CN109134514A - A kind of benzene-naphthalene diimide derivative and preparation method thereof, application - Google Patents
A kind of benzene-naphthalene diimide derivative and preparation method thereof, application Download PDFInfo
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- CN109134514A CN109134514A CN201811135872.3A CN201811135872A CN109134514A CN 109134514 A CN109134514 A CN 109134514A CN 201811135872 A CN201811135872 A CN 201811135872A CN 109134514 A CN109134514 A CN 109134514A
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- benzene
- naphthalene diimide
- diimide derivative
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- WINTXHPCODMMRI-UHFFFAOYSA-N benzene naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 WINTXHPCODMMRI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- -1 bis- selenium benzene Chemical compound 0.000 claims abstract description 17
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 11
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052759 nickel Chemical group 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- MQUNPMBEKMVOHA-UHFFFAOYSA-N (sodiodiselanyl)sodium Chemical compound [Na][Se][Se][Na] MQUNPMBEKMVOHA-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 239000011669 selenium Substances 0.000 abstract description 20
- 229910052711 selenium Inorganic materials 0.000 abstract description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 239000011592 zinc chloride Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- 235000005074 zinc chloride Nutrition 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 244000061458 Solanum melongena Species 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000005669 field effect Effects 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- 206010019133 Hangover Diseases 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 235000004237 Crocus Nutrition 0.000 description 2
- 241000596148 Crocus Species 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GTILXPRQNNYDHT-UHFFFAOYSA-N 2,3-dibromonaphthalene Chemical compound C1=CC=C2C=C(Br)C(Br)=CC2=C1 GTILXPRQNNYDHT-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
- C07D517/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains four or more hetero rings
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of benzene-naphthalene diimide derivatives and preparation method thereof, application, belong to organic semiconducting materials technical field.A kind of benzene-naphthalene diimide derivative, which is characterized in that there is the structure as shown in following formula I: where R1And R2Separately it is selected from 1,2- phenyl or 2,3- naphthalene；R3And R4It is separately selected from alkyl, the alkyl is the alkyl that carbon atom number is 1-20.The present invention introduces 1,2-, bis- selenium benzene and 2, bis- selenium naphthylene group of 3- greatly strengthens the interaction between molecule, is conducive to packing of molecules, forms the electron propagation ducts of long-range order by simple nucleophilic substitution on NDI core.
Description
Technical field
The present invention relates to a kind of benzene-naphthalene diimide derivatives and preparation method thereof, application, belong to organic semiconducting materials skill
Art field.
Background technique
Organic semiconducting materials are the semiconductor materials being made of organic molecule, are typically contained in molecular structure pi-conjugated
Structure has the characteristics that flexibility is strong, molecular structure is changeable and cheap, soluble, material is light, is easily worked, starts from big
Large-scale production.Compared with traditional inorganic semiconductor material, organic semiconducting materials are not only various in style, raw material is easy to get, prepare
Technique is relatively simple, good environmental stability, and is also equipped with good flexibility and elasticity, convenient for recycling, energy conservation
Environmental protection.Wherein, OFET is then considered as one of most important device in organic semiconductor, and development is also more mature, by widely
Applied to fields such as gas sensor, large scale integrated circuit and display drivings, organic field effect tube is in modern society
(Tang C W. " Two Layer Organic Photovoltaic Cell, " is played an important role in meeting
Appl.Phys.Lett.1986, 48:183.)。
Organic semiconducting materials are broadly divided into two major classes for organic field effect tube at present: organic polymer material with
And organic small molecule material.In view of small molecule material not only has high-purity, the mono-crystalline structures for being easy to parse but also is also equipped with
During preferable the features such as performance, therefore become one kind of the current most study of such material.But since polymer field-effect is brilliant
Body pipe has better mechanical performance, solution processing characteristics and thermodynamic stability, therefore also receives much attention in recent years,
Develop very swift and violent.For organic field effect tube, although molecular structure influences most important, load on its performance
The transport-type of stream is also an important factor for can not ignore, wherein mostly important with N-shaped and bipolar structure research.
For n-type organic semiconducting materials, most typically benzene-naphthalene diimide (NDI) not only has synthesis
Simply, preferable dissolubility and the advantages that preferable planes of molecules.
