CN107522725A - A kind of diaryl neighbour carborane derivative and preparation method thereof, application - Google Patents
A kind of diaryl neighbour carborane derivative and preparation method thereof, application Download PDFInfo
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- CN107522725A CN107522725A CN201710769167.8A CN201710769167A CN107522725A CN 107522725 A CN107522725 A CN 107522725A CN 201710769167 A CN201710769167 A CN 201710769167A CN 107522725 A CN107522725 A CN 107522725A
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- diaryl
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- carborane derivative
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- carborane
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- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000003287 optical effect Effects 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002585 base Substances 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- YJKJAYFKPIUBAW-UHFFFAOYSA-N 9h-carbazol-1-amine Chemical compound N1C2=CC=CC=C2C2=C1C(N)=CC=C2 YJKJAYFKPIUBAW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- -1 diaryl alkynes Chemical class 0.000 claims abstract description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical group CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 230000005284 excitation Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3611—Organic materials containing Nitrogen
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3619—Organometallic compounds
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The present invention relates to a kind of diaryl neighbour carborane derivative and preparation method thereof, application, belong to nonlinear optical material technical field.Diaryl neighbour's carborane derivative of the present invention, there is the structure as shown in formula (Ι), wherein, R1、R2、R3Separately it is selected from H, F, I, CO2Et, aminocarbazole base, carbazyl phenyl, triaryl amino or halo triaryl amino.The preparation method of diaryl neighbour's carborane derivative comprises the following steps：Decaborane Lewis alkali complex compound, diaryl alkynes, catalyst are well mixed in a solvent, the 24h of heating response 4, reaction temperature is 80 DEG C 140 DEG C, adds quencher to be quenched, and removes solvent, produces.Diaryl neighbour's carborane derivative of the present invention has good nonlinear optics (NLO) property, has larger polarizability β value, maximum up to 341.44 × 10‑30Esu, it can be applied to nonlinear optical material.
Description
Technical field
The present invention relates to a kind of diaryl neighbour carborane derivative and preparation method thereof, application, belong to nonlinear optics material
Expect technical field.
Background technology
With the development of modern information technologies, nonlinear optics (NLO) is with it in low cost, high-performance photoelectric communication equipment
The application of aspect, it has also become one of research field the most active, seeking research has strong second nonlinear optic response
New compound is also the study hotspot in this field.Nonlinear optical material is widely used in laser frequency conversion, four ripples mix
Frequently, light beam steering, image amplification, optical information processing, optical storage, optical-fibre communications, underwater communication, laser countermeasure (s) and nuclear fusion etc. are ground
Study carefully field.Wherein, nonlinear optical organic (NLO) material is obtained due to that can carry out flexible structure design on a molecular scale
To larger NLO responses and other specific photoelectric properties, the extensive interest of people is caused in recent years.
The miscellaneous borine of carbon is a kind of polyhedron caged borane clusters, by one or more top on carbon atom substitution boron cage
Point atom is formed.Wherein carborane and its derivative have special molecular structure and unique physico-chemical property, in many fields
There is preferable application prospect.Wherein adjacent carborane has the structure (structural formula is as follows) of regular dodecahedron, has heat steady
Qualitative good, the features such as modifiability is good, application prospect is good.
Nonlinear optical effect results from the photoelectricity physical behavio(u)r under excitation state, and the NLO responses of organic molecule are originating from altogether
The delocalization characteristic of pi-electron in yoke electronic structure, increase conjugated electrons bridge can improve second-order NLO coefficient and respond, the bigger delocalization of conjugated system,
Pi-electron more easily excites, the easier generation of nonlinear optical effect, and the electronic donor group by changing aryl branch can make
Its nonlinear optical response strengthens.Diaryl neighbour's carborane analog derivative have three-dimensional armaticity, empty p tracks electron deficient,
A large amount of polarizable electronics of height delocalization, it is easy to unique property such as functionalization, chemistry and optical stability, and has in ultra-violet (UV) band
The transparency well, diaryl neighbour carborane derivative may have preferable nonlinear optical effect, to diaryl neighbour's carbon boron
The research of the non-linear optical property of alkane derivatives has great importance.
