CN110028511B - Method for chemically protecting black phosphorus through covalent modification by using asymmetric fluorine-containing zinc phthalocyanine diazonium salt - Google Patents
Method for chemically protecting black phosphorus through covalent modification by using asymmetric fluorine-containing zinc phthalocyanine diazonium salt Download PDFInfo
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 80
- 239000011737 fluorine Substances 0.000 title claims abstract description 80
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- -1 zinc phthalocyanine diazonium salt Chemical class 0.000 title claims abstract description 43
- 239000012954 diazonium Substances 0.000 title claims abstract description 39
- 230000004048 modification Effects 0.000 title claims abstract description 14
- 238000012986 modification Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000011701 zinc Substances 0.000 title claims description 65
- 229910052725 zinc Inorganic materials 0.000 title claims description 65
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VNDYJBBGRKZCSX-UHFFFAOYSA-L Zinc bromide Inorganic materials Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229940125904 compound 1 Drugs 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 4
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- PMJMHCXAGMRGBZ-UHFFFAOYSA-N subphthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(=N3)N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C3=N1 PMJMHCXAGMRGBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 229910004039 HBF4 Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004435 EPR spectroscopy Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229940102001 zinc bromide Drugs 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/003—Phosphorus
- C01B25/006—Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention belongs to the technical field of synthesis of phthalocyanine materials and chemical protection of black phosphorus through covalent modification, and particularly relates to a method for chemically protecting black phosphorus through planar covalent modification by using asymmetric fluorine-containing phthalocyanine, and a preparation method of novel asymmetric fluorine-containing phthalocyanine diazonium salt. Compared with the defect of easy oxidation shown by a black phosphorus body, the composite material ZnPc-BP prepared by the invention has excellent environmental stability, and simultaneously has outstanding optical property and charge transmission property, so that the composite material has wide application prospect in the aspect of photoelectric devices.
Description
Technical Field
The invention belongs to the technical field of synthesis of phthalocyanine materials and chemical protection of black phosphorus through covalent modification, and particularly relates to novel asymmetric fluorine-containing phthalocyanine and a preparation method thereof, and also relates to a method for chemically protecting black phosphorus through planar covalent modification by using the asymmetric fluorine-containing phthalocyanine.
Background
Since the first successful separation of single-layer graphene by mechanical exfoliation in 2004, the research of two-dimensional materials has been rapidly developed for more than ten years and shows an exponentially increasing trend. These are only a few nanometers thick, and the sheet material typically has unique physical, chemical, and structural properties. Such as large specific surface area, excellent thermal and electrical conductivity, excellent flexibility and excellent nonlinear optical response, which makes two-dimensional materials have its wide application in the field of optoelectronics. Such as supercapacitors, information storage, organic light emitting diodes, solar cells, optical limiters, etc. Black phosphorus, one of the representative two-dimensional materials in the "post-graphene" era, has recently been extensively studied by the scientific research community. The first synthesis of black phosphorus was performed in 1914 by high temperature and high pressure treatment of red phosphorus. However, until 2014, the single-layer black phosphorus was not successfully stripped from the bulk black phosphorus, i.e., since then, the two-dimensional material has not gained wide academic attention. As a last-shown of the two-dimensional family of materials, black phosphorus has many excellent physicochemical properties, such as high carrier mobility, excellent photoelectric anisotropy, and nonlinear optical response. At the same time, black phosphorus has an adjustable band gap based on the number of layers. The band gap of the single layer of black phosphorus is about 1.8 ev, which shows a downward trend as the number of layers increases, and about 0.3 ev as the tenth layer. However, black phosphorus has the significant disadvantage that its crystals are highly susceptible to oxidation to form phosphorus oxide compounds when exposed to air, which further react with water to form phosphoric acid. Research shows that under the common environment of a laboratory, the few-layer black phosphorus can be completely oxidized and degraded in a few hours. Therefore, the chemical modification of black phosphorus is very important.
The phthalocyanine and its derivatives have a host composed of 18 highly delocalized conjugated pi-electrons and a two-dimensional symmetrical structure, which makes it very thermally and chemically stable. The phthalocyanine has strong absorption in visible light region and near infrared region, so it is widely used in biological fluorescent probe, optical limiter, chemical sensor and LED. Therefore, the phthalocyanine material is used for covalent modification of the black phosphorus, so that the effect of chemical protection of the black phosphorus can be achieved, and the application prospect of the phthalocyanine and the black phosphorus material in the aspect of photoelectricity can be widened. At present, the method for chemically protecting black phosphorus by covalent modification by phthalocyanine has not been reported in the literature.
Disclosure of Invention
The invention aims to provide a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt;
the second purpose of the invention is to provide a preparation method of the novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt;
the third purpose of the invention is to provide a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalently modified black phosphorus material;
the fourth purpose of the invention is to provide a preparation method of the novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalently modified black phosphorus material;
a fifth object of the present invention is to provide a method for chemically protecting black phosphorus by covalent modification using a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt.