The structural unit of Isosorbide-5-Nitrae, 5,8 benzene-naphthalene diimides (NDI) has four-membered ring planar conjugate design feature, contains in view of it
Four amide electron-withdrawing groups, benzene-naphthalene diimide structural unit has electron deficient, therefore can be used as electron acceptor unit.It removes
Except this, the easy modified of its structure of NDI provides excellent basis for its study on the modification, to obtain different performance and need
The derivative device asked.It, can also be to increase its dissolubility if both alkyl chain can have been modified on the N atom of two amides
The 2 of naphthalene nucleus, 3,6,7 introducing hetero-atoms functional groups, for adjusting HOMO, LUMO and spectral absorbance values of its molecule, thus
Adapt to the demand of multiple functions material.
Gao et al. reports the heterocyclic fused NDI class n-type organic semiconducting materials of sulphur, the OFET device to be formed a film with solwution method
Part, electron mobility is unexpectedly up to 0.1-3.5cm2V-1s-1, and device possesses preferable operational stability and air stability
(Gao X,Di C,Hu Y,et al.Core-expanded naphthalene diimides fused with 2-(1,3-
dithiol-2-ylidene)malonitrile groups for high-performance, ambient-stable,
solution-processed n-channel organic thin film transistors.J.Am.
Chem.Soc.2010,132:3697-3699).But NDI-DTYM2 series n-type material is to obtain optimal performance, very big
The high annealing (> 150 DEG C) of its film is relied in degree, this limits it in flexible electronic device to a certain extent
Using.The n-type organic semiconducting materials for how developing a kind of low temperature process are of great significance.
Summary of the invention
The present invention provides a kind of preferable benzene-naphthalene diimide derivative of low temperature process performance.It is sub- also to provide a kind of two acyl of naphthalene
The preparation method of amine derivative and its application in terms of organic semiconducting materials.
It is as follows that the present invention solves technical solution used by above-mentioned technical problem:
A kind of benzene-naphthalene diimide derivative has the structure as shown in following formula I:
Wherein, R1And R2Separately it is selected fromR3And R4Separately it is selected from alkane
Base, the alkyl are the alkyl that carbon atom number is 1-20.That is R1And R2Separately it is selected from 1,2- phenyl or 2,3- naphthalene.
The R3And R4At least one of be C20H41.It is further preferred that the R3And R4It is C20H41。
Preferably, above-mentioned C20H41For
A kind of preparation method of benzene-naphthalene diimide derivative includes the following steps: will have as shown in following formula II or formula III
The organic selenium metal reagent of structure and the NDI reagent hybrid reaction with structure shown in formula IV to get.
R3And R4It is separately selected from alkyl, the alkyl is the alkyl that carbon atom number is 1-20；The M be zinc or
Nickel.
The R3And R4At least one of be C20H41.It is further preferred that the R3And R4It is C20H41。
Preferably, above-mentioned C20H41For
The molar ratio of the organic selenium metal reagent and NDI reagent is 1:1.
The NDI reagent is benzene-naphthalene diimide or benzene-naphthalene diimide derivative.
The hybrid reaction is hybrid reaction in organic solvent.The organic solvent is tetrahydrofuran or methylene chloride.
The hybrid reaction carries out at 25-40 DEG C.
The hybrid reaction is that the NDI reagent of structure shown in formula IV is added in organic solvent, is uniformly dispersed at 40 DEG C, so
Organic selenium metal reagent hybrid reaction shown in formula II or formula III is added afterwards.
Be uniformly dispersed at described 40 DEG C is constantly to be stirred at 40 DEG C to evenly dispersed.
It is spaced setting time during the hybrid reaction and carries out contact plate test, until anti-there is no stopping when aubergine hangover
It answers.
Chromatographic solution is used when the contact plate is tested, the chromatographic solution is petroleum ether and methylene chloride with volume ratio for 1:1 group
At mixed liquor.
Evaporation drying is carried out after the hybrid reaction, obtaining solid is the benzene-naphthalene diimide derivative.
The mechanism of the reaction of organic selenium metal reagent shown in preparation formula II or formula III is as follows:
The organic selenium metal reagent of structure shown in the formula II is made by the method included the following steps: by o-dibromobenzene with
Na2Se2Reaction, recycle sodium borohydride reduction, then reacted again with metal halide, tetrabutyl ammonium halide to get.
