CN107353302A - A kind of carborane derivative material based on carbazole and preparation method and application - Google Patents
A kind of carborane derivative material based on carbazole and preparation method and application Download PDFInfo
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- CN107353302A CN107353302A CN201710533642.1A CN201710533642A CN107353302A CN 107353302 A CN107353302 A CN 107353302A CN 201710533642 A CN201710533642 A CN 201710533642A CN 107353302 A CN107353302 A CN 107353302A
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- Prior art keywords
- carbazole
- carbazoles
- compound
- nitrogen
- carborane
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims abstract description 25
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000005669 field effect Effects 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 74
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- 239000002904 solvent Substances 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 238000002390 rotary evaporation Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 18
- HKJBDZVNXYYHAK-UHFFFAOYSA-N CN(C1=CC=CC=C1)C.[N] Chemical compound CN(C1=CC=CC=C1)C.[N] HKJBDZVNXYYHAK-UHFFFAOYSA-N 0.000 claims description 16
- 239000012044 organic layer Substances 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 15
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 14
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- CGRJOQDFNTYSGH-UHFFFAOYSA-N tritylphosphane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(P)C1=CC=CC=C1 CGRJOQDFNTYSGH-UHFFFAOYSA-N 0.000 claims description 12
- 238000010898 silica gel chromatography Methods 0.000 claims description 11
- -1 Alkynyl benzene Chemical compound 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical group C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000011540 sensing material Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 2
- 230000008020 evaporation Effects 0.000 claims 2
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 claims 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 2
- 238000001378 electrochemiluminescence detection Methods 0.000 abstract description 32
- 238000000034 method Methods 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000007850 fluorescent dye Substances 0.000 abstract description 2
- 238000001215 fluorescent labelling Methods 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 150000001716 carbazoles Chemical class 0.000 abstract 3
- 125000000304 alkynyl group Chemical group 0.000 abstract 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 abstract 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 230000005284 excitation Effects 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000004607 11B NMR spectroscopy Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000005905 alkynylation reaction Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
-
- 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
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a kind of carborane derivative material and its methods for making and using same based on carbazole.Preparation method includes：9 (4 bromobenzene) 9 carbazoles, 9 (3 bromophenyl) 9 carbazole Tong Guo Yuan heads coupling reaction (Sonogashira coupling reaction) reaction alkynyl obtain 9 (4 acetylenylbenzene) 9 carbazoles, 9 (3 acetylenylbenzene) 9 carbazoles, and synthesis compound I, compound II are then reacted with carborane.In the present invention, the alkynyl derivatives of carbazole and the actual conditions and example of carborane reaction are given, high yield of the invention achievements exhibition to target product.Such compound prepares simple, intermediate cost is cheap, course of reaction is easily controlled, and product is easily isolated, high income, purity are high, has potential application value in sensor, electroluminescent device, organic solar batteries, organic field effect tube etc..Meanwhile such carborane derivative also has good application on electrogenerated chemiluminescence (ECL), small molecule biological fluorescent labeling can be used as.
Description
Technical field
The present invention relates to a kind of carborane derivative material based on carbazole and preparation method and application, belong to photoelectricity material
Expect technical field.
Background technology
Organic molecule has structure diversity and easily cutting property, can be had with binding molecule design and organic synthesis
The new compound of some particular characteristics.Because organic molecule designability is good, it is easy to functionalization, in the last few years, with molecule
Engineering and the development of organic synthesis, the research of electrogenerated chemiluminescence (ECL) material of organic molecule have obtained broad development, they
Great effect has been played in environmental pollution analyte detection, biological detection etc..
Electrogenerated chemiluminescence is a kind of the luminous of unique types, wherein the electronics transfer between the ion radical being electrically generated
Electron excitation product is produced near electrode, so as to launch light.Electrogenerated chemiluminescence and electrochemistry are conventional and sensitive instruments,
Available for acquisition on radical ion formation and stability and the valuable information of the delicate interaction of intramolecular.It is this
Information is useful in organic luminescent device (OLED) design, and wherein electric charge produces, and migration and restructuring are organic by activity
Similar electriferous state in layer determines.Another purposes of electrogenerated chemiluminescence is related to exploitation and is used to mark new ECL to launch
Body finds the ECL emitters of the species wavelength different from using at present in the bioanalysis application of different wave length.Therefore, ECL
It is a kind of important PhotoelectrochemicalTechnique Technique, has in terms of the fundamental analysis of organic and inorganic materials and in terms of bioanalysis more
Kind application.
