CN105622442A - Tert-butyl spirobifluorene compound and preparation method and application thereof - Google Patents
Tert-butyl spirobifluorene compound and preparation method and application thereof Download PDFInfo
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- CN105622442A CN105622442A CN201610098978.5A CN201610098978A CN105622442A CN 105622442 A CN105622442 A CN 105622442A CN 201610098978 A CN201610098978 A CN 201610098978A CN 105622442 A CN105622442 A CN 105622442A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/92—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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Abstract
The invention relates to a tert-butyl spirobifluorene compound and a preparation method and application thereof.The preparation method comprises the steps that 2,7-di-tert-butyl-2',7'-spirobifluorene, 4,4'-dimethoxyl diphenylamine, organic alkali, a palladium catalyst and a phosphine ligand are mixed according to the mole ratio 1:(2.0-2.5):4:(0.01-0.03):(0.02-0.06), then toluene is added, even mixing is performed, reflux reaction is performed under nitrogen protection, the reaction liquid produced after reaction is subjected to washing, drying, column passing, solvent removal and recrystallization to get the compound 2,7-di-tert-butyl-2',7'-di(N,N-bis-4-methoxyphenyl)-9,9'-spirobifluorene.The compound is low in cost, simple in synthetic route, high in yield and easy to produce industrially.The compound has better thermal stability, solubility and hydrophobicity, is used as a hole-transporting material for perovskite solar cells and has higher photoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of tert-butyl group Spirobifluorene compound and its preparation method and application, belong to the preparation field of solar cell material.
Background technology
Since entering new century, global energy composition there occurs great variety. The various new energy is flourish, constantly shakes with oil, and coal is the leading position of main traditional fossil energy. Wherein solar energy industry development is particularly swift and violent, has now become the important component part of novel energy.
As tradition heliotechnics, the development of silica-based solar cell is the most perfect, be most widely used, but it must use the HIGH-PURITY SILICON of costliness, thus be faced with cost height, the high difficult problem that consumes energy (electronic component and material, 2014,33,212-216).
Current people, in research and development novel solar battery, focus on the perovskite solaode grown up in recent years gradually. This battery is made up of transparency electrode, electron transfer layer, perovskite light-absorption layer, hole transmission layer, metal electrode five part. Its hole-transporting layer is as a kind of all solid state electrolyte, can with perovskite band structure perfect adaptation, avoid the problem that former I/I3-electrolyte decomposition perovskite light-absorption layer brings, and then improve stability and the process repeatability (Sci.Rep. of perovskite battery, 2012,2,591). Desirable hole transmission layer should have high hole transport efficiency, high thermodynamic stability, well dissolubility and film property; there is certain hydrophobicity simultaneously to protect perovskite absorbed layer (Phys.Chem.Lett.; 2013,4 (21), 3623-3630).
Prepare at present and filter out excellent hole mobile material and become the important development direction of perovskite solaode.
Summary of the invention
For above technical problem, present inventor for core, introduces the diaryl-amine group with methoxy substitution with 2,7-di-t-butyl-2', 7'-dibromo spiral shell fluorenes in its 2' and 7' position. Diaryl-amine is the desirable group with efficient hole transport performance, it is possible to provide higher carrier mobility; And the tert-butyl group can increase material dissolubility on the one hand, make it have hydrophobic function on the other hand, the film property of material so can be made to be greatly improved, protect calcium titanium ore bed simultaneously, and then improve cell photoelectric transformation efficiency and stability.
The technical scheme is that a kind of tert-butyl group Spirobifluorene compound, structure is as follows:
The preparation method that the present invention also provides for a kind of tert-butyl group Spirobifluorene compound, including:
By 2; 7-di-t-butyl-2'; 7'-dibromo spiral shell fluorenes, 4; 4'-dimethoxy diphenylamines, organic base, palladium catalyst and Phosphine ligands 1:(2.0��2.5 in molar ratio): 4:(0.01��0.03): (0.02��0.06) mixes; add toluene, mix homogeneously, back flow reaction under nitrogen protection; reaction finishes reactant liquor through washing; dry, cross post, desolventizing; recrystallization; obtain compound 2,7-di-t-butyl-2', 7'-bis-(N; double; two-4-the methoxyphenyl of N-)-9,9'-spiral shell two fluorenes.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described organic base is potassium tert-butoxide or sodium tert-butoxide.
