CN115028653B - Organic room-temperature phosphorescent material and application thereof - Google Patents
Organic room-temperature phosphorescent material and application thereof Download PDFInfo
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- CN115028653B CN115028653B CN202210624437.7A CN202210624437A CN115028653B CN 115028653 B CN115028653 B CN 115028653B CN 202210624437 A CN202210624437 A CN 202210624437A CN 115028653 B CN115028653 B CN 115028653B
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- 239000000463 material Substances 0.000 title claims abstract description 64
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- 238000012986 modification Methods 0.000 claims abstract description 5
- -1 cyano, amino, hydroxyl Chemical group 0.000 claims description 12
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
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- ZAYUOSICZWFJSW-UHFFFAOYSA-N 10h-phenothiazine 5,5-dioxide Chemical group C1=CC=C2S(=O)(=O)C3=CC=CC=C3NC2=C1 ZAYUOSICZWFJSW-UHFFFAOYSA-N 0.000 abstract description 2
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- 239000000843 powder Substances 0.000 description 13
- 230000005284 excitation Effects 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000001246 bromo group Chemical group Br* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
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- JEWIAYIESCUSKQ-UHFFFAOYSA-N 3-bromo-10h-phenothiazine Chemical compound C1=CC=C2SC3=CC(Br)=CC=C3NC2=C1 JEWIAYIESCUSKQ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
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- 239000012074 organic phase Substances 0.000 description 3
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- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 2
- CYPYTURSJDMMMP-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 CYPYTURSJDMMMP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 150000001875 compounds Chemical group 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 2
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- 238000004020 luminiscence type Methods 0.000 description 2
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- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- 238000007650 screen-printing Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KGNQDBQYEBMPFZ-UHFFFAOYSA-N 1-fluoro-4-iodobenzene Chemical compound FC1=CC=C(I)C=C1 KGNQDBQYEBMPFZ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241001116389 Aloe Species 0.000 description 1
- 235000002961 Aloe barbadensis Nutrition 0.000 description 1
- 244000186892 Aloe vera Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
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- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/34—[b, e]-condensed with two six-membered rings with hetero atoms directly attached to the ring sulfur atom
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses an organic room-temperature phosphorescent material and application thereof, and belongs to the technical field of photoelectric materials. The material contains an organic room temperature phosphorescence building unit phenothiazine 5, 5-dioxide group and a top end capping Ar group, and by introducing an R group modification group into a side group of the room temperature phosphorescence building unit, the close packing of phosphorescence chromophores is promoted, the intermolecular interaction is enhanced, the effective room temperature phosphorescence emission and the simultaneous fluorescence-delayed fluorescence-room temperature phosphorescence emission are realized, and the purposes of realizing the direct visual change of the stimulus-response organic ultralong room temperature phosphorescence and the luminous color under different external stimuli are achieved. The material has the advantages of easy control of reaction process and strong designability, and can be applied to the fields of information encryption, anti-counterfeiting, dynamic patterning, visual monitoring, biological imaging, organic electroluminescent devices and the like.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to an organic room-temperature phosphorescent material and application thereof.
Background
After the excitation is stopped, the organic room temperature phosphorescent material can still emit light for a period of time, and has abundant application value in the fields of information encryption, anti-counterfeiting biological imaging and the like. Although research and application of organic room temperature phosphorescent materials has progressed, such materials generally exhibit weak phosphorescent emission. And such materials are difficult to exhibit stimulus-responsive emission behavior because of the difficulty in simultaneously controlling triplet excitons and stimulus-responsive factors. In addition, the dynamic response of the luminous color under the external stimulus is more beneficial to direct visual monitoring. However, for organic super-long room temperature phosphorescent materials, it is more difficult to realize dynamic response of luminescent colors due to weak phosphorescence emission, competing relationship among excitons, and the like.
In recent years, research and development of organic phosphorescent materials are rapid, and the most deeply studied metal complex phosphorescent materials are taken as an example, and the materials can be applied to the fields of Organic Light Emitting Diode (OLED) devices, biological imaging, information encryption and the like, but due to the fact that noble metals are introduced, the materials have high cost, complex synthesis paths, unavoidable biotoxicity and shorter phosphorescence service life. Therefore, the development of organic room temperature phosphorescent materials, in particular organic room temperature phosphorescent materials with ultra-long service life, has wide economic value and application value.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the technical problems, the invention provides an organic room temperature phosphorescent material and application thereof, which realize effective room temperature phosphorescent emission and simultaneous fluorescence-delayed fluorescence-room temperature phosphorescent emission, and achieve the aim of realizing direct visual change of stimulus-responsive organic ultralong room temperature phosphorescence and luminescent color under different external stimuli.