It is the most extensive with pyridine (BPY) class application for as ECL emitters.Using pyridine as core, pass through introducing
Other aromatic hydrocarbons chains improve pi-conjugated performance, and then improve the ability of intermolecular charge transfer.Wherein pyridine provides stable excitation state
Required electronics free radical, so as to strengthen ECL intensity.However, the synthetic method of pyridines dyestuff is complicated, low yield, limit
Its ECL fields deeper into development and application.Due to including stable carborane unit in carborane class compound, so they
Equally can stably it provide because of excitation state electronics free radical caused by ionization.And caborane compounds can pass through phase mostly
Simple synthetic method is obtained, and the modification carried out to carborane in structure is also very easy to realize.But organic or
In person's inorganic solution, after ECL emitters slough a proton, it is difficult to redox reaction occur, in order that electrochemical process is suitable
Profit circulation is carried out, it usually needs is coated in tripropyl amine (TPA) (TPrA) and ECL emitters on the anode of electrode jointly.Wherein tripropyl amine (TPA) exists
Coreagent is used as during this, by discharging electronics oxidation reaction occurs for the TPrA of electrode surface to be excited as cation
The TPrA of state+, and it is rapid it is spontaneous slough a proton and form excitation state tripropyl amine (TPA), so, tool is there is in reaction system
There are the ECL emitters cation of strong oxidizing property and the excitation state tripropyl amine (TPA) with strong reducing property.When the ECL hairs with strong oxidizing property
Beam cation and the excitation state tripropyl amine (TPA) generation redox reaction with strong reducing property, the ECL emitters of excitation state pass through
Fluorescence decay mechanism is so as to producing fluorescence.Due to still suffering from stable ECL emitters and tripropyl amine (TPA) in above-mentioned reaction system so that
The electrochemical reaction and chemiluminescent process progresses of electrode surface can continue, and so, whole course of reaction can circulate progress.
By above-mentioned cyclic process, measure signal constantly amplifies, so that detection sensitivity greatly improves.Although boracic is organic
Compound has had been reported that as ECL emitters；But application of the material containing carborane group on ECL, it yet there are no report
Road.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of carborane derivative material based on carbazole and its prepare and answer
Use method.The improvement of the invention first passage synthetic method improves the yield of aromatic hydrocarbons carborane derivative, and by carbon containing boron
The material of alkane unit is used for ECL emitters, passes through the stability being introduced into carborane group increase electrochemical process.Provide one
Kind is based on high intensity, the electrogenerated chemiluminescence emitter of high stability, and the system of the carborane derivative of easily prepared carbazole
Preparation Method, it is complicated to solve the problems, such as prepared by current ECL emitter materials.
Technical scheme：The present invention provides a kind of carborane derivative material based on carbazole and preparation method and application.
The present invention a kind of carborane derivative material based on carbazole be containing carbazole structure system, by Carborane skeleton from it is different
Site phenyl unit link；Such material has following compound I or II formula structure：
Wherein：Compound I is that the 4- positions of the phenyl carbazole on nitrogen-atoms 9- positions in carbazole are connected with carborane；Compound
II is to be connected in the 3- positions of the phenyl ring of phenyl carbazole with carborane；C is carbon, and N is nitrogen.
Wherein,
The material of the compound I and compound II contain a carbazole unit and a carborane unit.
The 3- positions of phenyl ring or 4- positions are linked with the carbon atom on carborane by carbon-carbon bond on the phenyl carbazole.
In the preparation method of the carborane derivative material based on carbazole of the present invention, the compound I preparation method bags
Include following steps：
Step 1：The preparation of 9- (4- acetylenylbenzenes) -9- carbazoles：Under nitrogen protective condition, by 9- (4- bromobenzenes) -9- clicks
Azoles, acetylenylbenzene and adds cuprous iodide in dry reaction bulb four (trityl) phosphine palladiums, in nitrogen and lucifuge atmosphere
Under, triethylamine solution is then injected into mixture, is flowed back 10~14 hours at 100 DEG C~120 DEG C, terminating reaction is cooled to room
Wen Hou, reactant mixture are added to the water and extracted with dichloromethane, and remaining organic layer anhydrous magnesium sulfate is dry and filters；Will
Solvent rotary evaporation is dried, and solid is purified by silica gel chromatographic column, finally gives 9- (4- acetylenylbenzenes) -9- carbazoles, be micro- Huang
Color powder；
Step 2：Compound I preparation：In nitrogen atmosphere, to reaction bulb in add dry toluene distillation to dissolve
Decaborane and nitrogen, nitrogen-dimethylaniline, in 35 DEG C~45 DEG C stirrings, temperature is then risen into 100 DEG C~120 DEG C holdings, then
After being cooled to 35 DEG C~45 DEG C, injection compound 9- (4- acetylenylbenzenes) -9- carbazoles of toluene distillation solvent dissolving, it will react
Mixture flows back 10~12 hours under the conditions of 100 DEG C~120 DEG C, after terminating reaction, mixture is cooled into room temperature and uses first
Alcohol is quenched, and removes solvent using rotary evaporation, residue is added to the water, organic layer is extracted with dichloromethane, uses anhydrous slufuric acid
Magnesium is dry and filters, and solvent is dried with rotary evaporation, solid silica gel chromatography, obtains the compound I of yellow powder.
