CN109575062B - Dinaphthyl carborane compound and preparation method and application thereof - Google Patents
Dinaphthyl carborane compound and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 23
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims abstract description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
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- 239000000126 substance Substances 0.000 abstract description 6
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- 238000002845 discoloration Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 46
- 229940125904 compound 1 Drugs 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
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- 239000000243 solution Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 238000004020 luminiscence type Methods 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 238000012746 preparative thin layer chromatography Methods 0.000 description 4
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
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- 238000000926 separation method Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
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- 150000002894 organic compounds Chemical class 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 2
- 238000004607 11B NMR spectroscopy Methods 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OQOLNSMRZSCCFZ-FLFKKZLDSA-N 9,10-bis[(e)-2-phenylethenyl]anthracene Chemical compound C=1C=CC=CC=1/C=C/C(C1=CC=CC=C11)=C2C=CC=CC2=C1\C=C\C1=CC=CC=C1 OQOLNSMRZSCCFZ-FLFKKZLDSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
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- 125000005620 boronic acid group Chemical class 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C07F5/027—Organoboranes and organoborohydrides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/1011—Condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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Abstract
The invention discloses a preparation method and application of a dinaphthyl carborane compound, belonging to the field of organic synthesis and luminescent materials. The preparation method comprises the steps of dissolving 1, 2-di (4-bromophenyl) o-carborane, 1-naphthalene boric acid, a phase transfer catalyst, alkali and a catalyst in a solvent, heating for reaction, and carrying out post-treatment after the reaction is finished to obtain the dinaphthyl carborane compound. The preparation method of the invention has simple operation and mild conditions. The dinaphthyl carborane compound obtained by the invention not only has aggregation-induced emission property, but also has the characteristic of fluorescence discoloration, is a better aggregation-induced emission material, can be used in the fields of luminescent materials, biological probes and chemical sensing, and has wide application prospect.
Description
Technical Field
The invention relates to the field of organic synthesis and luminescent materials, in particular to a dinaphthyl carborane compound and a preparation method and application thereof.
Background
With the discovery and study of aggregation-induced emission (AIE) phenomenon, researchers have synthesized a large number of compounds with AIE properties and have begun to refer to the synthesis and application of novel AIE materials in different high-tech fields.
Aggregation-induced emission materials have wide applications in the fields of chemistry, materials, life sciences, and the like, and include biological probes, chemical sensors, optoelectronic devices, stimulus-responsive materials, and the like. The AIE organic compound systems which are currently being studied are mainly tetraphenylethylene, silole, namely silacyclopentadiene (silole), 9, 10-distyrylanthracene and the like.
Organoboron compounds refer to a series of organic compounds containing a boron-carbon bond and can be broadly classified into the following groups: boron hydride (also known as borane) and organoborane BR3(R is a hydrocarbon group) Organoborates, boronic acids (i.e., organoboron oxide compounds), organoborane heterocyclic compounds, carboranes, and the like. Many organoboron compounds have many unique properties, particularly optoelectronic properties, due to the specific electronic and chemical properties of the boron atom.
The most common carborane compound is o-carborane (o-C)2B10H12) The structure has an icosahedron cage structure with two adjacent carbon atoms, and the structural formula is shown as follows:
By introducing the naphthalene ring into a bis-phenyl carborane structure, not only can a high-efficiency aggregation-induced luminescent material be obtained, but also the application field of carborane compounds can be expanded.
Disclosure of Invention
The invention aims to provide a dinaphthyl carborane compound, a preparation method and application thereof, and overcomes the technical defects of less carborane compound AIE materials, lower luminous efficiency and the like in the prior art.
In order to achieve the above object or other objects, the present invention is achieved by the following aspects.
A method for preparing a dinaphthyl carborane compound, comprising the steps of:
further, the method comprises the steps of: under the protection of inert gas, 1, 2-di (4-bromophenyl) o-carborane, 1-naphthalene boric acid, a phase transfer catalyst, alkali and a catalyst are dissolved in a solvent, heated for reaction, and subjected to post-treatment after the reaction is finished.
Further, the inert gas is selected from any one of high-purity nitrogen, argon and helium.
Preferably, the inert gas is argon.
Further, the solvent is a mixed solution of toluene and water.