The technical scheme of the invention is as follows: a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt with the structural formula of ZnPc-N2 +BF4 -Shown in the figure:
the invention also provides a novel asymmetric fluorine-containing zinc phthalocyanine covalent modified black phosphorus material, which has a structural formula shown as the following black phosphorus composite material ZnPc-BP:
the invention relates to a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N2 +BF4 -The asymmetric fluorine-containing phthalocyanine Pc-NO is obtained by the reaction of subphthalocyanine and 1, 3-diiminoindole2Subsequently by reaction with zinc bromide ZnBr2Obtaining the asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO by reaction2Finally sodium sulfide nonahydrate Na is used2S·9H2Reducing O to obtain asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH2Further diazotization reaction is carried out to obtain asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N2 +BF4 -. The obtained asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N2 +BF4 -And reacting with few layers of black phosphorus nanosheets to obtain the asymmetric fluorine-containing zinc phthalocyanine covalently modified black phosphorus composite material ZnPc-BP. Compared with the defect of extremely easy oxidation shown by a black phosphorus body, the obtained composite material ZnPc-BP has excellent environmental stability, and simultaneously has outstanding optical property and charge transmission property, so that the composite material can be applied to lightHas wide application prospect in the aspect of electric devices.
The preparation method of the novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt provided by the invention comprises the following steps:
1) under the inert gas atmosphere, subphthalocyanine (compound 1, 1eq.) and 1, 3-diiminoindole (compound 2,3eq.) are added into dimethyl sulfoxide solvent (10ml) to react at 60 ℃, and asymmetric fluorine-containing phthalocyanine Pc-NO is obtained through separation and purification2(ii) a Compound 1, compound 2, asymmetric fluorine-containing phthalocyanine Pc-NO2The structural formula of (A) is as follows:
2) under the inert gas atmosphere, adding asymmetric fluorine-containing phthalocyanine Pc-NO2(1eq.), zinc bromide ZnBr2(3eq.) is added into N, N-dimethylformamide solvent (10ml) for reaction at 40 ℃, and asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO is obtained by separation and purification2(ii) a Asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO2The structural formula of (A) is as follows:
3) asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO2(1eq.) in N, N-dimethylformamide (20ml) at 60 deg.C for reduction reaction (reducing agent is 12eq.), separation and purification to obtain asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH2(ii) a Asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH2The structural formula of (A) is as follows:
4) asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH2(1eq.), HBF tetrafluoroborate4(0.5ml) and isoamyl nitrite (5ml) are added into acid to react under the condition of ice salt bath, and the asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N is obtained by separation and purification2 +BF4 -(ii) a Asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N2 +BF4 -The structural formula of (A) is as follows:
the invention further provides a preparation method of the novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalent modification black phosphorus material, which comprises the following steps:
steps 1) -4) are as above;
5) under the nitrogen atmosphere, asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N is added2 +BF4 -(100mg), adding a few layers of black phosphorus (50mg) into an N, N-dimethylformamide solvent for reaction, and separating and purifying to obtain an asymmetric fluorine-containing zinc phthalocyanine covalently modified black phosphorus material ZnPc-BP; the structural formula of the asymmetric fluorine-containing zinc phthalocyanine covalently modified black phosphorus composite material ZnPc-BP is as follows:
the specific synthetic route is as follows:
the reducing agent used is sodium sulfide nonahydrate Na2S·9H2O。
The acid used is glacial acetic acid.
The invention also provides application of the novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt in photoelectric devices, particularly nonlinear optics.
The invention also provides application of the novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalent modified black phosphorus material in photoelectric devices.
The asymmetric fluorine-containing zinc phthalocyanine covalently modified black phosphorus composite ZnPc-BP material prepared by the invention has excellent environmentStability, outstanding optical properties, and the presence of charge transfer phenomena in the system was observed. FIG. 1 is a Raman spectrum of the material, and compared with a few-layer black phosphorus nanosheet, three characteristic peaks of the covalently modified ZnPc-BP material are subjected to a certain degree of blue shift. Wherein A is1 g/A2 gIs 0.72(>0.6), which shows that the modified material ZnPc-BP is not oxidized and has excellent environmental stability. The ultraviolet absorption of the material is measured by taking NMP as a solvent, as shown in figure 2, compared with ZnPc-NH phthalocyanine2The absorption of the B band and the Q band of the covalently modified material ZnPc-BP is respectively red-shifted by 3nm and blue-shifted by 7nm, which shows that the black phosphorus composite material ZnPc-BP has electronic interaction. As shown in an electron paramagnetic resonance spectrogram of FIG. 3, the few-layer black phosphorus nanosheets do not show EPR signals, which are higher than ZnPc-NH phthalocyanine2The result shows that light-induced intramolecular electron transfer occurs in a ZnPc-BP composite material system.