Further, described palladium catalyst is palladium, Pd2dba3(three (dibenzalacetone) two palladium) or Pd (dppf) Cl2One in (1,1 '-bis-Diphenyl phosphino ferrocene palladium chlorides).
Further, described Phosphine ligands is (t-Bu)3PH��BF4One in (tri-butyl phosphine tetrafluoroborate) or Xantphos (the double; two diphenylphosphine-9,9-dimethyl xanthene of 4,5-).
Further, the temperature of described back flow reaction is 105 DEG C��110 DEG C.
Further, the solvent of described recrystallization is the mixture of a kind of in normal hexane, toluene, ethyl acetate, ethanol or any two kinds.
The present invention also provides for the application in perovskite solar cell device of a kind of above-mentioned tert-butyl group Spirobifluorene compound.
The present invention also provides for a kind of perovskite solar cell device, including: the glass substrate that sets gradually, FTO negative electrode, TiO2Electron transfer layer, calcium titanium ore bed, hole transmission layer and Ag electrode, described hole transmission layer adopts above-mentioned tert-butyl group Spirobifluorene compound to make.
The preparation method that the present invention also provides for a kind of perovskite solar cell device, including:
Adopt HCl/Zn etching method to process FTO glass substrate, then clean, dry and process standby with ultraviolet-ozone; By the mixed solution spin-coating film of 0.25mol/L tetrabutyl titanate once, at 125 DEG C of dry 5min, FTO glass substrates at 450 DEG C of calcination 1h, form fine and close TiO2Layer; It is then spin coated onto TiO2The ethanol solution of slurry, TiO2The mass ratio of slurry and dehydrated alcohol is 2:7,500 DEG C of calcination 30min, forms TiO2Electron transfer layer; Again FTO glass substrate is proceeded in glove box, spin coating 462mg/LPbI2DMF solution, 90 DEG C dry 15min, finally the FTO glass substrate of above-mentioned drying is immersed in 6mg/mLCH3NH320-30s in the aqueous isopropanol of I, after isopropanol drip washing, dries 10min and cools down standby for 70 DEG C. The chlorobenzene solution of the preparation 72.3mg/mL compound containing tertiary butyl groups, and add the acetonitrile solution of 29 �� L520mg/mLLi-TFSI (two (trifluoromethane sulfonic acid acyl) imine lithium), 28.8 �� L4-tert .-butylpyridine, 24 �� L300mg/mL tri-(2-(1H pyrazol-1-yl) pyridine) close the acetonitrile solution of cobalt, the above-mentioned solution prepared is carried out spin coating operation, and proceed to vacuum evaporation room evaporation Ag electrode, prepare perovskite solar cell device.
Raw material of the present invention all can be commercially available or synthesize according to prior art.
The invention has the beneficial effects as follows:
1) compound of the present invention is with low cost, synthetic route is simple, yield is high, be prone to refining, it is appreciated that in industrialized production;
2) compound dissolution of the present invention and better heat stability, glass transition temperature is higher, it is possible to form good amorphous membrance, is conducive to stablizing of battery properties. The macroscopic property of this compound
As shown in the table:
The macroscopic property of table 1 compound
| Tg/�� | Tm/�� | Td/�� 2 --> |
| 140 | 228 | 491 |
Wherein, Tg represents that glass transition temperature, Tm represent fusing point, and Td represents decomposition temperature.
3) compound of the present invention is higher in the photoelectric transformation efficiency of perovskite solar cell device, illustrates that compound of the present invention is the hole mobile material of a class function admirable.
Accompanying drawing explanation
Fig. 1 is the structure chart of the perovskite solar cell device that compound of the present invention is made as hole mobile material, and wherein, the parts representated by each label are as follows:
1, glass substrate, 2, FTO negative electrode, 3, TiO2Electron transfer layer, 4, calcium titanium ore bed, 5, hole transmission layer, 6, Ag electrode.
Fig. 2 is the current density voltage curve figure of the perovskite solaode being made up as hole mobile material of compound of the present invention.