Described react with metal halide, tetrabutyl ammonium halide is in 25-40 DEG C of reaction 1-2h.
The metal halide is zinc chloride or nickel chloride.
The molar ratio of the o-dibromobenzene and tetrabutyl ammonium halide is 1:1-2.
The tetrabutyl ammonium halide is four butyl bromation amine or tetrabutylammonium chloride.
It is described reacted with tetrabutyl ammonium halide after be separated by solid-liquid separation, wash.It is described to be separated by solid-liquid separation as centrifuge separation.
The intermediate A A is made by the method included the following steps: intermediate B B and zinc chloride or chlorination nickel reactant are obtained
To intermediate A A.
The intermediate B B is to react 0.5-1h at 0-25 DEG C with zinc chloride or chlorination nickel reactant.
The molar ratio of the intermediate B B and zinc chloride or nickel chloride is 1:2.
The intermediate B B is made by the method included the following steps: reacting intermediate CC and sodium borohydride to obtain centre
Body BB.
It is in 0 DEG C of reaction 1-3h that the intermediate CC is reacted with sodium borohydride.
The molar ratio of the intermediate CC and sodium borohydride is 1:13.
It is to react in organic solvent that the intermediate CC is reacted with sodium borohydride.The organic solvent is methanol.
The intermediate CC is made by the method included the following steps: by sub- sodium selenide and 1,2- dibromobenzene in inert atmosphere
Lower reaction obtains intermediate CC.
It is in 120-140 DEG C of reaction 30-40h that the Asia sodium selenide reacts under an inert atmosphere with 1,2- dibromobenzene.
The molar ratio of the Asia sodium selenide and 1,2- dibromobenzene is 1:1.
It is described Asia sodium selenide be made by the method included the following steps: by selenium and sodium react under an inert atmosphere to get.
It is in 100-120 DEG C of reaction 2-4h that the selenium and sodium react under an inert atmosphere.
The molar ratio of the selenium and sodium is 1:1.05.
It is to react in organic solvent that the selenium and sodium react under an inert atmosphere.The organic solvent is DMF.
The inert atmosphere is nitrogen atmosphere.
The organic selenium metal reagent of structure shown in the formula III is made by the method included the following steps: by intermediate A A '
Reacted with tetrabutyl ammonium halide to get.
It is in 25-40 DEG C of reaction 1-2h that the intermediate A A ' is reacted with tetrabutyl ammonium halide.
The molar ratio of the intermediate A A ' and tetrabutyl ammonium halide is 1:1.
The tetrabutyl ammonium halide is four butyl bromation amine or tetrabutylammonium chloride.
The intermediate A A ' is separated by solid-liquid separation after reacting with tetrabutyl ammonium halide, washing.It is described to be separated by solid-liquid separation as centrifugation
Separation.
The intermediate A A ' is made by the method included the following steps: by intermediate B B ' and zinc chloride or chlorination nickel reactant
Obtain intermediate A A '.
The intermediate B B ' is to react 0.5-1h at 0-25 DEG C with zinc chloride or chlorination nickel reactant.
The molar ratio of the intermediate B B ' and zinc chloride or nickel chloride is 1:2.
The intermediate B B ' is made by the method included the following steps: in intermediate CC ' being reacted with sodium borohydride obtain
Mesosome BB '.
It is in 0 DEG C of reaction 1-3h that the intermediate CC ' is reacted with sodium borohydride.
The molar ratio of the intermediate CC ' and sodium borohydride is 1:13.
It is to react in organic solvent that the intermediate CC ' is reacted with sodium borohydride.The organic solvent is methanol.
The intermediate CC ' is made by the method included the following steps: by sub- sodium selenide and 2,3- dibromine naphthalene in indifferent gas
Reaction obtains intermediate CC ' under atmosphere.
It is in 120-140 DEG C of reaction 30-40h that how the Asia sodium selenide reacts under an inert atmosphere with 2,3- dibromo.
The molar ratio of the Asia sodium selenide and 1,2- dibromobenzene is 1:1.
It is described Asia sodium selenide be made by the method included the following steps: by selenium and sodium react under an inert atmosphere to get.
It is in 100-120 DEG C of reaction 2-4h that the selenium and sodium react under an inert atmosphere.
It is to react in organic solvent that the selenium and sodium react under an inert atmosphere.The organic solvent is DMF.