Preferably, the volume ratio of toluene to water is 3: 1.
further, the mass-to-volume ratio (mg: mL) of the 1, 2-bis (4-bromophenyl) o-carborane to the solvent is 5-10.
Further, the molar ratio of the 1, 2-bis (4-bromophenyl) o-carborane to the 1-naphthalene boric acid is 1: (2-3).
Further, the phase transfer catalyst is selected from any one of tetrabutylammonium fluoride, tetrabutylammonium chloride and tetrabutylammonium bromide.
Preferably, the phase transfer catalyst is tetrabutylammonium bromide.
Further, the base is selected from any one of sodium carbonate, potassium carbonate and cesium carbonate.
Preferably, the base is potassium carbonate.
Further, the catalyst is tetrakis (triphenylphosphine) palladium.
Further, the molar ratio of the 1, 2-bis (4-bromophenyl) o-carborane to the phase transfer catalyst is (4-5): 1.
further, the molar ratio of 1, 2-bis (4-bromophenyl) o-carborane to base is 1: (4-5).
Further, the molar ratio of 1, 2-bis (4-bromophenyl) o-carborane to tetrakis (triphenylphosphine) palladium was 5: 1.
further, the reaction temperature is 100-120 ℃.
Preferably, the reaction temperature is 110 ℃.
Further, the reaction time is 20-30 hours.
Preferably, the reaction time is 24 hours.
Further, the post-processing comprises: quenching reaction, separating liquid, extracting and separating by thin-layer chromatography.
Preferably, after the reaction is finished, adding water to quench the reaction, standing for layering, extracting an aqueous phase with ethyl acetate, combining organic phases, adding anhydrous sodium sulfate for drying, filtering, and separating by adopting preparative thin-layer chromatography, wherein the selected developing solvent is a mixed solvent of dichloromethane and n-hexane.
Preferably, the volume of water added for quenching reaction is 2-3 times of the volume of the reaction solvent.
Preferably, the volume ratio of the water phase to the ethyl acetate for each extraction is (3-4): 1.
preferably, the volume ratio of the dichloromethane to the n-hexane in the mixed solvent of the dichloromethane and the n-hexane as the developing agent is 1: 4.
in a second aspect, the invention provides a dinaphthyl carborane compound prepared by the preparation method.
The third aspect of the invention also provides application of the dinaphthyl carborane compound prepared by the preparation method in the fields of luminescent materials, biological probes and chemical sensing.
The invention provides a dinaphthyl carborane compound, which is obtained by reacting an o-carborane derivative with 1-naphthalene boric acid, and the preparation method has simple operation and mild conditions. The dinaphthyl carborane compound obtained by the invention not only has AIE property, but also has the characteristic of force-induced fluorescence discoloration, is a better AIE material, can be used in the fields of luminescent materials, biological probes and chemical sensing, and has wide application prospect.
Drawings
FIG. 1 shows an IR spectrum of Compound 1 obtained in example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of Compound 1 obtained in example 1 of the present invention;
FIG. 3 is a nuclear magnetic boron spectrum of Compound 1 obtained in example 1 of the present invention;
FIG. 4 is a nuclear magnetic carbon spectrum of Compound 1 obtained in example 1 of the present invention;
FIG. 5 is a mass spectrum of Compound 1 obtained in example 1 of the present invention;
FIG. 6 shows the crystal structure of Compound 1 obtained in example 1 of the present invention (solvent molecules not shown);
FIG. 7 shows UV-VIS absorption spectra (concentration: 1X 10) of Compound 1 obtained in example 1 of the present invention in various solvents-5mol/L, DCM is dichloromethane, THF is tetrahydrofuran, and DMSO is dimethyl sulfoxide);
FIG. 8 shows a solid emission spectrum (excitation wavelength: 330nm) of Compound 1 obtained in example 1 of the present invention;
FIG. 9 shows an emission spectrum (excitation wavelength of 310nm) of a compound 1 solution (tetrahydrofuran is a good solvent and water is a poor solvent) obtained in example 1 of the present invention;
FIG. 10 shows the emission spectra of compound 1 powder obtained in example 1 of the present invention before and after grinding (DCM is dichloromethane);
FIG. 11 shows X-ray diffraction patterns before and after grinding of compound 1 powder obtained in example 1 of the present invention;
FIG. 12 shows emission spectra (excitation wavelength 330nm) of compound 1 thin film obtained in example 1 at different temperatures.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
The preparation method of the thin layer chromatography in the embodiment of the invention is a conventional method, and the single crystal culture method is also a conventional method in the field.