Wherein,
The acetylenylbenzene is 1 with 9- (4- bromobenzenes) -9- carbazoles mol ratio:1~1.2:1；Described four (trityl) phosphine
Palladium is 0.05 with 9- (4- bromobenzenes) -9- carbazoles mol ratio:1~0.1:1, the cuprous iodide rubs with 9- (4- bromobenzenes) -9- carbazoles
You are than being 0.1:1~0.2:1；Every mM of 9- (4- bromobenzenes) -9- carbazole adds 10~15mL of triethylamine solvent.
In the step 2, the decaborane is 1 with 9- (4- acetylenylbenzenes) -9- carbazoles mol ratio:1~1.1:1, nitrogen,
Nitrogen-dimethylaniline is 1.5 with 9- (4- acetylenylbenzenes) -9- carbazoles mol ratio:1~1.7:1, every mM of 9- (4- acetenyl
Benzene) 10~15mL of -9- carbazoles addition toluene distillation solvent.
In the preparation method of the carborane derivative material based on carbazole of the present invention, the preparation method of the compound II
Comprise the following steps：
Step 1：The preparation of 9- (3- acetylenylbenzenes) -9- carbazoles：Under nitrogen protective condition, by 9- (3- bromobenzenes) -9- clicks
Azoles, acetylenylbenzene and adds cuprous iodide in dry reaction bulb four (trityl) phosphine palladiums, in nitrogen and lucifuge atmosphere
Under, triethylamine solution is then injected into mixture, is flowed back 10~14 hours at 100 DEG C~120 DEG C, terminating reaction is cooled to room
Wen Hou, reactant mixture are added to the water and extracted with dichloromethane, and remaining organic layer anhydrous magnesium sulfate is dry and filters；Will
Solvent rotary evaporation is dried, and solid is purified by silica gel chromatographic column, finally gives 9- (3- acetylenylbenzenes) -9- carbazoles, be micro- Huang
Color powder；
Step 2：Compound II preparation：In nitrogen atmosphere, to reaction bulb in add dry toluene distillation to dissolve
Decaborane and nitrogen, nitrogen-dimethylaniline, in 35 DEG C~45 DEG C stirrings, temperature is then risen into 100 DEG C~120 DEG C holdings, then
After being cooled to 35 DEG C~45 DEG C, injection compound 9- (3- acetylenylbenzenes) -9- carbazoles of toluene distillation solvent dissolving, it will react
Mixture flows back 10~12 hours under the conditions of 100 DEG C~120 DEG C, after terminating reaction, mixture is cooled into room temperature and uses first
Alcohol is quenched, and removes solvent using rotary evaporation, residue is added to the water, organic layer is extracted with dichloromethane, uses anhydrous slufuric acid
Magnesium is dry and filters, and solvent is dried with rotary evaporation, solid silica gel chromatography, obtains the compound of yellow powder
II。
Wherein,
The acetylenylbenzene is 1 with 9- (3- bromobenzenes) -9- carbazoles mol ratio:1~1.2:1；Described four (trityl) phosphine
Palladium is 0.05 with 9- (3- bromobenzenes) -9- carbazoles mol ratio:1~0.1:1, the cuprous iodide rubs with 9- (3- bromobenzenes) -9- carbazoles
You are than being 0.1:1~0.2:1；Every mM of 9- (3- bromobenzenes) -9- carbazole adds 10~15mL of triethylamine solvent.
In the step 2, the decaborane is 1 with 9- (3- acetylenylbenzenes) -9- carbazoles mol ratio:1~1.1:1, nitrogen,
Nitrogen-dimethylaniline is 1.5 with 9- (3- acetylenylbenzenes) -9- carbazoles mol ratio:1~1.7:1, every mM of 9- (3- acetenyl
Benzene) 10~15mL of -9- carbazoles addition toluene distillation solvent.
Carborane derivative materials application of the invention based on carbazole is in sensor, electroluminescent device, organic solar
In terms of battery or organic field effect tube, or as electrochromic material, photochromic material, biological sensing material, hole
Transmission material, nonlinear optical material, anti-fake material or camouflage material are applied to organic photoelectric field.