Detailed description of the invention
Hereinafter principles of the invention and feature being described, example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
Embodiment one prepares 2,7-di-t-butyl-2', 7'-bis-(double; two-4-methoxyphenyl of N, N-)-9,9'-spiral shell two fluorenes
Reaction scheme is as follows:
Scheme one:
250ml there-necked flask adds 5.8g (0.01mol) 2,7-di-t-butyl-2', 7'-dibromo spiral shell fluorenes, 4.6g (0.02mol) 4,4'-dimethoxy diphenylamines, 4.5g (0.04mol) potassium tert-butoxide, 100.0g toluene. 0.09g (1.0 �� 10 is added under nitrogen protection-4mol)Pd2(dba)3, 0.06g (2.0 �� 10-4mol)(t-Bu)3PH��BF4. Being warming up to 105 DEG C��110 DEG C to react 7 hours, reaction is finished, filtering reacting liquid, and filtrate is washed with 100g �� 2 water. Organic facies dries through anhydrous sodium sulfate, and post crossed by silica gel, and reduce pressure desolventizing, and dehydrated alcohol recrystallization obtains yellow powdery solid 6.13g, yield 69.4%. LC-MS:[M]+=883.56.1H-NMR (500MHz, d6-DMSO) ��/ppm:7.65��7.68 (m, 4H), 7.34��7.37 (d, 2H), 6.73��6.76 (m, 10H), 6.66��6.69 (m, 10H), 6.05 (s, 2H), 3.65 (s, 12H), 1.19 (s, 18H).
Scheme two:
250ml there-necked flask adds 8.8g (0.015mol) 2,7-di-t-butyl-2', 7'-dibromo spiral shell fluorenes, 7.8g (0.034mol) 4,4'-dimethoxy diphenylamines, 5.8g (0.06mol) sodium tert-butoxide, 120.0g toluene. 0.067g (3.0 �� 10 is added under nitrogen protection-4Mol) palladium, 0.17g (6.0 �� 10-4mol)(t-Bu)3PH��BF4. Being warming up to 105 DEG C��110 DEG C to react 5 hours, reaction is finished, filtering reacting liquid, and filtrate is washed with 120g �� 2 water. Organic facies dries through anhydrous sodium sulfate, and post crossed by silica gel, and reduce pressure desolventizing, toluene and dehydrated alcohol (mass ratio 2:3) recrystallization, obtains yellow powdery solid 9.57g, yield 72.3%. LC-MS:[M]+=883.56.1H-NMR (500MHz, d6-DMSO) ��/ppm:7.65��7.68 (m, 4H), 7.34��7.37 (d, 2H), 6.73��6.76 (m, 10H), 6.66��6.69 (m, 10H), 6.05 (s, 2H), 3.65 (s, 12H), 1.19 (s, 18H).
Scheme three:
250ml there-necked flask adds 9.3g (0.016mol) 2,7-di-t-butyl-2', 7'-dibromo spiral shell fluorenes, 9.1g (0.04mol) 4,4'-dimethoxy diphenylamines, 6.2g (0.064mol) sodium tert-butoxide, 120.0g toluene. 0.35g (4.8 �� 10 is added under nitrogen protection-4mol)Pd(dppf)Cl2, 0.55g (9.6 �� 10-4Mol) Xantphos. Being warming up to 105 DEG C��110 DEG C to react 6 hours, reaction is finished, filtering reacting liquid, and filtrate is washed with 120g �� 2 water. Organic facies dries through anhydrous sodium sulfate, and post crossed by silica gel, and reduce pressure desolventizing, ethyl acetate and dehydrated alcohol (mass ratio 1:3) recrystallization, obtains yellow powdery solid 9.22g, yield 65.3%. LC-MS:[M]+=883.56.1H-NMR (500MHz, d6-DMSO) ��/ppm:7.65��7.68 (m, 4H), 7.34��7.37 (d, 2H), 6.73��6.76 (m, 10H), 6.66��6.69 (m, 10H), 6.05 (s, 2H), 3.65 (s, 12H), 1.19 (s, 18H).
The perovskite solar cell device of embodiment two compound
Fig. 1 illustrates the perovskite solar cell device prepared by compound of the present invention as hole transmission layer, including: glass substrate, FTO negative electrode, TiO2Electron transfer layer, calcium titanium ore bed, hole transmission layer and Ag electrode.