Preferably, the preparation method of the thin layer chromatography comprises the following steps: pouring GF254 silica gel into the prepared 0.5% sodium carboxymethylcellulose solution, fully stirring and grinding, uniformly spreading the silica gel on a square glass plate, vibrating the glass plate to flatten the silica gel, placing the glass plate in a shade, airing, placing the glass plate in an oven, drying, and cooling to room temperature. Wherein the volume weight ratio of the 0.5% sodium carboxymethylcellulose solution to the silica gel is 2.5: 1; airing at a cool place at the temperature of 20-30 ℃; the drying temperature of the drying oven is 100-120 ℃; the drying time of the drying oven is 2-3 h.
Preferably, the method of single crystal cultivation is: dissolving the product in a test tube by using dichloromethane, adding a solvent, and obtaining the single crystal by using a solvent diffusion method. Wherein the mass-volume ratio (M: V) of a product used for culturing the single crystal to dichloromethane is 50: 1 (g: L). The additional solvent is one of n-pentane, n-hexane and n-heptane. Preferably, the additional solvent is n-hexane; the mass-to-volume ratio (M: V) of the cultured single crystal product to the additional solvent used is 50: 4 (g: L); the time for culturing the single crystal is 24-48 h.
The instruments used in the examples of the present invention are: shanghai Shenguang SGW X-4A micro melting point apparatus, Edinburgh FLS920 combined steady state/transient state fluorescence spectrometer, Perkin Elmer RX I Fourier transform infrared spectrometer, Bruker D8 FOCUS powder X-ray diffractometer, Oxford Diffraction single crystal X-ray diffractometer, Beijing general analysis TU-1900 double-beam ultraviolet-visible spectrophotometer and Bruker Avance III 400MHz nuclear magnetic resonance apparatus.
The 1, 2-bis (4-bromophenyl) o-carborane adopted in the embodiment of the invention is prepared by a method reported in Marcomolecules,2010,43:6463-6468 by Yoshiki Chujo et al.
Example 1
1, 2-bis (4-bromophenyl) o-carborane (152mg, 0.34mmol), 1-naphthalene boric acid (138.6mg, 0.81mmol), tetrabutylammonium bromide (22.7mg, 0.07mmol), anhydrous potassium carbonate (187.5mg, 1.36mmol) and tetrakis (triphenylphosphine) palladium (19mg, 0.16mmol) were placed in 15mL of toluene and 5mL of water under argon to give a two-phase system of a brownish yellow organic phase and a clear aqueous phase, heated in an oil bath (110 ℃) and reacted for 24 hours. 50mL of water was added, the mixture was allowed to stand for separation, the aqueous phase was extracted with ethyl acetate (15 mL. times.3), and the organic phases were combined and dried over anhydrous sodium sulfate. Filtering, concentrating to about 5mL by rotary evaporation, separating by preparative thin-layer chromatography with a developing solvent of dichloromethane: n-hexane ═ 1: 4 (V: V) to give a white solid, compound 1(28mg, 15.3%), melting point: 208 ℃ and 209 ℃.
The infrared spectrum (KBr tablet method), nuclear magnetic hydrogen spectrum, boron spectrum and carbon spectrum of the compound 1 are respectively detected, and the results are shown in fig. 1 to 4.
2590cm in FIG. 1-1Is treated as the stretching vibration peak of carborane B-H, 1604cm-1And 1504cm-1773cm of skeleton vibration and C ═ C bond stretching vibration-1The peak at (a) is the out-of-plane bending vibration peak of the naphthalene ring.
1H NMR(400MHz,CDCl3)δ7.86(t,J＝8.5Hz,4H),7.61(d,J＝8.5Hz,4H),7.57(d,J＝8.6Hz,2H),7.47(t,J＝7.8Hz,2H),7.43(t,J＝7.1Hz,2H),7.33(d,J＝8.4Hz,4H),7.28(dd,J＝7.1,1.0Hz,2H),7.20(t,J＝7.7Hz,2H)；
11B NMR(128MHz,CDCl3)δ-2.07,-10.26；
13C NMR(100MHz,CDCl3)δ142.88,138.46,133.72,131.15,130.71,129.87,129.71,128.39,128.3,126.85,126.43,125.93,125.26,85.20。
The obtained compound 1 was subjected to mass spectrometry, and as shown in fig. 5, the result showed that M/z was 549.3571([ M-1 ])]+) And the calculated value 549.3356, performing anastomosis.