The technical scheme is as follows: an organic room temperature phosphorescent material has a structural general formula shown in the following formula I:
wherein, the R group is a side group modification unit and is selected from any one of pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carboxyl of C 1-C30, ester of C 1-C30 and alkoxy of C 1-C30;
Ar is a top end capping group selected from any one of C 1-C30 linear or branched alkyl, C 1-C30 linear or branched ester, substituted or unsubstituted C 1-C30 acyl, substituted or unsubstituted C 6-C60 aryl derivative.
Preferably, the top end capping group Ar is selected from one of the following ①-⑨ structures:
wherein X is any one of hydrogen atom, pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carbonyl, ester group of C 1-C30 and alkyl of C 1-C30;
preferably, the side unit R is selected from any one of the following structures:
-F、-Cl、-Br、-CN、-NH2、-OH、-COOH、-COOCnH2n+1、 Where n=a natural number from 1 to 30.
Preferably, the material has a general structural formula shown in the following formula II:
Wherein X is any one of hydrogen atom, pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carbonyl, C 1-C30 ester group and C 1-C30 alkyl.
Preferably, the material has a structural formula as shown in formula III below:
Preferably, the material is in the form of a single crystal, the single crystal is in the form of a triclinic system, the space group is P-1, and the unit cell parameter is α＝85.87(3)°,β＝87.51(3)°,γ＝70.20(3)°；Z＝2。
The organic room temperature phosphorescent material is applied to the preparation of information encryption, anti-counterfeiting and dynamic display patterns.
The application of the organic room temperature phosphorescent material in visual monitoring.
The beneficial effects are that: the organic room temperature phosphorescent material of the invention provides sites for constructing effective intermolecular interactions (such as C-H … pi and C-H … O interactions) by carrying out top end capping of Ar groups on the phenothiazine 5, 5-dioxide groups of the organic room temperature phosphorescent construction unit and introducing R group modification groups into side groups, can realize close packing of phosphorescent chromophores, and is beneficial to realizing multi-mode emission of organic ultra-long room temperature phosphorescence and fluorescence-delayed fluorescence-room temperature phosphorescence.
The material has the characteristics of time-dependent response, force stimulus response, temperature-dependent response and the like in a crystalline powder state, and can realize the direct visual change of the luminous color under different stimulus. For example, the emission color increases with the excitation time, and the emission color is dynamically switched; turning off the excitation source to generate long-life organic phosphorescence of a third color; after mechanical grinding, color-variable luminescence and spectra are produced; color-variable luminescence and emission spectra can be achieved at varying temperatures due to simultaneous fluorescence-delayed fluorescence-room temperature phosphorescence multi-mode emission. The organic room temperature phosphorescent material with the stimulus response characteristic can be further applied to the fields of multiple information encryption, dynamic pattern display and visual monitoring, such as ultraviolet excitation wavelength visual monitoring, temperature visual monitoring, aggregation state visual monitoring, biological imaging, organic electroluminescent devices and the like.
Drawings
FIG. 1 is a material of example 1
1 H NMR spectrum of PhP-B (10-phenyl-3- (4, 5-tetramethyl-1,3, 2-dioxaborolan-2-yl) -10H-phenothiazine, 5-dioxide);
FIG. 2 is a graph of the steady state and phosphorescent emission spectra of the crystalline powder of example 1 material PhP-B;
FIG. 3 is an ultralong phosphorescent lifetime decay curve of the crystalline powder of material PhP-B of example 1;
FIG. 4 is a time resolved transient emission plot of the crystalline powder of example 1 material PhP-B;
FIG. 5 is a graph showing the emission spectra of the crystalline powder of example 1 material PhP-B before and after milling;
FIG. 6 is a graph showing the decay of the ultra-long phosphorescence lifetime after milling of the crystalline powder of example 1 material PhP-B;
FIG. 7 is a graph of the excitation dependent emission spectra of the crystalline powder of example 1 material PhP-B;
FIG. 8 is a graph of the temperature dependent emission spectrum of the crystalline powder of example 1 material PhP-B.
Detailed Description
The invention is further described below with reference to the drawings and specific embodiments.