Drawings
FIG. 1 is a Raman spectrum of a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalently modified black phosphorus material ZnPc-BP prepared by the invention.
FIG. 2 is a few-layer black phosphorus crystal, a novel asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH prepared by the invention2The ultraviolet visible light near infrared absorption spectrogram of the novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalently modified black phosphorus material ZnPc-BP prepared by the invention.
FIG. 3 is a few layers of black phosphorus crystal, a novel asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH prepared by the invention2And an electron paramagnetic resonance spectrogram (EPR) of a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalently modified black phosphorus material ZnPc-BP prepared by the invention.
Detailed description of the preferred embodiments
Example 1: a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt and a specific synthetic method of a novel asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalent modified black phosphorus material are disclosed:
1) asymmetric fluorine-containing phthalocyanine Pc-NO2The synthesis of (2): under nitrogen protectionUnder the conditions, compound 1(690mg, 1mmol) and compound 2(570mg, 3mmol) were added to dimethyl sulfoxide (DMSO, 10ml), and the reaction was stirred at 60 ℃ for 12 hours. After the reaction is finished, dropwise adding the reaction solution into glacial methanol, performing suction filtration by using a 0.2-micron filter membrane, and washing a filter cake by using N, N-dimethylformamide (DMF, 50ml) to obtain a green solid which is asymmetric fluorine-containing phthalocyanine Pc-NO2。MALDI-TOF-MS:776[M+H]+；IR:1338，1519cm-1(νNO2)。
2) Asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO2The synthesis of (2): under the protection of nitrogen, asymmetric fluorine-containing phthalocyanine Pc-NO is added2(775mg, 1mmol), zinc bromide ZnBr2(676mg, 3mmol) was added to DMF (10ml) and the reaction stirred at 40 ℃ for 4 hours. After the reaction is finished, the solvent is removed from the reaction liquid by rotary evaporation, and the obtained solid is respectively washed by dilute hydrochloric acid (1M, 50ml) and a large amount of deionized water (200ml) to obtain the asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO2。MALDI-TOF-MS:838[M+H]+；IR:1338，1519cm-1(νNO2)。
3) Asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH2Synthesizing: asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO2(837mg, 1mmol), sodium sulfide nonahydrate Na2S·9H2O (2882mg, 12.0mmol) was added to DMF (20ml) and the reaction stirred at 60 ℃ for 2 h. After the reaction is finished, dropwise adding the reaction liquid into deionized water (400ml), then performing suction filtration operation by using a 0.2-micron filter membrane, and washing the obtained solid by using dilute hydrochloric acid (1M, 50ml) and a large amount of deionized water (200ml) respectively to obtain the asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH2。IR:1606cm-1(νN-H)。
4) Asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N2 +BF4 -The synthesis of (2): under the condition of ice salt bath, asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH is added2(200mg, 0.25mmol), HBF tetrafluoroborate4(0.5ml), isoamyl nitrite (5ml) was added to glacial acetic acid (25ml), and the reaction was stirred at an ice salt bath temperature for 0.5 hour. The reaction was then quenched by the addition of anhydrous ether (20ml) and the reaction was held at-22 ℃ for 6 hours. The mixed solution is filtered by a 0.2 micron filter membraneSuction filtering, washing the filter cake with diethyl ether to obtain the asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N2 +BF4 -。MALDI-TOF-MS:792[M+H]+；IR:2240cm-1(ν-N+≡N)。
5) Synthesizing a black phosphorus composite material ZnPc-BP: taking asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N under the protection of nitrogen2 +BF4 -(100mg), adding the few-layer black phosphorus nanosheet (50mg) into anhydrous oxygen-free DMF, stirring at room temperature for reaction for 24 hours, heating to 50 ℃, and continuing to react for 24 hours. After the reaction is finished, a 0.2-micron filter membrane is used for carrying out suction filtration on the reaction liquid, and a filter cake is washed by DMF, so that the obtained solid is the black phosphorus composite material ZnPc-BP.