The crystal of Compound 1 was grown by single crystal growth and its crystal structure was determined by X-ray diffraction method, as shown in FIG. 6. The results show that the distance between two carbon atoms on the carborane cage, C1-C2, is
The corresponding torsion angle C1-C2-C3-C4 is-98.34 degrees, and the torsion angle C2-C1-C19-C20 is-95.93 degrees; the twist angle between the benzene ring and the naphthalene ring is 100.06 degrees from C7 to C8 to C9 to C10 degrees and 45.40 degrees from C23 to C24 to C25 to C26 degrees, and the larger difference indicates that the twisting of the naphthalene ring and the benzene ring is relatively large, which can cause the rotation of molecules to be hindered.
Example 2
Under the protection of argon, 1, 2-bis (4-bromophenyl) o-carborane (152mg, 0.34mmol), 1-naphthalene boric acid (120.4mg, 0.70mmol), tetrabutylammonium chloride (19.5mg, 0.07mmol), anhydrous potassium carbonate (234.9mg, 1.70mmol) and tetrakis (triphenylphosphine) palladium (19mg, 0.16mmol) are placed in 15mL of toluene and 5mL of water to obtain a brown yellow organic phase and clear aqueous phase two-phase system, and the two-phase system is heated in an oil bath (110 ℃) and reacted for 24 hours. 50mL of water was added, the mixture was allowed to stand for separation, the aqueous phase was extracted with ethyl acetate (15 mL. times.3), and the organic phases were combined and dried over anhydrous sodium sulfate. Filtering, concentrating to about 5mL by rotary evaporation, separating by preparative thin-layer chromatography with a developing solvent of dichloromethane: n-hexane ═ 1: 4 (V: V) to obtain a white solid, namely the compound 1.
Example 3
1, 2-bis (4-bromophenyl) o-carborane (152mg, 0.34mmol), 1-naphthalene boric acid (175.4mg, 1.02mmol), tetrabutylammonium bromide (22.7mg, 0.07mmol), anhydrous sodium carbonate (162.2mg, 1.53mmol), and tetrakis (triphenylphosphine) palladium (19mg, 0.16mmol) were placed in 15mL of toluene and 5mL of water under argon to give a brown-yellow organic phase and clear aqueous phase two-phase system, heated in an oil bath (110 ℃) and reacted for 24 hours. 50mL of water was added, the mixture was allowed to stand for separation, the aqueous phase was extracted with ethyl acetate (15 mL. times.3), and the organic phases were combined and dried over anhydrous sodium sulfate. Filtering, concentrating to about 5mL by rotary evaporation, separating by preparative thin-layer chromatography with a developing solvent of dichloromethane: n-hexane ═ 1: 4 (V: V) to obtain a white solid, namely the compound 1.
Performance testing
1. Optical Performance testing
1) The compound 1 obtained in example 1 was dissolved in dichloromethane, tetrahydrofuran, and dimethyl sulfoxide, respectively, to prepare a solution having a concentration of 1X 10-5The solution of mol/L is subjected to absorption spectrum test, and the test result is shown in FIG. 7. As can be seen from the figure, the absorption peaks of Compound 1 in methylene chloride solution are 229nm and 294nm, in tetrahydrofuran solution are 233nm and 294nm, and in dimethyl sulfoxide solution are 297 nm. The absorption peaks of compound 1 are all in the ultraviolet region and slightly red-shifted with increasing polarity of the solvent.
2) The fluorescence spectrum test of the compound 1 powder obtained in example 1 was carried out, and the results are shown in FIG. 8, in which it can be seen that the compound 1 powder had a maximum emission wavelength of 491nm at an excitation wavelength of 330nm, and when it was observed under 365nm ultraviolet light, the powder showed bluish green color. And dispersing the powder sample on a quartz plate by using normal hexane, naturally volatilizing to form a film, and testing the luminous quantum yield of the film to obtain a result of more than 0.99. Further, the powder of compound 1 was subjected to luminescence decay curve test and the decay curve was fitted to obtain a luminescence lifetime of 5.57ns (table 1), and the luminescence of compound 1 was attributed to fluorescence.