Beneficial effect：The present invention provides a kind of carborane derivative material based on carbazole, such compounds process for production thereof
Simply, easy to operate, course of reaction is easily controlled, and product is easily isolated, high income, purity are high, and particularly it has very
High electrogenerated chemiluminescence intensity.It is in sensor, electroluminescent device, organic solar batteries, organic field effect tube
Etc. there is potential application value, and electrochromic material, photochromic material, hole mobile material, non-thread can be used as
Property optical material, anti-fake material, camouflage material etc. are applied to organic photoelectric field.
Brief description of the drawings
Fig. 1 is the continuous ECL spectrograms of material I, when illustration is corresponding maximum intensity, the emission peak of electrogenerated chemiluminescence.
Fig. 2 be material I under given conditions photomultiplier (PMT) obtain cyclic voltammogram, test scope be 0V~
2.5V。
Fig. 3 is the continuous ECL spectrograms of material II, when illustration is corresponding maximum intensity, the emission peak of electrogenerated chemiluminescence.
Fig. 4 be material II under the conditions of characteristic test photomultiplier (PMT) obtain cyclic voltammogram, test scope
For -1.8V-2.5V.
Test condition：Material I and material II is in the dichloromethane lysate that concentration is 0.1 mM, and in positive electricity
20 mMs of tripropyl amine (TPA) and 0.1 mole of tetrabutyl ammonium hexafluorophosphate are coated on extremely, is entered with 20 millivolts of sweep speeds per second
Row electrogenerated chemiluminescence collection of illustrative plates scans.
Embodiment
Preparation method includes：9- (4- bromobenzenes) -9- carbazoles, 9- (3- bromophenyls) -9- carbazole Tong Guo Yuan head coupling reaction alkynes
Base obtains 9- (4- acetylenylbenzenes) -9- carbazoles, 9- (3- acetylenylbenzenes) -9- carbazoles, and synthesis chemical combination is then reacted with carborane
Thing I, II.Such carborane derivative has good application on electrogenerated chemiluminescence, can be used as small molecule biological fluorescent labeling,
Such carborane derivative has high electrogenerated chemiluminescence intensity and good stability.
The preparation method of the material of the carborane derivative of such carbazole, comprises the following steps：
Step 1：The preparation of 9- (4- acetylenylbenzenes) -9- carbazoles, 9- (3- acetylenylbenzenes) -9- carbazoles, with 9- (4- acetylene
Base benzene) -9- carbazoles preparation exemplified by：Under the conditions of nitrogen atmosphere and lucifuge, by 1 mM of 9- (4- bromobenzenes) -9- carbazoles,
The catalyst, 0.1~0.2 mM of cuprous iodide and 1.0~1.2 millis of 0.05-0.1 mMs four (trityl) phosphine palladiums
Mole acetylenylbenzene be dissolved in 10~15mL triethylamine, 110 DEG C flow back 10-14 hours.Terminating reaction is cooled to room
Wen Hou, reactant mixture are added to the water and extracted with dichloromethane.Remaining organic layer anhydrous magnesium sulfate is dry and filters.Will
Solvent rotary evaporation is dried, and solid is purified by silica gel chromatographic column, finally gives 9- (4- acetylenylbenzenes) -9- carbazoles, be micro- Huang
Color powder；
Step 2：The preparation of compound I, II, by taking compound I preparation as an example：Under nitrogen protective condition, 1.0~1.2 millis
Mole l decaborane and 1.5~1.7 mMs of nitrogen, nitrogen-dimethylaniline are dissolved in 5mL drying and distilling toluene solvant,
Stirred 30 minutes at 35 DEG C~45 DEG C.Then temperature is risen into 100 DEG C~120 DEG C to be kept for 2 hours, is subsequently cooled to 35 DEG C~45
After DEG C, compound 9- (4- acetylenylbenzenes) -9- carbazoles of injection 5~10mL toluene distillations solvent dissolving, by reactant mixture
Flowed back under the conditions of 100 DEG C~120 DEG C 10-12 hours.After terminating reaction, mixture is cooled to room temperature and is quenched with methanol.
Solvent is removed using rotary evaporation, residue is added to the water, organic layer is extracted with dichloromethane, is dried simultaneously with anhydrous magnesium sulfate
Filtering.Solvent is dried with rotary evaporation, solid silica gel chromatography.The compound I of yellow powder is obtained, with methanol weight
Crystallization obtains more pure compound I.
Wherein, i is the alkynylation reaction under the effect of four (trityl) phosphine palladiums, cuprous iodide and acetylenylbenzene；Ii is
In the nitrogen of decaborane sum, the lower compound I of nitrogen-dimethylaniline effect, compound II prepare reaction.