The production process of described perovskite solar cell device:
1) FTO negative electrode is prepared in etching conductive substrate: need area to be protected to cling FTO electro-conductive glass with Kapton Tape, Zn powder is uniformly applied to the FTO glass surface needing etching again, HCl solution is dropped on the Zn powder on FTO glass, react immediately; After question response completes, wiping etch areas, unreacted for surface solution is wiped;
2) TiO is prepared2Electron transfer layer:
Preparation TiO2Fine and close TiO in electron transfer layer2Layer:
1. organosol is prepared:
A liquid: butyl titanate and diethanolamine are dissolved in dehydrated alcohol, strong agitation under room temperature condition, obtain homogeneous solution; Wherein, butyl titanate: diethanolamine: the volume ratio of dehydrated alcohol is 5:3:13;
B liquid: deionized water is mixed with dehydrated alcohol 1:28 by volume; When strong agitation, being added dropwise in A liquid by B liquid with the speed of 5mL/min, the volume ratio of A liquid and B liquid is 2.8:1, obtains clear pale yellow solution, and the molar concentration of this solution is 0.5M, is placed in-5 DEG C of storages; Dilute with the dehydrated alcohol of equal-volume ratio before using, obtain compacted zone organosol;
2. spin coating organosol: organosol step 1. obtained uniformly drops in the FTO substrate of glass of cleaning, carries out spin coating, is then placed under 450 DEG C of conditions and sinters 1h;
Preparation TiO2Porous TiO in electron transfer layer2Layer: spin coating TiO2The suspension that slurry and dehydrated alcohol (2:7, m/m) are made into, then 500 DEG C of calcination 30min, form porous TiO2Layer;
3) preparing calcium titanium ore bed: be first dissolved in DMF by lead iodide, the concentration of lead iodide is 462mg/mL, and 70 DEG C of heated and stirred are until PbI2It is completely dissolved, with organic membrane filtration of 0.22 ��m, by PbI2Solution drops in TiO2On perforated membrane, then carrying out spin coating, spin coating is complete to be transferred on 90 DEG C of hot plates, heats 15min; Heat complete be cooled to 25 DEG C after, the PbI that will prepare2Thin film is moistening in aqueous isopropanol, is placed in the aqueous isopropanol of 6mg/mL iodine methylamine at once, PbI after taking-up2Thin film color is become black from yellow gradually; Then thin film is transferred in aqueous isopropanol and slightly rinse, be spin-coated to solvent volatilization, be finally transferred on 70 DEG C of hot plates and heat 10min, obtain organic and inorganic calcium titanium ore bed.
4) hole transmission layer is prepared: preparation 2,7-di-t-butyl-2', 7'-bis-(N, double; two-4-methoxyphenyl the benzene of N-)-9, the chlorobenzene solution that concentration is 72.3mg/mL that 9'-spiral shell two fluorenes (is prepared by scheme 1), add three kinds of additives: the respectively acetonitrile solution of 29 �� L520mg/mLLi-TFSI (two (trifluoromethane sulfonic acid acyl) imine lithium), 28.8 �� L4-tert .-butylpyridine, 24 �� L300mg/mL tri-(2-(1H pyrazol-1-yl) pyridine) close the acetonitrile solution of cobalt, 20 DEG C of stirring 1h. Then the solution configured is spun to step 3) calcium titanium ore bed on.
5) it is placed in vacuum evaporation room, vacuum evaporation metal Ag, prepares perovskite solar cell device.
In embodiment one, the compound of scheme one preparation illustrates as the hole transmission layer of above-mentioned solar cell device (perovskite solaode), and the structure of described perovskite solar cell device is: glass substrate, FTO negative electrode, TiO2Electron transfer layer, calcium titanium ore bed, hole transmission layer and Ag electrode, shown in the units test data prepared such as table 2 and Fig. 2:
The device data of table 2 compound
V in table 2oc[V] is open-circuit voltage, Jsc[mA/cm-2] it is fill factor, curve factor for short-circuit current density, FF [%], Eff [%] is photoelectric transformation efficiency, and the photoelectric transformation efficiency of this patent material, up to 15.98%, has a good application prospect.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (9)
1. a tert-butyl group Spirobifluorene compound, it is characterised in that structure is as follows:
2. the preparation method of a tert-butyl group Spirobifluorene compound, it is characterised in that including:
By 2; 7-di-t-butyl-2 '; 7 '-dibromo spiral shell fluorenes, 4; 4 '-dimethoxy diphenylamines, organic base, palladium catalyst and Phosphine ligands 1:(2.0��2.5 in molar ratio): 4:(0.01��0.03): (0.02��0.06) mixes; add toluene, mix homogeneously, back flow reaction under nitrogen protection; reaction finishes reactant liquor through washing; dry, cross post, desolventizing; recrystallization; obtain compound 2,7-di-t-butyl-2 ', 7 '-two (N; double; two-4-the methoxyphenyl of N-)-9,9 '-spiral shell two fluorenes.
3. preparation method according to claim 2, it is characterised in that described organic base is potassium tert-butoxide or sodium tert-butoxide.
