment four
2the upper conversion testing realistic picture of/Rubrene bicomponent system;
Figure 12 is PtPc in embodiment four
2the upconversion emission of/Rubrene bicomponent system is with luminous agent change in concentration spectrogram;
Figure 13 is PtPc in embodiment four
2the upconversion emission of/Rubrene bicomponent system is with sending out excitation light source power density change spectrogram;
Figure 14 is PdPc in embodiment five
2the upconversion emission of/anthracene-boron fluoride bicomponent system is with sending out excitation light source power density change spectrogram.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described:
In the present embodiment, the mensuration of thermal weight loss performance: measure on the permanent thermogravimetric analyzer HKG that is rapidly heated in Beijing, when the weightless horizontal tangent that reduces phlegm and internal heat is the fastest with weightlessness, the intersection point of tangent line goes out corresponding temperature is critical decomposition temperature.The mensuration of infrared spectra: measure on ATR-FTAK Nicolet Fourier transformation infrared spectrometer.Excite, emmission spectrum and the mensuration in life-span: measure on Edinburgh FLS 920 fluorophotometer, cuvette thickness is 1 cm, and test solvent is spectrum level trichloromethane.
Embodiment one sandwich type palladium phthalocyanine title complex (PdPc
2) preparation
Take phthalonitrile 0.9 g and 40 mL Pentyl alcohols join in three-necked bottle, be heated to it under stirring and all dissolve.Taking palladium acetylacetonate 0.25g again joins in three-necked bottle, finally adds catalyzer DBU volume 0.4 mL.Under nitrogen protection, be heated to reflux temperature, react 24 hours.Reaction system becomes black-and-blue.Point plate follows the trail of to obtain phthalonitrile and palladium acetylacetonate complete reaction.Underpressure distillation is except desolventizing Pentyl alcohol, and column chromatography for separation, moving phase is CHCl3: Hexane=5: 1.Purification obtains black-and-blue pressed powder 0.68g, productive rate about 59%.Accompanying drawing 1 is the MALDI-TOF mass spectrum of above-mentioned sandwich type phthalocyanine metal complex, and MALDI-TOF mass spectrum obtains molecular mass 1130.In the life-span: 3.0099 μ s account for 15.82%, 16.8535 μ s account for 84.18%.
Embodiment two sandwich type phthalocyanine platinum complex (PtPc
2) preparation
Take phthalonitrile 0.9 g and 40 mL Pentyl alcohols join in three-necked bottle, be heated to it under stirring and all dissolve.Taking potassium platinichloride 0.29 g again joins in three-necked bottle, finally adds catalyzer DBU volume 0.4 mL.Under nitrogen protection, be heated to reflux temperature, react 24 hours.Reaction system becomes black-and-blue.Underpressure distillation is except desolventizing Pentyl alcohol, and column chromatography for separation, moving phase is CHCl
3: Hexane=5:1.Purification obtains black-and-blue pressed powder 0.52 g, productive rate about 43.6%.Accompanying drawing 2 is the MALDI-TOF mass spectrum of above-mentioned sandwich type phthalocyanine metal complex; MALDI-TOF mass spectrum obtains molecular mass 1219.In the life-span: 2.3474 μ s account for 7.91%, 14.7226 μ s account for 92.09%.
Accompanying drawing 3 is the thermogravimetric curve figure of above-mentioned sandwich type palladium phthalocyanine/platinum complex; Can find out, PdPc
2initial decomposition temperature and complete decomposition temperature are respectively 435 DEG C, 524 DEG C; PtPc
2initial decomposition temperature and complete decomposition temperature are respectively 415 DEG C, 475 DEG C.Visible, decomposition temperature is far away higher than common organic compound, and when reaching critical decomposition temperature, title complex of the present invention is still kept intact, and the excellent heat stability of title complex is described.