Embodiment 1：
Reaction condition one：Under nitrogen and lucifuge protective condition, by 9- (4- bromobenzenes) -9- carbazoles (322.6 milligrams, 1.0 mmoles
You), four (trityl) phosphine palladiums (57 milligrams, 0.05 mM), cuprous iodide (19 milligrams, 0.1 mM) and acetylene
Base benzene (112 milligrams, 1.0 mMs) is dissolved in 10mL triethylamine (Et3N in), flowed back 12 hours at 110 DEG C.Terminating reaction
After being cooled to room temperature, reactant mixture is added to the water and extracted with dichloromethane.Remaining organic layer is dried with anhydrous magnesium sulfate
And filter.Solvent rotary evaporation is dried, solid is purified by silica gel chromatographic column.Finally give to obtain 9- (4- acetylenylbenzenes)-
9- carbazoles, are micro-yellow powder (265 milligrams), yield 61%
Reaction condition two：Under nitrogen and lucifuge protective condition, by 9- (4- bromobenzenes) -9- carbazoles (322.6 milligrams, 1.0 mmoles
You), four (trityl) phosphine palladiums (104 milligrams, 0.01 mM), cuprous iodide (19 milligrams, 0.1 mM) and acetylene
Base benzene (112 milligrams, 1.0 mMs) is dissolved in 10mL triethylamine, is flowed back 12 hours at 110 DEG C.Terminating reaction is cooled to
After room temperature, reactant mixture is added to the water and extracted with dichloromethane.Remaining organic layer anhydrous magnesium sulfate is dry and filters.
Solvent rotary evaporation is dried, solid is purified by silica gel chromatographic column.9- (4- acetylenylbenzenes) -9- carbazoles are finally given, are micro-
Yellow powder (304 milligrams), yield 70%.
Reaction condition three：Under nitrogen and lucifuge protective condition, by 9- (4- bromobenzenes) -9- carbazoles (322.6 milligrams, 1.0 mmoles
You), four (trityl) phosphine palladiums (57 milligrams, 0.01 mM), cuprous iodide (19 milligrams, 0.1 mM) and acetylene
Base benzene (123 milligrams, 1.1 mMs) is dissolved in 10mL triethylamine, is flowed back 12 hours at 110 DEG C.Terminating reaction is cooled to
After room temperature, reactant mixture is added to the water and extracted with dichloromethane.Remaining organic layer anhydrous magnesium sulfate is dry and filters.
Solvent rotary evaporation is dried, solid is purified by silica gel chromatographic column.9- (4- acetylenylbenzenes) -9- carbazoles are finally given, are micro-
Yellow powder (325 milligrams), yield 72.9%.
Reaction condition four：Under nitrogen protective condition, by 9- (4- bromobenzenes) -9- carbazoles (322.6 milligrams, 1.0 mMs),
Four (trityl) phosphine palladiums (57 milligrams, 0.01 mM), cuprous iodide (19 milligrams, 0.1 mM) and acetylenylbenzene
(134.4 milligrams, 1.2 mMs) are dissolved in 15mL triethylamine, are flowed back 12 hours at 110 DEG C.Terminating reaction is cooled to room
Wen Hou, reactant mixture are added to the water and extracted with dichloromethane.Remaining organic layer anhydrous magnesium sulfate is dry and filters.Will
Solvent rotary evaporation is dried, and solid is purified by silica gel chromatographic column.9- (4- acetylenylbenzenes) -9- carbazoles are finally given, are micro- Huang
Color powder (297 milligrams), yield 65%.
Embodiment 2
Reaction condition one：Under nitrogen protective condition, by decaborane (121.3 milligrams, 1.0 mMs) and nitrogen, nitrogen-dimethyl
Aniline (181.4 milligrams, 1.5 mMs) is dissolved in 5mL drying and distilling toluene solvant, is stirred 30 minutes at 35 DEG C.Then
Compound 9- (4- acetylenylbenzenes) -9- carbazoles (345 milligrams, 1.0 mMs) of 10mL toluene distillations solvent dissolving are injected, will be anti-
Mixture is answered to be flowed back 10 hours under the conditions of 100 DEG C.After terminating reaction, mixture is cooled to room temperature and is quenched with methanol.Make
Solvent is removed with rotary evaporation, residue is added to the water, organic layer is extracted with dichloromethane, and mistake dry with anhydrous magnesium sulfate
Filter.Solvent is dried with rotary evaporation, solid silica gel chromatography.The compound I of yellow powder is obtained, is tied again with methanol
Crystalline substance obtains 107 milligrams of more pure compound I, yield 23%.