An organic room temperature phosphorescent material has a structural general formula shown in the following formula I:
wherein, the R group is a side group modification unit and is selected from any one of pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carboxyl of C 1-C30, ester of C 1-C30 and alkoxy of C 1-C30;
Ar is a top end capping group selected from any one of C 1-C30 linear or branched alkyl, C 1-C30 linear or branched ester, substituted or unsubstituted C 1-C30 acyl, substituted or unsubstituted C 6-C60 aryl derivative.
Preferably, the top end capping group Ar is selected from one of the following ①-⑨ structures:
wherein X is any one of hydrogen atom, pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carbonyl, ester group of C 1-C30 and alkyl of C 1-C30;
preferably, the side unit R is selected from any one of the following structures:
-F、-Cl、-Br、-CN、-NH2、-OH、-COOH、-COOCnH2n+１、 Where n=a natural number from 1 to 30.
The invention is further illustrated below by specific several specific compound structures, which do not limit the scope of coverage of this invention. The organic room temperature phosphorescent light-emitting material provided by the invention can be any one of the following compounds:
When the R group is selected from pinacol borate, an organic room temperature phosphorescent material may be, but is not limited to, any of the following structures:
In addition, when the R group is selected from other structures, an organic room temperature phosphorescent light-emitting material has various combination forms, and can be any one of the following structures without limitation:
the invention discloses a preparation method of an organic room-temperature phosphorescent material, which is shown in the following formula II as an example:
Wherein X is any one of hydrogen atom, pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carbonyl, C 1-C30 ester group and C 1-C30 alkyl.
The preparation method of the material comprises the following steps:
(1) Under the protection of nitrogen and in the dark, toluene solvent is injected into any one of R groups with bromo or iodo, 3-bromo 10H-phenothiazine, sodium tert-butoxide, tris (dibenzylideneacetone) dipalladium catalyst and tri-tert-butyl tetrafluoroboric acid, and the mixture reacts for 2 to 6 hours at the temperature of between 90 and 120 ℃;
The molar ratio of the 3-bromine 10H-phenothiazine to the R group raw material with bromo or iodo, the sodium tert-butoxide and the dipalladium tris (dibenzylideneacetone) is 1:2-1:4, 1:2-1:2.5, 1:0.05-1:0.2, the molar ratio of the dipalladium tris (dibenzylideneacetone) to the tri-tert-butyltetrafluoroboric acid is 1:2-1:4, and toluene is added in an amount of 4-6mL per millimole;
(2) Cooling to room temperature after the reaction is finished, extracting with dichloromethane and saturated saline, drying with anhydrous sodium sulfate, and removing an organic phase solvent; then, the petroleum ether and the methylene dichloride are used as eluent to carry out column chromatography purification and recrystallization to obtain the precursor product
The volume ratio of the petroleum ether to the dichloromethane eluent is 6:1-3:1, and the mesh number of silica gel used for column chromatography is 100-200 meshes or 200-300 meshes;
(3) The precursor product is processed Adding the mixture into acetic acid and 30 percent hydrogen peroxide mixed solvent for reaction for 4 to 8 hours at the temperature of 100 to 120 ℃. Then, the mixture was recrystallized from methylene chloride and n-hexane to obtain the objective product.
When the organic room temperature phosphorescence material is in a single crystal form, the non-radiative transition can be more effectively restrained, the room temperature phosphorescence has longer excited state life and higher phosphorescence efficiency, the single crystal is in a triclinic system, the space group is P-1, and the unit cell parameter isα＝85.87(3)°,β＝87.51(3)°,γ＝70.20(3)°；Z＝2。
The invention discloses an application mode of the organic room temperature phosphorescent material, which comprises the following aspects: when the organic room temperature phosphorescent material is applied to information encryption, anti-counterfeiting and dynamic patterning, the organic room temperature phosphorescent material is uniformly dispersed in a medium such as polyvinyl alcohol or aloe gel, and corresponding information, patterns and the like are prepared on filter paper or other paper in a screen printing mode; or dissolving in solvent such as ethyl acetate, tetrahydrofuran, cyclohexanone, etc. to prepare ink, and printing corresponding information, patterns, etc. on the substrate without background light in an ink-jet printing mode; meanwhile, the organic room temperature phosphorescent material disclosed by the invention can be used for visual monitoring, such as ultraviolet excitation wavelength visual monitoring, temperature visual monitoring, especially extreme temperature visual monitoring, aggregation state visual monitoring and other applications.