The inert atmosphere is nitrogen atmosphere.
The molar ratio of the selenium and sodium is 1:1.05.
A kind of above-mentioned benzene-naphthalene diimide derivative is as organic semi-conductor application.
The present invention introduces 1,2-, bis- selenium benzene and 2 by simple nucleophilic substitution on NDI core, bis- selenium naphthylene group of 3-,
Two kinds of novel NDI based semiconductor materials are obtained.The NDI derivative modified by core position introduces Se atom, expands NDI
Conjugated system, reduce the band gap of molecule.The material is due to mutual between biggish conjugated system and Se-Se
Effect, greatly strengthens the interaction between molecule, is conducive to packing of molecules, form the electron propagation ducts of long-range order.
Selenium and sulphur are all oxygen group elements, and the compound of their counter structures has similar chemical and physical features, equally
All kinds of derivatives can be carried out, but selenium has the following characteristics that (1) atomic radius is bigger again compared with sulphur, it is easier to polarize；(2)
There is stronger interaction between Se-Se, be very beneficial for the transmission of carrier；(3) more charge notes can be accommodated
Enter.The present invention modifies benzene-naphthalene diimide (NDI) chemical combination objects system by selenium hetero atom, provides that a kind of raw material is cheap, synthesis road
Line is simply clear, easy to operate, reaction condition is mild, convenient for the organic photoelectric intermediate of fairly large synthesis --- the miscellaneous original containing selenium
The method of the benzene-naphthalene diimide derivative of son.
Specific embodiment
In order to be easier to understand the technical problems, technical solutions and beneficial effects solved by the present invention, below with reference to tool
The present invention is described in detail for body embodiment.
Embodiment 1
The benzene-naphthalene diimide derivative of the present embodiment has the structure being shown below:
The preparation principle of the benzene-naphthalene diimide derivative of the present embodiment is as follows:
The preparation method of the benzene-naphthalene diimide derivative of the present embodiment includes the following steps:
1) negate and answer eggplant-shape bottle, the dry DMF of 40mL is added, be then added 1g Se powder (12.66mmol, 1equiv),
The solid sodium (13.29mmol, 1.05equiv) of 306mg, is sealed eggplant-shape bottle with rubber stopper, after vacuumizing, is filled with nitrogen, and
Insertion is full of the balloon of nitrogen on rubber stopper.
By above-mentioned eggplant-shape bottle, oil bath heating is to 100 DEG C under magnetic stirrer, and then constant temperature stirs 2h again, reacts
Solution colour becomes brownish black by colourless in journey.
2) with the syringe of 1mL draw 1.49g 1,2- dibromobenzene (1,2-dibromobenzene, 6.33mmol,
0.5equiv), it is injected into the eggplant-shape bottle in step 1) after reaction, reaction temperature is increased to 140 DEG C, then constant temperature stirs
40h is cooled to room temperature.
It is centrifugated 3min, solid is rinsed with methanol.Repeated centrifugation separates 3min and methanol rinsing step three times.Finally
To faint yellow solid.
3) faint yellow solid for obtaining step 2) is transferred in the round-bottomed flask of 100mL, 50mL methanol is added, slowly
It is added 3.11g sodium borohydride (82.28mmol, 6.5equiv), is put into stirring 1h in ice-water bath system and obtains mixed liquor.
Then 1.73g zinc chloride (ZnCl is weighed2, 12.66mmol, 1equiv), it is added in above-mentioned mixed liquor, in ice water
Continue in bath stir 1h, add later 4.08g four butyl bromation amine (12.66mmol, 1equiv), stir and slowly restore to
Room temperature continues to stir 2h, obtains crocus precipitating, is centrifuged 3min, and solid is cleaned three times with methanol, and it is thick to obtain yellow solid zinc salt
Product.
4) 100mL round-bottomed flask is taken, 50mL tetrahydrofuran is added, two acyl of naphthalene as shown in formula IV that 83mg is then added is sub-
Aminated compounds (NDI reagent), wherein R3And R4It is
It is stirred at 40 DEG C of constant temperature on magnetic stirring apparatus, while being slowly added to yellow solid zinc salt crude product made from step 3)
It is reacted.Solution colour gradually becomes aubergine by faint yellow in reaction process, eventually becomes blue.