Accompanying drawing 4 is the infrared spectrum of above-mentioned sandwich type palladium phthalocyanine/platinum complex; Can find out, PdPc
2in 1513 be C=C, 1615 is C=N, and 3289 is C-H.723,754,866,1012,1126 belong to phthalocyanine ring skeletal vibration absorption peak.PtPc
2in 1513 be C=C, 1645 is C=N, and 3430 is C-H.709,730,873,1002,1118 belong to phthalocyanine ring skeletal vibration absorption peak.
Accompanying drawing 5 is the Absorption and emission spectra figure (trichloromethane solvent, 10 mM) of above-mentioned sandwich type palladium phthalocyanine/platinum complex.Can find out, PdPc
2b band absorb peak position at 340 nm places, Q be be absorbed in 597 ~ 656 nm regions, fluorescent emission peak position is at 697 nm places.PtPc
2b band absorb peak position at 340 nm places, Q band absorption peak position in the broad peak region of 595 ~ 656 nm, fluorescent emission peak position is at 692 nm places.
Accompanying drawing 6 is the phosphor-decay curve of above-mentioned sandwich type palladium phthalocyanine/platinum complex; Wherein PdPc
2long phosphorescent lifetime is 16.85 μ s(accounting 84.18 %), PdPc
2long phosphorescent lifetime is 14.72 μ s(accounting 92.09 %).
The title complex that accompanying drawing 7 is formed for a single layer structure PdPc(i.e. phthalocyanine ring and a palladium ion) and the palladium/platinum phthalocyanine (PdPc of sandwich structure provided by the invention
2and PtPc
2) deliquescent comparison test.Visible, under same molar ratio, the PdPc of single layer structure does not dissolve at trichloromethane solvent, in Granular composite state; Palladium/platinum phthalocyanine (the PdPc of sandwich structure
2and PtPc
2) in trichloromethane solvent, solubility property is good, obtain uniform and stable solution, its maximum concentration of ordinary dissolution reaches 1mM.
Embodiment three sensitizing agents/luminous agent binary triplet state buries in oblivion preparation and the test of system
PdPc
2as Triplet Sensitizers, meanwhile, rubrene (Rubrene) is as triplet emission agent.Solvent used in test process is trichloromethane.
Preparation mixing changes solution, wherein PdPc
2be 4 × 10
-6mol/L, Rubrene are 1 × 10
-2mol/L, mixed dissolution is in spectrum level trichloromethane.
Mixing solutions is placed in the cuvette of the quartz of 1 cm light path, after degassed pre-treatment, at red laser (634 nm, power density 35 mW/cm
2) exciting under, test bicomponent system rubrene/PdPc
2upconversion emission figure.Accompanying drawing 8 is through after 634 nm monochromatic filter removing excitation light sources, bicomponent system PdPc
2/ Rubrene triplet state buries in oblivion upper conversion diagram, can know and see yellow fluorescence, demonstrates bicomponent system and achieves on the red turn of yellow low light level and change.
Sensitizing agent PdPc in the trichloromethane of deoxygenation measured by accompanying drawing 9
2(4 × 10
-6mol/L) with the upper transformational relation of different concns rubrene (being increased to 9 mM from 0 mM) bicomponent system incident laser source (634 nm) excites.Along with rubrene concentration is increased to 9 mM from 0 mM, can observe, strengthened successively by the intensity red (634 nm) being transformed into yellow photons (600 nm).
By changing the power density of excitation light source from 10.89 mW/cm
2to 34.13 mW/cm
2, measure the power density of bicomponent system incident light source (634 nm) and the relation of upper shift strength.Rubrene (10 × 10 in the trichloromethane of deoxygenation measured by accompanying drawing 10
-3and sensitizing agent PdPc mol/L)
2(4 × 10
-6mol/L) power density of bicomponent system at incident light source (634 nm) and the relation of upper shift strength.Along with the power density of excitation light source is from 10.89 mW/cm
2to 34.13 mW/cm
2, can observe, strengthened successively by the intensity red (634 nm) being transformed into yellow photons (600 nm).