4. preparation method according to claim 2, it is characterised in that described palladium catalyst is palladium, Pd2dba3Or Pd (dppf) Cl2In one.
5. preparation method according to claim 2, it is characterised in that described Phosphine ligands is (t-Bu)3PH��BF4Or the one in Xantphos.
6. preparation method according to claim 2, it is characterised in that the temperature of described back flow reaction is 105 DEG C��110 DEG C.
7. preparation method according to claim 2, it is characterised in that the solvent of described recrystallization is the mixture of a kind of in normal hexane, toluene, ethyl acetate, ethanol or any two kinds.
8. a tert-butyl group Spirobifluorene compound as claimed in claim 1 application in perovskite solar cell device.
9. a perovskite solar cell device, it is characterised in that including: the glass substrate that sets gradually, FTO negative electrode, TiO2Electron transfer layer, calcium titanium ore bed, hole transmission layer and Ag electrode, described hole transmission layer adopts the tert-butyl group Spirobifluorene compound described in claim 1 to make.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957381A (en) * | 2017-05-12 | 2017-07-18 | 南京工业大学 | Design, synthesis and application of hole transport material of perovskite solar cell |
| WO2018009771A1 (en) * | 2016-07-07 | 2018-01-11 | Qatar Foundation For Education, Science And Community Development | Dispiro-oxepine/thiapine derivatives for optoelectronic semiconductors |
| CN109244249A (en) * | 2018-10-15 | 2019-01-18 | 南京邮电大学 | The perovskite solar cell device and preparation method thereof that hole transmission layer is modified |
| CN109438259A (en) * | 2018-11-19 | 2019-03-08 | 哈尔滨工业大学 | A kind of novel spiro fluorene anil and preparation method thereof |
| CN115286520A (en) * | 2022-08-19 | 2022-11-04 | 黑龙江省科学院石油化学研究院 | Preparation method of hole transport material Spiro-OMeTAD |
| CN115340520A (en) * | 2022-06-27 | 2022-11-15 | 太原理工大学 | Hole transport material of small-hysteresis perovskite battery and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1947274A (en) * | 2004-04-26 | 2007-04-11 | 默克专利有限公司 | Electroluminescent polymers containing planar arylamine units, the preparation and use thereof |
| CN102633610A (en) * | 2011-12-31 | 2012-08-15 | 上海师范大学 | 'Vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on fluorene loop and preparation method and application thereof |
| CN205028929U (en) * | 2015-08-19 | 2016-02-10 | 辽宁工业大学 | Perovskite type solar cell |
-
2016
- 2016-02-23 CN CN201610098978.5A patent/CN105622442A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1947274A (en) * | 2004-04-26 | 2007-04-11 | 默克专利有限公司 | Electroluminescent polymers containing planar arylamine units, the preparation and use thereof |
| CN102633610A (en) * | 2011-12-31 | 2012-08-15 | 上海师范大学 | 'Vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on fluorene loop and preparation method and application thereof |
| CN205028929U (en) * | 2015-08-19 | 2016-02-10 | 辽宁工业大学 | Perovskite type solar cell |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018009771A1 (en) * | 2016-07-07 | 2018-01-11 | Qatar Foundation For Education, Science And Community Development | Dispiro-oxepine/thiapine derivatives for optoelectronic semiconductors |
| CN106957381A (en) * | 2017-05-12 | 2017-07-18 | 南京工业大学 | Design, synthesis and application of hole transport material of perovskite solar cell |
| CN109244249A (en) * | 2018-10-15 | 2019-01-18 | 南京邮电大学 | The perovskite solar cell device and preparation method thereof that hole transmission layer is modified |
| CN109438259A (en) * | 2018-11-19 | 2019-03-08 | 哈尔滨工业大学 | A kind of novel spiro fluorene anil and preparation method thereof |
| CN109438259B (en) * | 2018-11-19 | 2021-02-26 | 哈尔滨工业大学 | Spirofluorene aniline derivative and preparation method thereof |
| CN115340520A (en) * | 2022-06-27 | 2022-11-15 | 太原理工大学 | Hole transport material of small-hysteresis perovskite battery and preparation and application thereof |
| CN115340520B (en) * | 2022-06-27 | 2023-10-10 | 太原理工大学 | Hole transport material of small hysteresis perovskite battery and preparation and application thereof |
| CN115286520A (en) * | 2022-08-19 | 2022-11-04 | 黑龙江省科学院石油化学研究院 | Preparation method of hole transport material Spiro-OMeTAD |
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