Reaction process constantly carries out contact plate test, and it with volume ratio is what 1:1 was formed that chromatographic solution, which is petroleum ether and methylene chloride,
Mixed liquor, contact plate test is until there is no until aubergine hangover.
Solution after fully reacting is evaporated in Rotary Evaporators, obtains blue solid powder, as benzene-naphthalene diimide
Derivative (BSeNDI).
The yield that the benzene-naphthalene diimide derivative (BSeNDI) of the present embodiment is calculated is 45%.
The nuclear magnetic data of the benzene-naphthalene diimide derivative (BSeNDI) of the present embodiment is as follows:
BSeNDI:1H NMR(400MHz,CDCl3) δ 7.51 (d, 4H, J=4Hz), 7.18 (d, 4H, J=4Hz), 4.25
(d, 4H, J=4Hz), 2.04 (s, 2H), 1.43-1.21 (m, 32H), 0.89-0.83 (m, 12H) .MS (MALDI-TOF):
1293.7(M)+.
Embodiment 2
The benzene-naphthalene diimide derivative of the present embodiment is identical as the benzene-naphthalene diimide derivative in embodiment 1.
The preparation method of the benzene-naphthalene diimide derivative of the present embodiment and the system of the benzene-naphthalene diimide derivative in embodiment 1
Preparation Method is different only in that: replacing 1.73g zinc chloride with 1.64g nickel chloride (12.66mmol, 1equiv) in step 3)
(ZnCl2, 12.66mmol, 1equiv), it is other identical as in embodiment 1.
The yield of benzene-naphthalene diimide derivative (BSeNDI) is 51% in the present embodiment, and nuclear magnetic data is as follows:
BSeNDI:1H NMR(400MHz,CDCl3) δ 7.51 (d, 4H, J=4Hz), 7.18 (d, 4H, J=4Hz), 4.25
(d, 4H, J=4Hz), 2.04 (s, 2H), 1.43-1.21 (m, 32H), 0.89-0.83 (m, 12H) .MS (MALDI-TOF):
1293.7(M)+.
Embodiment 3
The benzene-naphthalene diimide derivative of the present embodiment is identical as the benzene-naphthalene diimide derivative in embodiment 1.
The preparation method of the benzene-naphthalene diimide derivative of the present embodiment and the system of the benzene-naphthalene diimide derivative in embodiment 1
Preparation Method is different only in that: replacing 4.08g tetra- with 3.52g tetrabutylammonium chloride (12.66mmol, 1equiv) in step 3)
Butyl amine bromide (12.66mmol, 1equiv) is other identical as in embodiment 1.
The yield of benzene-naphthalene diimide derivative (BSeNDI) is 42% in the present embodiment, and nuclear magnetic data is as follows:
BSeNDI:1H NMR(400MHz,CDCl3) δ 7.51 (d, 4H, J=4Hz), 7.18 (d, 4H, J=4Hz), 4.25
(d, 4H, J=4Hz), 2.04 (s, 2H), 1.43-1.21 (m, 32H), 0.89-0.83 (m, 12H) .MS (MALDI-TOF):
1293.7(M)+.
Embodiment 4
The benzene-naphthalene diimide derivative of the present embodiment is identical as the benzene-naphthalene diimide derivative in embodiment 1.
The preparation method of the benzene-naphthalene diimide derivative of the present embodiment and the system of the benzene-naphthalene diimide derivative in embodiment 1
Preparation Method is different only in that: replacing 50mL tetrahydrofuran with 50mL methylene chloride in step 4), others are and in embodiment 1
It is identical.
The yield of benzene-naphthalene diimide derivative (BSeNDI) is 46% in the present embodiment, and nuclear magnetic data is as follows:
BSeNDI:1H NMR(400MHz,CDCl3) δ 7.51 (d, 4H, J=4Hz), 7.18 (d, 4H, J=4Hz), 4.25
(d, 4H, J=4Hz), 2.04 (s, 2H), 1.43-1.21 (m, 32H), 0.89-0.83 (m, 12H) .MS (MALDI-TOF):
1293.7(M)+.