Example 1
Organic room temperature phosphorescent materials
Synthesis of PhP-B (10-phenyl-3- (4, 5-tetramethyl-1,3, 2-dioxaborolan-2-yl) -10H-phenothiazine, 5-dioxide)
Step one: 3-bromo-10H-phenothiazine (1.12 g,4 mmol), iodobenzene (2.45 g,12 mmol), sodium tert-butoxide (0.77 g,8 mmol), tris (dibenzylideneacetone) dipalladium catalyst (0.18 g,0.2 mmol), and tris (t-butyltetrafluoroboric acid (0.12 g,0.4 mmol) were added to the flask under nitrogen protection and light shielding, 25mL toluene solvent was injected, and the reaction was carried out at 110℃for 2 hours.
After the completion of the reaction, the mixture was cooled to room temperature, extracted with dichloromethane and saturated brine, dried over anhydrous sodium sulfate, and the organic phase solvent was removed. Then, petroleum ether and methylene dichloride are used as eluent (volume ratio, 4:1) to carry out column chromatography (100-200 meshes of silica gel) purification, and recrystallization is carried out, thus obtaining the precursor product(1.06 G, 75% yield).
Step two: the precursor product is processed(1.06 G,3 mmol) was added to a mixed solvent containing acetic acid (20 mL) and hydrogen peroxide (3 mL) at a concentration of 30% by volume, and the mixture was reacted at 120℃for 4 hours. Subsequently, the mixture was recrystallized from methylene chloride and n-hexane to give the objective intermediate(1.03 G, 90% yield).
Step three: under the protection of nitrogen and in the dark, the dried intermediate is added into a dried reaction bottle(1.04 G,2.7 mmol), pinacol diboronate (1.37 g,5.4 mmol), potassium acetate (0.79 g,8.1 mmol) and [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (II) (0.37 g,0.5 mmol). Then 25mL of redistilled and bubbled 1, 4-dioxane was injected and reacted at 100℃for 24 hours.
After the completion of the reaction, the mixture was cooled to room temperature, extracted with dichloromethane and saturated brine, dried over anhydrous sodium sulfate, and the organic phase solvent was removed. Then, purifying by column chromatography (100-200 mesh silica gel) with petroleum ether and ethyl acetate (volume ratio, 2:1) as eluent, and recrystallizing with dichloromethane and ethanol to obtain white target final product(0.94 G, 80% yield).
1H NMR(400MHz,CDCl3)δ8.10-8.22(m,4H),7.30-7.44(m,5H),7.24(d,1H),6.60-6.66(d,2H).13C NMR(100MHz,CDCl3)δ142.44,140.51,138.85,138.57,132.72,131.36,130.82,130.35,129.79,123.56,123.25,122.30,122.14,117.36,116.25,84.15,24.85.HR-MS(m/z):calcd.For C24H24BNO4S,Molecular Weight:433.33. The 1 H NMR spectrum in CDCl 3 can be confirmed by FIG. 1. The photophysical properties of the crystalline powder can be confirmed by the steady state and phosphorescence emission spectra of fig. 2, the decay curve of the ultra-long phosphorescence lifetime of fig. 3, and the time-resolved transient emission map of fig. 4, respectively; the crystalline powder has the characteristics of changing photophysical properties after grinding and force stimulus response, and can be respectively confirmed by the emission spectrograms before and after grinding in the graph of FIG. 5 and the decay curve of the super-long phosphorescence life after grinding in the graph of FIG. 6; the crystalline powder has the characteristic of excitation dependence, can be confirmed by an excitation dependence emission spectrum chart of FIG. 7, and can be used for visual monitoring of excitation wavelength; the crystalline powder has the characteristic of excitation dependence, can be confirmed by the temperature-dependent emission spectrum of FIG. 8, and can be used for visual monitoring of temperature, especially extreme temperature.
Example 2
Single crystal cultivation of organic room temperature phosphorescent material PhP-B
50Mg of PhP-B product was dissolved in 15mL of methylene chloride good solvent, and then 8mL of methanol was added as a solvent to evaporate the mixed solution slowly. Finally, colorless and transparent needle-like crystals are formed in the solution. The single crystal is triclinic system, the space group is P-1, and the unit cell parameter isΑ= 85.87 (3) °, β= 87.51 (3) °, γ= 70.20 (3) °; z=2. The single crystal state can more effectively inhibit the non-radiative transition, and the room temperature phosphorescence has longer excited state life and higher phosphorescence efficiency.