FIG. 1 is a Raman spectrum of the material, and compared with a few-layer black phosphorus nanosheet, three characteristic peaks of the covalently modified ZnPc-BP material are subjected to a certain degree of blue shift. Wherein A is1 g/A2 gIs 0.72(>0.6), which shows that the modified material ZnPc-BP is not oxidized and has excellent environmental stability. The ultraviolet absorption of the material is measured by taking NMP as a solvent, as shown in figure 2, compared with ZnPc-NH phthalocyanine2The absorption of the B band and the Q band of the covalently modified material ZnPc-BP is respectively red-shifted by 3nm and blue-shifted by 7nm, which shows that the black phosphorus composite material ZnPc-BP has electronic interaction. As shown in an electron paramagnetic resonance spectrogram of FIG. 3, the few-layer black phosphorus nanosheets do not show EPR signals, which are higher than ZnPc-NH phthalocyanine2The result shows that light-induced intramolecular electron transfer occurs in a ZnPc-BP conforming material system.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (9)
1. An asymmetric fluorine-containing zinc phthalocyanine diazonium salt, which is characterized in that: the structural formula is ZnPc-N2 +BF4 -Shown in the figure:
2. a method for preparing an asymmetric fluorine-containing zinc phthalocyanine diazonium salt according to claim 1, which comprises the following steps: comprises the following steps:
1) under the inert gas atmosphere, subphthalocyanine (compound 1), 1, 3-diiminoindole (compound 2) are added into dimethyl sulfoxide solvent for reaction, and asymmetric fluorine-containing phthalocyanine Pc-NO is obtained by separation and purification2(ii) a Compound 1, compound 2, asymmetric fluorine-containing phthalocyanine Pc-NO2The structural formula of (A) is as follows:
2) under the inert gas atmosphere, adding asymmetric fluorine-containing phthalocyanine Pc-NO2Zinc bromide ZnBr2Adding the mixture into an N, N-dimethylformamide solvent for reaction, separating and purifying to obtain the asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO2(ii) a Asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO2The structural formula of (A) is as follows:
3) asymmetric fluorine-containing zinc phthalocyanine ZnPc-NO2Carrying out reduction reaction in N, N-dimethylformamide solvent, separating and purifying to obtain asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH2(ii) a Asymmetric fluorine-containing zinc phthalocyanine ZnPc-NH2The structural formula of (A) is as follows:
4) asymmetric fluorine-containing zincPhthalocyanine ZnPc-NH2Tetrafluoroboric acid HBF4Adding isoamyl nitrite into acid for reaction, separating and purifying to obtain the asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N2 +BF4 -(ii) a Asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N2 +BF4 -The structural formula of (A) is as follows:
3. the method for preparing the asymmetric fluorine-containing zinc phthalocyanine diazonium salt according to claim 2, characterized in that: in the step 3), the reducing agent is sodium sulfide nonahydrate Na2S·9H2O。
4. The method for preparing the asymmetric fluorine-containing zinc phthalocyanine diazonium salt according to claim 2, characterized in that: in the step 4), the acid is glacial acetic acid.
5. An asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalent modification black phosphorus material is characterized in that: the structural formula is shown as the following formula, namely the black phosphorus composite material ZnPc-BP:
6. a method for preparing the asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalent modification black phosphorus material of claim 5, which is characterized in that: the preparation method comprises the following steps: under the nitrogen atmosphere, asymmetric fluorine-containing zinc phthalocyanine diazonium salt ZnPc-N is added2 +BF4 -Adding a small layer of black phosphorus into an N, N-dimethylformamide solvent for reaction, and separating and purifying to obtain an asymmetric fluorine-containing zinc phthalocyanine covalently modified black phosphorus material ZnPc-BP; the structural formula of the asymmetric fluorine-containing zinc phthalocyanine covalently modified black phosphorus composite material ZnPc-BP is as follows:
7. use of an asymmetric fluorine-containing zinc phthalocyanine diazonium salt according to claim 1 in an optoelectronic device.
8. The use of an asymmetric fluoro-zinc phthalocyanine diazonium salt according to claim 7 in optoelectronic devices, characterized by the use in nonlinear optics.
9. Use of an asymmetric fluorine-containing zinc phthalocyanine diazonium salt covalently modified black phosphorus material according to claim 5 in an optoelectronic device.
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| CN106315531A (en) * | 2016-08-23 | 2017-01-11 | 深圳先进技术研究院 | Black phosphorus modified by aromatic compound and preparation method and application thereof |
| WO2018090329A1 (en) * | 2016-11-18 | 2018-05-24 | 深圳先进技术研究院 | Functionalized flexible electrode and fabrication method therefor |
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| CN106315531A (en) * | 2016-08-23 | 2017-01-11 | 深圳先进技术研究院 | Black phosphorus modified by aromatic compound and preparation method and application thereof |
| WO2018090329A1 (en) * | 2016-11-18 | 2018-05-24 | 深圳先进技术研究院 | Functionalized flexible electrode and fabrication method therefor |
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| Synthesis and characterization of tetra-substituted palladium phthalocyanine complexes;Koodlur Sannegowda Lokesh，等;《Dyes and Pigments》;20120824;第96卷(第1期);269-277 * |
| Synthesis and photoconductivity study of VKCuPc monomer and its homopolymer;M. Wang，等;《Journal of Photochemistry and Photobiology A: Chemistry》;19961231;第94卷;249-251 * |
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