Embodiment 5
The benzene-naphthalene diimide derivative of the present embodiment has the structure being shown below:
The preparation principle of the benzene-naphthalene diimide derivative of the present embodiment is as follows:
The preparation method of the benzene-naphthalene diimide derivative of the present embodiment includes the following steps:
1) negate and answer eggplant-shape bottle, the dry DMF of 40mL is added, be then added 1g Se powder (12.66mmol, 1equiv),
The solid sodium (13.29mmol, 1.05equiv) of 306mg, is sealed eggplant-shape bottle with rubber stopper, after vacuumizing, is filled with nitrogen, and
Insertion is full of the balloon of nitrogen on rubber stopper.
By above-mentioned eggplant-shape bottle, oil bath heating is to 100 DEG C under magnetic stirrer, and then constant temperature stirs 2h again, reacts
Solution colour becomes brownish black by colourless in journey.
2) with the syringe of 1mL draw 1.81g 2,3- dibromo how (2,3-dibromonaphthalene,
6.33mmol, 0.5equiv), it is injected into the eggplant-shape bottle in step 1) after reaction, reaction temperature is increased to 140 DEG C, then
Constant temperature stirs 40h, is cooled to room temperature.
It is centrifugated 3min, solid is rinsed with methanol.Repeated centrifugation separates 3min and methanol rinsing step three times.Finally
To faint yellow solid.
3) faint yellow solid for obtaining step 2) is transferred in the round-bottomed flask of 100mL, 50mL methanol is added, slowly
It is added 3.11g sodium borohydride (82.28mmol, 6.5equiv), is put into stirring 1h in ice-water bath system and obtains mixed liquor.
Then 1.73g zinc chloride (ZnCl is weighed2, 12.66mmol, 1equiv), it is added in above-mentioned mixed liquor, in ice water
Continue in bath stir 1h, add later 4.08g four butyl bromation amine (12.66mmol, 1equiv), stir and slowly restore to
Room temperature continues to stir 2h, obtains crocus precipitating, is centrifuged 3min, and solid is cleaned three times with methanol, and it is thick to obtain yellow solid zinc salt
Product.
4) 100mL round-bottomed flask is taken, 50mL tetrahydrofuran is added, 83mg benzene-naphthalene diimide as shown in formula IV is then added
Class compound (NDI reagent), wherein R3And R4It is
It is stirred at 40 DEG C of constant temperature on magnetic stirring apparatus, while being slowly added to yellow solid zinc salt crude product made from step 3)
It is reacted.Solution colour gradually becomes aubergine by faint yellow in reaction process, eventually becomes blue.
Reaction process constantly carries out contact plate test, and it with volume ratio is what 1:1 was formed that chromatographic solution, which is petroleum ether and methylene chloride,
Mixed liquor, contact plate test is until there is no until aubergine hangover.
Solution after fully reacting is evaporated in Rotary Evaporators, obtains blue solid powder, as benzene-naphthalene diimide
Derivative (NSeNDI).
The yield that the benzene-naphthalene diimide derivative (NSeNDI) of the present embodiment is calculated is 42%.
The nuclear magnetic data of the benzene-naphthalene diimide derivative (NSeNDI) of the present embodiment is as follows:
NSeNDI:1H NMR(400MHz,CDCl3) δ 7.82 (s, 4H), 7.43 (s, 4H), 7.22 (s, 4H, J=4Hz),
2.03(s,2H),1.40-1.17(m,32H),0.86-0.81(m,12H).MS(MALDI-TOF): 1393.6(M)+.
Embodiment 6
The benzene-naphthalene diimide derivative of the present embodiment is identical as the benzene-naphthalene diimide derivative in embodiment 5.
The preparation method of the benzene-naphthalene diimide derivative of the present embodiment and the system of the benzene-naphthalene diimide derivative in embodiment 5
Preparation Method is different only in that: replacing 1.73g zinc chloride with 1.64g nickel chloride (12.66mmol, 1equiv) in step 3)
(ZnCl2, 12.66mmol, 1equiv), it is other identical as in embodiment 5.
The yield of benzene-naphthalene diimide derivative (NSeNDI) is 60% in the present embodiment, and nuclear magnetic data is as follows:
NSeNDI:1H NMR(400MHz,CDCl3) δ 7.82 (s, 4H), 7.43 (s, 4H), 7.22 (s, 4H, J=4Hz),
2.03(s,2H),1.40-1.17(m,32H),0.86-0.81(m,12H).MS(MALDI-TOF): 1393.6(M)+.
Embodiment 7
The benzene-naphthalene diimide derivative of the present embodiment is identical as the benzene-naphthalene diimide derivative in embodiment 5.