Embodiment four sensitizing agents/luminous agent binary triplet state buries in oblivion preparation and the test of system
PtPc
2as Triplet Sensitizers, meanwhile, rubrene (Rubrene) is as triplet emission agent.Solvent used in test process is trichloromethane.
Preparation mixing changes solution, wherein PtPc
2be 4 × 10
-6mol/L, Rubrene are 1 × 10
-2mol/L, mixed dissolution is in spectrum level trichloromethane.
Mixing solutions is placed in the cuvette of the quartz of 1 cm light path, after degassed pre-treatment, at red laser (634 nm, power density 35 mW/cm
2) exciting under, test bicomponent system rubrene/PtPc
2upconversion emission figure.Accompanying drawing 11 is bicomponent system PtPc
2/ Rubrene triplet state buries in oblivion upper conversion pictorial diagram, after 634 nm monochromatic filters removing excitation light sources, can know and see yellow up-conversion fluorescence, demonstrate bicomponent system and achieve on the low light level and change.
Sensitizing agent PtPc in the trichloromethane of deoxygenation measured by accompanying drawing 12
2(4 × 10
-6mol/L) with the upper transformational relation of different concns rubrene (being increased to 9 mM from 0 mM) bicomponent system incident laser source (634 nm) excites.Along with rubrene concentration is increased to 9 mM from 0 mM, can observe, strengthened successively by the intensity red (634 nm) being transformed into yellow photons (600 nm).
By changing the power density of excitation light source from 10.89 mW/cm
2to 34.13 mW/cm
2, measure the power density of bicomponent system incident light source (634 nm) and the relation of upper shift strength.Rubrene (10 × 10 in the trichloromethane of deoxygenation measured by accompanying drawing 13
-3and sensitizing agent PtPc mol/L)
2(4 × 10
-6mol/L) power density of bicomponent system at incident light source (634 nm) and the relation of upper shift strength.Along with the power density of excitation light source is from 10.89 mW/cm
2to 34.13 mW/cm
2, can observe, strengthened successively by the intensity red (634 nm) being transformed into yellow photons (600 nm).
Embodiment five sensitizing agents/luminous agent binary triplet state buries in oblivion preparation and the test of system
PdPc
2as Triplet Sensitizers, meanwhile, anthracene-boron fluoride is as triplet emission agent.Solvent used in test process is trichloromethane.
Preparation mixing changes solution, wherein PdPc
2concentration is 4 × 10
-6mol/L, anthracene-boron fluoride is 1 × 10
-3mol/L, mixed dissolution is in spectrum level trichloromethane.
Mixing solutions is placed in the cuvette of the quartz of 1 cm light path, after degassed pre-treatment, at red laser (634 nm, power density 35 mW/cm
2) exciting under, test bicomponent system anthracene-boron fluorine derivative/PdPc
2upconversion emission figure, test obtain 600 nm.And by changing the power density of excitation light source from 10.89 mW/cm
2to 34.13 mW/cm
2, measure the power density of bicomponent system incident light source (634 nm) and the relation of upper shift strength.Anthracene-boron fluorine derivative (10 × 10 in the trichloromethane of deoxygenation measured by accompanying drawing 14
-3and sensitizing agent PdPc mol/L)
2(4 × 10
-6mol/L) power density of bicomponent system at incident light source (634 nm) and the relation of upper shift strength.Along with the power density of excitation light source is from 10.89 mW/cm
2to 34.13 mW/cm
2, can observe, strengthened successively by the intensity red (634 nm) being transformed into yellow photons (600 nm).
Phthalonitrile is replaced by all the other phthalonitrile analog derivatives:
According to the preparation method of embodiment one or embodiment two, the sandwich type phthalocyanine metal complex of different substituents can be obtained:
Wherein R is nitro, methyl, carboxyl or chlorine; M is palladium or platinum.