Example 3
Preparation of dynamic display pattern of organic room temperature phosphorescent material PhP-B
150Mg of PhP-B powder was uniformly dispersed in 300mg of commercially available aloe vera gel and stirred until uniformly mixed to a gel form. The preset information and the pattern are printed on the commercial filter paper by a screen printing technology. The light is irradiated by a 365nm portable ultraviolet lamp, the light-emitting color is changed from ultraviolet to blue-green along with the increase of the excitation time; the excitation source is turned off, producing green long-life organic phosphorescence.
Example 4:
Organic room temperature phosphorescent materials
FPhP-B(10-(4-fluorophenyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-phenothiazine5,5-dioxide) Is synthesized by (a)
This example is essentially the same as example 1 except that p-fluoroiodobenzene is selected as the starting material in a molar ratio of 4:1 to 3-bromo-10H-phenothiazine.
HR-MS(m/z):calcd.For C24H23BFNO4S，Molecular Weight:451.32。
Example 5
Organic room temperature phosphorescent materials
Synthesis of PhP-B (10-phenyl-3- (4, 5-tetramethyl-1,3, 2-dioxaborolan-2-yl) -10H-phenothiazine, 5-dioxide)
The synthesis of this example intermediate was identical to the preparation of example 1, except that methoxy was used as the pendant substituent. Sodium methoxide was selected as a starting material and refluxed in an ultra-dry methanol solvent overnight. The molar ratio of sodium methoxide to bromine-bearing intermediate was 1.5:1.
HR-MS(m/z):calcd.For C19H15NO3S Molecular Weight:337.39。
Example 6
Organic room temperature phosphorescent materials
AzobenzeneP-B((E)-10-(4-(phenyldiazenyl)phenyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-phenothiazine 5,5-dioxide) Is synthesized by (a)
The synthesis of this example intermediate was identical to the preparation of example 1, except that cyano was used as the pendant substituent. Cuprous cyanide is selected as a raw material, and the raw material is refluxed in a super-dry N, N-Dimethylformamide (DMF) solvent for 18 hours. The molar ratio of cuprous cyanide to bromine-bearing intermediate was 1.5:1.
HR-MS(m/z):calcd.For C19H12N2O2S Molecular Weight:332.38。
Example 7
Organic room temperature phosphorescent materials
AzobenzeneP-B((E)-10-(4-(phenyldiazenyl)phenyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-phenothiazine 5,5-dioxide) Is synthesized by (a)
This example is essentially the same as example 1 except that p-4-iodoazobenzene is selected as the starting material and 3-bromo-10H-phenothiazine is used in a molar ratio of 2:1.
MALDI-TOF-MS(m/z):calcd.For C30H28BN3O4S Molecular Weight:537.44。
Claims (5)
1. The application of the organic room temperature phosphorescent material in preparing information encryption, anti-counterfeiting and dynamic display patterns and visual monitoring is characterized in that the material has a structural general formula shown in the following formula I:
wherein, the R group is a side group modification unit and is selected from any one of pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carboxyl of C 1-C30, ester of C 1-C30 and alkoxy of C 1-C30;
the top end capping group Ar is selected from one of the following ①-⑨ structures:
wherein X is any one of hydrogen atom, pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carbonyl, ester group of C 1-C30 and alkyl of C 1-C30;
2. The use of an organic room temperature phosphorescent material according to claim 1 for the preparation of information encryption, security and dynamic display patterns and visual monitoring, wherein the R group is selected from any one of the following structures:
Where n=a natural number from 1 to 30.
3. The use of an organic room temperature phosphorescent material according to claim 1 for the preparation of information encryption, anti-counterfeiting and dynamic display patterns and visual monitoring, wherein the material has the general structural formula shown in the following formula II:
Wherein X is any one of hydrogen atom, pinacol borate, boric acid, halogen, cyano, amino, hydroxyl, carbonyl, C 1-C30 ester group and C 1-C30 alkyl.
4. The use of an organic room temperature phosphorescent material according to claim 1 for the preparation of information encryption, security and dynamic display patterns and visual monitoring, characterized in that the material has the structural formula shown in the following formula III:
5. The application of the organic room temperature phosphorescent material in preparing information encryption, anti-counterfeiting and dynamic display patterns and visual monitoring according to claim 4, wherein the material is in a single crystal form, the single crystal is in a triclinic system, a space group is P-1, and unit cell parameters are that α＝85.87(3)°,β＝87.51(3)°,γ＝70.20(3)°；Z＝2。
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