Reaction condition two：Under nitrogen protective condition, by decaborane (133.4 milligrams, 1.1 mMs) and nitrogen, nitrogen-dimethyl
Aniline (181.4 milligrams, 1.5 mMs) is dissolved in 5mL drying and distilling toluene solvant, is stirred 30 minutes at 40 DEG C.Then
Temperature is risen into 110 DEG C to be kept for 2 hours, after being cooled to 40 DEG C, compound 9- (the 4- second of injection 10mL toluene distillations solvent dissolving
Alkynyl benzene) -9- carbazoles (345 milligrams, 1.0 mMs), reactant mixture is flowed back 12 hours under the conditions of 110 DEG C.Terminate anti-
Ying Hou, mixture is cooled to room temperature and is quenched with methanol.Solvent is removed using rotary evaporation, residue is added to the water, had
Machine layer is extracted with dichloromethane, with anhydrous magnesium sulfate drying and is filtered.Solvent is dried with rotary evaporation, solid silica gel column chromatography
Purifying.The compound I of yellow powder is obtained, 358.8 milligrams of more pure compound I, yield are obtained with recrystallizing methanol
For 75%.
Reaction condition three：Under nitrogen protective condition, by decaborane (145.5 milligrams, 1.2 mMs) and nitrogen, nitrogen-dimethyl
Aniline (205.4 milligrams, 1.7 mMs) is dissolved in 5mL drying and distilling toluene solvant, is stirred 30 minutes at 45 DEG C.Then
Temperature is risen into 120 DEG C to be kept for 2 hours, after being cooled to 40 DEG C, compound 9- (the 4- second of injection 10mL toluene distillations solvent dissolving
Alkynyl benzene) -9- carbazoles (345 milligrams, 1.0 mMs), reactant mixture is flowed back 14 hours under the conditions of 120 DEG C.Terminate anti-
Ying Hou, mixture is cooled to room temperature and is quenched with methanol.Solvent is removed using rotary evaporation, residue is added to the water, had
Machine layer is extracted with dichloromethane, with anhydrous magnesium sulfate drying and is filtered.Solvent is dried with rotary evaporation, solid silica gel column chromatography
Purifying.The compound I of yellow powder is obtained, obtains 343 milligrams of more pure compound I with recrystallizing methanol, yield is
70%.
1H NMR(400MHz,CDCl3):δ 8.10 (d, J=7.6Hz, 2H), 7.64 (d, J=8.8Hz, 2H), 7.50 (d, J
=7.4Hz, 2H), 7.35 (ddd, J=25.7,10.1,4.1Hz, 7H), 7.22 (t, J=6.9Hz, 4H)；13C NMR
(101MHz,CDCl3)δ140.15,139.53,132.20,130.70,130.57,130.34,129.33,128.39,
126.27,126.08,123.66,120.46,120.43,109.47,85.39,84.35；11B NMR(128MHz,CDCl3)δ-
2.45,-10.52.
Embodiment 3
Reaction condition one：Under nitrogen protective condition, by decaborane (121.3 milligrams, 1.0 mMs) and nitrogen, nitrogen-dimethyl
Aniline (181.4 milligrams, 1.5 mMs) is dissolved in 5mL drying and distilling toluene solvant, is stirred 30 minutes at 35 DEG C.Then
Compound 9- (3- acetylenylbenzenes) -9- carbazoles (345 milligrams, 1.0 mMs) of 10mL toluene distillations solvent dissolving are injected, will be anti-
Mixture is answered to be flowed back 10 hours under the conditions of 100 DEG C.After terminating reaction, mixture is cooled to room temperature and is quenched with methanol.Make
Solvent is removed with rotary evaporation, residue is added to the water, organic layer is extracted with dichloromethane, and mistake dry with anhydrous magnesium sulfate
Filter.Solvent is dried with rotary evaporation, solid silica gel chromatography.The compound II of yellow powder is obtained, with methanol weight
Crystallization obtains 88.6 milligrams of more pure compound II, yield 19%.
Reaction condition two：Under nitrogen protective condition, by decaborane (133.4 milligrams, 1.1 mMs) and nitrogen, nitrogen-dimethyl
Aniline (181.4 milligrams, 1.5 mMs) is dissolved in 5mL drying and distilling toluene solvant, is stirred 30 minutes at 40 DEG C.Then
Temperature is risen into 110 DEG C to be kept for 2 hours, after being cooled to 40 DEG C, compound 9- (the 3- second of injection 10mL toluene distillations solvent dissolving
Alkynyl benzene) -9- carbazoles (345 milligrams, 1.0 mMs), reactant mixture is flowed back 12 hours under the conditions of 110 DEG C.Terminate anti-
Ying Hou, mixture is cooled to room temperature and is quenched with methanol.Solvent is removed using rotary evaporation, residue is added to the water, had
Machine layer is extracted with dichloromethane, with anhydrous magnesium sulfate drying and is filtered.Solvent is dried with rotary evaporation, solid silica gel column chromatography
Purifying.The compound II of yellow powder is obtained, 330.1 milligrams of more pure compound II are obtained with recrystallizing methanol, is produced
Rate is 69%.