Embodiment six sensitizing agents/luminous agent binary triplet state buries in oblivion preparation and the test of system
PtPc
2as Triplet Sensitizers, meanwhile, rubrene (Rubrene) is as triplet emission agent.Solvent used in test process is trichloromethane.PtPc
2structural formula be:
Preparation mixing changes solution, wherein PtPc
2be 4 × 10
-6mol/L, Rubrene are 1 × 10
-2mol/L, mixed dissolution is in spectrum level trichloromethane.
Mixing solutions is placed in the cuvette of the quartz of 1 cm light path, after degassed pre-treatment, at red laser (634 nm, power density 35 mW/cm
2) exciting under, test bicomponent system rubrene/PtPc
2upconversion emission figure.According to bicomponent system PtPc
2/ Rubrene triplet state buries in oblivion upper conversion pictorial diagram, after 634 nm monochromatic filters removing excitation light sources, can know and see yellow up-conversion fluorescence, demonstrate bicomponent system and achieve on the low light level and change.
Embodiment seven sensitizing agents/luminous agent binary triplet state buries in oblivion preparation and the test of system
PtPc
2as Triplet Sensitizers, meanwhile, rubrene (Rubrene) is as triplet emission agent.Solvent used in test process is trichloromethane.PtPc
2structural formula be:
Preparation mixing changes solution, wherein PtPc
2be 4 × 10
-6mol/L, Rubrene are 1 × 10
-2mol/L, mixed dissolution is in spectrum level trichloromethane.
Mixing solutions is placed in the cuvette of the quartz of 1 cm light path, after degassed pre-treatment, at red laser (634 nm, power density 35 mW/cm
2) exciting under, test bicomponent system rubrene/PtPc
2upconversion emission figure.According to bicomponent system PtPc
2/ Rubrene triplet state buries in oblivion upper conversion pictorial diagram, after 634 nm monochromatic filters removing excitation light sources, can know and see yellow up-conversion fluorescence, demonstrate bicomponent system and achieve on the low light level and change.
Embodiment eight sensitizing agents/luminous agent binary triplet state buries in oblivion preparation and the test of system
PdPc
2as Triplet Sensitizers, meanwhile, rubrene (Rubrene) is as triplet emission agent.Solvent used in test process is trichloromethane.PdPc
2structural formula be:
Preparation mixing changes solution, wherein PdPc
2be 4 × 10
-6mol/L, Rubrene are 1 × 10
-2mol/L, mixed dissolution is in spectrum level trichloromethane.
Mixing solutions is placed in the cuvette of the quartz of 1 cm light path, after degassed pre-treatment, at red laser (634 nm, power density 35 mW/cm
2) exciting under, test bicomponent system rubrene/PdPc
2upconversion emission figure.According to bicomponent system PdPc
2/ Rubrene triplet state buries in oblivion upper conversion pictorial diagram, after 634 nm monochromatic filters removing excitation light sources, can know and see yellow up-conversion fluorescence, demonstrate bicomponent system and achieve on the low light level and change.
Embodiment nine sensitizing agents/luminous agent binary triplet state buries in oblivion preparation and the test of system
PdPc
2as Triplet Sensitizers, meanwhile, rubrene (Rubrene) is as triplet emission agent.Solvent used in test process is trichloromethane.PdPc
2structural formula be:
Preparation mixing changes solution, wherein PdPc
2be 4 × 10
-6mol/L, Rubrene are 1 × 10
-2mol/L, mixed dissolution is in spectrum level trichloromethane.
Mixing solutions is placed in the cuvette of the quartz of 1 cm light path, after degassed pre-treatment, at red laser (634 nm, power density 35 mW/cm
2) exciting under, test bicomponent system rubrene/PdPc
2upconversion emission figure.According to bicomponent system PdPc
2/ Rubrene triplet state buries in oblivion upper conversion pictorial diagram, after 634 nm monochromatic filters removing excitation light sources, can know and see yellow up-conversion fluorescence, demonstrate bicomponent system and achieve on the low light level and change.
Claims (10)
1. a sandwich type phthalocyanine metal complex, is characterized in that, the general structure of this sandwich type phthalocyanine metal complex is as follows:
Wherein R is selected from hydrogen, nitro, methyl, carboxyl or chlorine; M is atoms metal, is selected from palladium or platinum.