The preparation method of the benzene-naphthalene diimide derivative of the present embodiment and the system of the benzene-naphthalene diimide derivative in embodiment 5
Preparation Method is different only in that: replacing 4.08g tetra- with 3.52g tetrabutylammonium chloride (12.66mmol, 1equiv) in step 3)
Butyl amine bromide (12.66mmol, 1equiv) is other identical as in embodiment 5.
The yield of benzene-naphthalene diimide derivative (NSeNDI) is 43% in the present embodiment, and nuclear magnetic data is as follows:
NSeNDI:1H NMR(400MHz,CDCl3) δ 7.82 (s, 4H), 7.43 (s, 4H), 7.22 (s, 4H, J=4Hz),
2.03(s,2H),1.40-1.17(m,32H),0.86-0.81(m,12H).MS(MALDI-TOF): 1393.6(M)+.
Embodiment 8
The benzene-naphthalene diimide derivative of the present embodiment is identical as the benzene-naphthalene diimide derivative in embodiment 5.
The preparation method of the benzene-naphthalene diimide derivative of the present embodiment and the system of the benzene-naphthalene diimide derivative in embodiment 5
Preparation Method is different only in that: replacing 50mL tetrahydrofuran with 50mL methylene chloride in step 4), others are and in embodiment 5
It is identical.
The yield of benzene-naphthalene diimide derivative (NSeNDI) is 51% in the present embodiment, and nuclear magnetic data is as follows:
NSeNDI:1H NMR(400MHz,CDCl3) δ 7.82 (s, 4H), 7.43 (s, 4H), 7.22 (s, 4H, J=4Hz),
2.03(s,2H),1.40-1.17(m,32H),0.86-0.81(m,12H).MS(MALDI-TOF): 1393.6(M)+.
Benzene-naphthalene diimide derivative of the invention may be used as organic semiconducting materials, and the member as flexible electronic device
Part.
Claims (10)
1. a kind of benzene-naphthalene diimide derivative, which is characterized in that have the structure as shown in following formula I:
Wherein, R1And R2Separately it is selected fromOrR3And R4Separately it is selected from alkyl, institute
Stating alkyl is the alkyl that carbon atom number is 1-20.
2. a kind of preparation method of benzene-naphthalene diimide derivative, which comprises the steps of: will have such as following formula II or
The organic selenium metal reagent of structure shown in formula III and the NDI reagent hybrid reaction with structure shown in formula IV to get.
R3And R4It is separately selected from alkyl, the alkyl is the alkyl that carbon atom number is 1-20；The M is zinc or nickel.
3. the preparation method of benzene-naphthalene diimide derivative according to claim 2, which is characterized in that the organic selenium metal
The molar ratio of reagent and NDI reagent is 1:1.
4. the preparation method of benzene-naphthalene diimide derivative according to claim 2, which is characterized in that the hybrid reaction is
Hybrid reaction in organic solvent.
5. the preparation method of benzene-naphthalene diimide derivative according to claim 2, which is characterized in that the hybrid reaction exists
It is carried out at 40 DEG C.
6. the preparation method of benzene-naphthalene diimide derivative according to claim 2, which is characterized in that the formula II or formula III
The organic selenium metal reagent of shown structure is made by the method included the following steps: by o-dibromobenzene or 2,3 dibromine naphthalenes and Na2Se2
Reaction, recycle sodium borohydride reduction, then reacted again with metal halide, tetrabutyl ammonium halide to get.
7. the preparation method of benzene-naphthalene diimide derivative according to claim 6, which is characterized in that the o-dibromobenzene or
It is in 120-140 DEG C of reaction 30-40h that 2,3 dibromine naphthalenes are reacted with sub- sodium selenide.
8. the preparation method of benzene-naphthalene diimide derivative according to claim 7, which is characterized in that the tetrabutyl halogenation
Ammonium is four butyl bromation amine or tetrabutylammonium chloride.
9. the preparation method of benzene-naphthalene diimide derivative according to claim 6, which is characterized in that the o-dibromobenzene or
The molar ratio of 2,3 dibromine naphthalenes and tetrabutyl ammonium halide is 1:1-2.
10. a kind of benzene-naphthalene diimide derivative as described in claim 1 is as organic semi-conductor application.
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