Reaction condition three：Under nitrogen protective condition, by decaborane (145.5 milligrams, 1.2 mMs) and nitrogen, nitrogen-dimethyl
Aniline (205.4 milligrams, 1.7 mMs) is dissolved in 5mL drying and distilling toluene solvant, is stirred 30 minutes at 45 DEG C.Then
Temperature is risen into 110 DEG C to be kept for 2 hours, after being cooled to 40 DEG C, compound 9- (the 3- second of injection 10mL toluene distillations solvent dissolving
Alkynyl benzene) -9- carbazoles (345 milligrams, 1.0 mMs), reactant mixture is flowed back 14 hours under the conditions of 120 DEG C.Terminate anti-
Ying Hou, mixture is cooled to room temperature and is quenched with methanol.Solvent is removed using rotary evaporation, residue is added to the water, had
Machine layer is extracted with dichloromethane, with anhydrous magnesium sulfate drying and is filtered.Solvent is dried with rotary evaporation, solid silica gel column chromatography
Purifying.The compound II of yellow powder is obtained, 299.2 milligrams of more pure compound II are obtained with recrystallizing methanol, is produced
Rate is 61%.
1H NMR(400MHz,CDCl3):δ 8.10 (d, J=7.6Hz, 2H), 7.65-7.62 (m, 2H), 7.52-7.48 (m,
2H),7.40–7.28(m,7H),7.24–7.20(m,4H)；13C NMR(101MHz,CDCl3)δ140.49,137.77,
132.67,130.70,130.41,130.11,129.94,129.22,128.88,128.57,126.08,123.44,120.43,
120.32,109.27,85.18,84.10；11B NMR(128MHz,CDCl3)δ-2.39,-10.41.
Above is embodiments of the invention, it is necessary to explanation be the invention is not restricted to these examples, these examples only for
The present invention is better understood from, any equivalent transformation made according to technical scheme, belongs to the scope of the present invention.
Claims (10)
1. a kind of carborane derivative material based on carbazole, it is characterised in that the material is containing carbazole structure system, is passed through
Carborane skeleton links with different loci phenyl unit；Such material has following compound I or II formula structure：
Wherein：Compound I is that the 4- positions of the phenyl carbazole on nitrogen-atoms 9- positions in carbazole are connected with carborane；Compound II is
It is connected in the 3- positions of the phenyl ring of phenyl carbazole with carborane；C is carbon, and N is nitrogen.
2. the carborane derivative material based on carbazole according to claim 1, it is characterised in that the compound I and change
Compound II material contains a carbazole unit and a carborane unit.
A kind of 3. carborane derivative material based on carbazole according to claim 1, it is characterised in that the phenyl carbazole
3- positions or 4- positions and the carbon atom on carborane of upper phenyl ring are linked by carbon-carbon bond.
A kind of 4. preparation method of the carborane derivative material based on carbazole as claimed in claim 1, it is characterised in that institute
Compound I preparation methods are stated to comprise the following steps：
Step 1：The preparation of 9- (4- acetylenylbenzenes) -9- carbazoles：Under nitrogen protective condition, by 9- (4- bromobenzenes) -9- carbazoles, second
Alkynyl benzene, four (trityl) phosphine palladiums and adds cuprous iodide in dry reaction bulb, under nitrogen and lucifuge atmosphere, then
Triethylamine solution is injected into mixture, is flowed back 10~14 hours at 100 DEG C~120 DEG C, after terminating reaction is cooled to room temperature, instead
Mixture is answered to be added to the water and extracted with dichloromethane, remaining organic layer anhydrous magnesium sulfate is dry and filters；Solvent is revolved
Turn evaporation drying, solid is purified by silica gel chromatographic column, is finally given 9- (4- acetylenylbenzenes) -9- carbazoles, is micro-yellow powder；
Step 2：Compound I preparation：In nitrogen atmosphere, to reaction bulb in add dry toluene distillation to dissolve ten boron
Alkane and nitrogen, nitrogen-dimethylaniline, in 35 DEG C~45 DEG C stirrings, temperature is then risen into 100 DEG C~120 DEG C holdings, then cooled down
To after 35 DEG C~45 DEG C, compound 9- (4- acetylenylbenzenes) -9- carbazoles of injection toluene distillation solvent dissolving, reaction is mixed
Thing flows back 10~12 hours under the conditions of 100 DEG C~120 DEG C, after terminating reaction, mixture is cooled into room temperature and quenched with methanol
Go out, remove solvent using rotary evaporation, residue is added to the water, organic layer is extracted with dichloromethane, is done with anhydrous magnesium sulfate
Dry and filter, solvent is dried with rotary evaporation, solid silica gel chromatography, obtains the compound I of yellow powder.