TABLE 1
3) Compound 1 obtained in example 1 was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1X 10-4mol/L solution. The maximum emission wavelength at an excitation wavelength of 310nm is 402nm, but the solution luminescence is weak.
The compound 1 obtained in example 1 was dissolved in tetrahydrofuran as a good solvent and water as a poor solvent to prepare a mixture having water contents of 0, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 97%, 99%, respectively, at a concentration of 1X 10- 4The emission spectra of the mixed system at mol/L and the excitation wavelength of 310nm were measured, and the results are shown in FIG. 9. As can be seen from the figure, the water content is lower thanAt 90%, the solution did not give significant luminescence. When the water content is increased to more than 95%, the light emission of the mixed system is gradually enhanced, and the emission wavelength is in the range of 508-524 nm. As the water content is increased, the luminous intensity of the system is increased, and the blue shift of the luminescence is generated. The higher the water content, the greater the luminous intensity of the system.
Similarly, the prepared raw material 1, 2-bis (4-bromophenyl) o-carborane is prepared into a mixed system with tetrahydrofuran as a good solvent and water as a poor solvent according to the method, and an emission spectrum test is carried out, so that the 1, 2-bis (4-bromophenyl) o-carborane does not have aggregation-induced luminescence behavior.
2. Fluorescent and color-changing property due to force
The powder of compound 1 obtained in example 1 was pulverized in a mortar and subjected to an emission spectrum test (excitation wavelength of 330nm), and the result is shown in 10, from which it can be seen that the emission wavelength of compound 1 was red-shifted from 491nm before pulverization to 505nm after pulverization. Fumigating the ground sample with dichloromethane to restore to 488 nm; heating at 100 deg.C for 1min can recover to 494nm, and it can be seen that the two treatment modes can recover the luminescence of compound 1 to the luminescence wavelength of its powder. It can be seen that compound 1 has reversible mechanochromatic properties.
The samples before and after the above-mentioned grinding were subjected to an X-ray diffraction test, and the results are shown in FIG. 11. The diffraction peak of the sample before grinding is obvious, and the sample after grinding only shows the diffraction peak of the glass background, which proves that the grinding changes the accumulation mode of molecules.
Further, a dichloromethane solution of the compound 1 was volatilized on a quartz plate to form a film, and a temperature-variable emission spectrum test was performed. In a certain temperature range, the luminous intensity increases with increasing temperature, and the emission wavelength hardly changes, as shown in fig. 12.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (7)
1. A preparation method of a dinaphthyl carborane compound is characterized by comprising the following steps:
under the protection of inert gas, dissolving 1, 2-bis (4-bromophenyl) o-carborane, 1-naphthalene boric acid, a phase transfer catalyst, alkali and a catalyst in a solvent, heating for reaction, and performing post-treatment after the reaction is finished to obtain the product;
wherein the molar ratio of the 1, 2-bis (4-bromophenyl) o-carborane to the 1-naphthalene boric acid is 1: 2-1: 3.
2. the method according to claim 1, wherein the phase transfer catalyst is selected from the group consisting of tetrabutylammonium fluoride, tetrabutylammonium chloride and tetrabutylammonium bromide.
3. The method according to claim 1, wherein the base is selected from any one of sodium carbonate, potassium carbonate and cesium carbonate.
4. The method according to claim 1, wherein the reaction temperature is 100 to 120 ℃.
5. The method according to claim 1, wherein the solvent is a mixture of toluene and water.
6. The method of claim 5, wherein the volume ratio of toluene to water is 3: 1.
7. a dinaphthylcarboborane compound produced by the production method according to any one of claims 1 to 6.
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| SU869290A1 (en) * | 1980-05-08 | 1982-08-15 | Ордена Ленина Институт Элементоорганических Соединений Ан Ссср | Bis-aryl-o-carborane as intermediate product in synthesis of polymers of polyphenylene type |
| JP2005166574A (en) * | 2003-12-05 | 2005-06-23 | Canon Inc | Organic luminescent element |
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| SU869290A1 (en) * | 1980-05-08 | 1982-08-15 | Ордена Ленина Институт Элементоорганических Соединений Ан Ссср | Bis-aryl-o-carborane as intermediate product in synthesis of polymers of polyphenylene type |
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