2. sandwich type phthalocyanine metal complex according to claim 1, is characterized in that: the mode with coordinate bond between described atoms metal and phthalocyanine is interconnected.
3. the preparation method of sandwich type phthalocyanine metal complex described in claim 1, is characterized in that, comprise the following steps: in nitrogen atmosphere, under the effect of catalyzer, in organic solvent, phthalonitrile analog derivative metallizing thing is reacted, obtains sandwich type phthalocyanine metal complex;
The structural formula of described phthalonitrile analog derivative is:
;
Described metallic compound is palladium acetylacetonate or potassium platinichloride;
Described catalyzer is 1,8-diazabicylo 11 carbon-7-alkene;
The boiling point of described organic solvent is 130 DEG C ~ 150 DEG C.
4. the preparation method of sandwich type phthalocyanine metal complex according to claim 3, is characterized in that: described temperature of reaction is organic solvent reflux temperature; Reaction times is 24 hours.
5. the preparation method of sandwich type phthalocyanine metal complex according to claim 3, is characterized in that: described organic solvent is Pentyl alcohol.
6. sandwich type phthalocyanine metal complex according to claim 1 buries in oblivion the application in up-conversion in preparation triplet state.
7. application according to claim 6, is characterized in that: it is that triplet state ruddiness being converted to gold-tinted buries in oblivion up-conversion that described triplet state buries in oblivion up-conversion.
8. triplet state buries in oblivion the two Component System of upper conversion, comprises sensitizing agent and luminous agent, it is characterized in that: described sensitizing agent is sandwich type phthalocyanine metal complex described in claim 1.
9. triplet state buries in oblivion the two Component System of upper conversion according to claim 8, it is characterized in that: it is that triplet state ruddiness being converted to gold-tinted buries in oblivion the two Component System of upper conversion that described triplet state buries in oblivion the two Component System of upper conversion.
10. triplet state buries in oblivion the two Component System of upper conversion according to claim 8, it is characterized in that: the mol ratio of described sensitizing agent and luminous agent is 1: 250 ~ 2500.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105503887A (en) * | 2016-01-28 | 2016-04-20 | 苏州科技学院 | Sandwich type porphyrin complex and low-light upconversion system prepared from same |
| CN105567220A (en) * | 2016-01-22 | 2016-05-11 | 苏州科技学院 | Efficient red-to-yellow weak light up-conversion system and preparation method and application thereof |
| CN105601560A (en) * | 2015-12-31 | 2016-05-25 | 苏州科技学院 | Weak light frequency upconversion triplet state sensitizer and use of sensitizer |
| JP2017082063A (en) * | 2015-10-26 | 2017-05-18 | 日本化薬株式会社 | Light wavelength conversion element comprising deep eutectic solvent and article comprising the light wavelength conversion element |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017082063A (en) * | 2015-10-26 | 2017-05-18 | 日本化薬株式会社 | Light wavelength conversion element comprising deep eutectic solvent and article comprising the light wavelength conversion element |
| CN105601560A (en) * | 2015-12-31 | 2016-05-25 | 苏州科技学院 | Weak light frequency upconversion triplet state sensitizer and use of sensitizer |
| CN105601560B (en) * | 2015-12-31 | 2018-01-23 | 苏州科技学院 | Dim light frequency upooaversion Triplet Sensitizers and its application |
| CN105567220A (en) * | 2016-01-22 | 2016-05-11 | 苏州科技学院 | Efficient red-to-yellow weak light up-conversion system and preparation method and application thereof |
| CN105503887A (en) * | 2016-01-28 | 2016-04-20 | 苏州科技学院 | Sandwich type porphyrin complex and low-light upconversion system prepared from same |
| CN105503887B (en) * | 2016-01-28 | 2018-05-04 | 苏州科技学院 | Converting system on sandwich type metalloporphyrin complex and dim light prepared therefrom |
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