5. the preparation method of the carborane derivative material according to claim 4 based on carbazole, it is characterised in that described
Acetylenylbenzene is 1 with 9- (4- bromobenzenes) -9- carbazoles mol ratio:1~1.2:1；Four (trityl) the phosphine palladium and 9- (4- bromines
Benzene) -9- carbazoles mol ratio be 0.05:1~0.1:1, the cuprous iodide is 0.1 with 9- (4- bromobenzenes) -9- carbazoles mol ratio:1
~0.2:1；Every mM of 9- (4- bromobenzenes) -9- carbazole adds 10~15mL of triethylamine solvent.
6. the preparation method of the carborane derivative material according to claim 4 based on carbazole, it is characterised in that described
In step 2, the decaborane is 1 with 9- (4- acetylenylbenzenes) -9- carbazoles mol ratio:1~1.1:1, nitrogen, nitrogen-dimethylaniline
It is 1.5 with 9- (4- acetylenylbenzenes) -9- carbazoles mol ratio:1~1.7:1, every mM of 9- (4- acetylenylbenzenes) -9- carbazole adds
10~15mL of toluene distillation solvent.
A kind of 7. preparation method of the carborane derivative material based on carbazole as claimed in claim 1, it is characterised in that institute
The preparation method for stating compound II comprises the following steps：
Step 1：The preparation of 9- (3- acetylenylbenzenes) -9- carbazoles：Under nitrogen protective condition, by 9- (3- bromobenzenes) -9- carbazoles, second
Alkynyl benzene, four (trityl) phosphine palladiums and adds cuprous iodide in dry reaction bulb, under nitrogen and lucifuge atmosphere, then
Triethylamine solution is injected into mixture, is flowed back 10~14 hours at 100 DEG C~120 DEG C, after terminating reaction is cooled to room temperature, instead
Mixture is answered to be added to the water and extracted with dichloromethane, remaining organic layer anhydrous magnesium sulfate is dry and filters；Solvent is revolved
Turn evaporation drying, solid is purified by silica gel chromatographic column, is finally given 9- (3- acetylenylbenzenes) -9- carbazoles, is micro-yellow powder；
Step 2：Compound II preparation：In nitrogen atmosphere, to reaction bulb in add dry toluene distillation to dissolve ten boron
Alkane and nitrogen, nitrogen-dimethylaniline, in 35 DEG C~45 DEG C stirrings, temperature is then risen into 100 DEG C~120 DEG C holdings, then cooled down
To after 35 DEG C~45 DEG C, compound 9- (3- acetylenylbenzenes) -9- carbazoles of injection toluene distillation solvent dissolving, reaction is mixed
Thing flows back 10~12 hours under the conditions of 100 DEG C~120 DEG C, after terminating reaction, mixture is cooled into room temperature and quenched with methanol
Go out, remove solvent using rotary evaporation, residue is added to the water, organic layer is extracted with dichloromethane, is done with anhydrous magnesium sulfate
Dry and filter, solvent is dried with rotary evaporation, solid silica gel chromatography, obtains the compound II of yellow powder.
8. the preparation method of the carborane derivative material according to claim 7 based on carbazole, it is characterised in that described
Acetylenylbenzene is 1 with 9- (3- bromobenzenes) -9- carbazoles mol ratio:1~1.2:1；Four (trityl) the phosphine palladium and 9- (3- bromines
Benzene) -9- carbazoles mol ratio be 0.05:1~0.1:1, the cuprous iodide is 0.1 with 9- (3- bromobenzenes) -9- carbazoles mol ratio:1
~0.2:1；Every mM of 9- (3- bromobenzenes) -9- carbazole adds 10~15mL of triethylamine solvent.
9. the preparation method of the carborane derivative material according to claim 7 based on carbazole, it is characterised in that described
In step 2, the decaborane is 1 with 9- (3- acetylenylbenzenes) -9- carbazoles mol ratio:1~1.1:1, nitrogen, nitrogen-dimethylaniline
It is 1.5 with 9- (3- acetylenylbenzenes) -9- carbazoles mol ratio:1~1.7:1, every mM of 9- (3- acetylenylbenzenes) -9- carbazole adds
10~15mL of toluene distillation solvent.
A kind of 10. application of the carborane derivative material based on carbazole as claimed in claim 1, it is characterised in that such
Compound is applied in terms of sensor, electroluminescent device, organic solar batteries or organic field effect tube, or as electricity
Cause off-color material, photochromic material, biological sensing material, hole mobile material, nonlinear optical material, anti-fake material or puppet
Package material is applied to organic photoelectric field.
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