The content of the invention
It is an object of the invention to provide a kind of good diaryl neighbour's carborane derivative of non-linear optical property.
It is another object of the present invention to provide a kind of preparation method of above-mentioned diaryl neighbour carborane derivative and answer
With.
To achieve the above object, the technical scheme of diaryl neighbour's carborane derivative of the invention is：
A kind of diaryl neighbour carborane derivative, there is the structure as shown in formula (Ι)：
Wherein, R1、R2、R3Separately it is selected from H, F, I, CO2Et, aminocarbazole base, carbazyl phenyl, triaryl ammonia
Base or halo triaryl amino.
Diaryl neighbour's carborane derivative of the present invention has good non-linear optical property, has larger polarizability β
Value.
Preferably, R1Selected from H, F, I, CO2Et, aminocarbazole base, carbazyl phenyl, triaryl amino or halo triaryl
Amino, R2、R3It is H.Or R2Selected from H, F, I, CO2Et, aminocarbazole base, carbazyl phenyl, triaryl amino or the virtue of halo three
Base amino, R1、R3It is H.Or R3Selected from H, F, I, CO2Et, aminocarbazole base, carbazyl phenyl, triaryl amino or halo three
Arylamino, R1、R2It is H.
Preferably, above-mentioned aminocarbazole base is 9- (3,6- diaminourea) carbazyl.
Preferably, above-mentioned carbazyl phenyl is one kind in 4- (9- carbazyls) phenyl, 3- (9- carbazyls) phenyl.
Preferably, the triaryl amino is：
Preferably, halo triaryl amino is the halides of the substituent shown in formula II.
Preferably, the diaryl neighbour carborane derivative is selected from：
The technical scheme of the preparation method of diaryl neighbour's carborane derivative of the present invention is as follows：
The preparation method of above-mentioned diaryl neighbour's carborane derivative, comprises the following steps：
Decaborane Lewis alkali complex compound, diaryl alkynes, catalyst are well mixed in a solvent, at 80 DEG C~140 DEG C
4h~24h is reacted, adds quencher to be quenched, solvent is removed, produces.
After removing solvent, recrystallized with n-hexane.After being recrystallized with n-hexane, the pure of product can be further improved
Degree.
The catalyst is [BMIM] AuCl4。
The decaborane Lewis alkali complex compound is B10H12(CH3CN)2、B10H12(CH3CH2=CHCN)2、B10H12
(Et2S)2、B10H12(Ph3P)2、B10H12(Ph2PN3)2、B10H12(Ph2PH)2、B10H12(Ph2POH)2、B10H12(Ph2PCl)2、
B10H12(Bu3P)2In one kind.
The solvent is one kind in toluene, dimethylbenzene, n-butyl ether.Solvent can provide good reaction ring for reaction
Border, be advantageous to improve reaction efficiency.
The quencher is one kind in methanol, ethanol, isopropanol, n-butanol.
Diaryl alkynes, the mass ratio of catalyst are 1:0.01~0.05.Decaborane Lewis alkali complex compound, diaryl alkynes
The mol ratio of hydrocarbon is 1:1~3.Decaborane Lewis alkali complex compound, solvent, the mass ratio of quencher are 1:10~13:0.5~1.
Crude product is obtained after removing solvent, gained crude product is 1 with n-hexane mass ratio:3~5.
The technical scheme of the application of diaryl neighbour's carborane derivative of the present invention is as follows：
A kind of application of above-mentioned diaryl neighbour carborane derivative in terms of nonlinear optical material.
The beneficial effects of the invention are as follows：
Diaryl neighbour's carborane derivative of the present invention has good nonlinear optics (NLO) property, has larger pole
Rate β value, it is maximum up to 341.44 × 10-30Esu, it can be applied to nonlinear optical material.
Embodiment
Embodiments of the present invention are described further below.
It is as follows to prepare reaction principle for diaryl neighbour carborane derivative in example below：
R1、R2、R3Separately it is selected from H, F, I, CO2Et, aminocarbazole base, carbazyl phenyl, triaryl amino or halogen
For triaryl amino.
Embodiment 1
The diaryl neighbour carborane derivative of the present embodiment has the structure as shown in formula (1)：
Diaryl neighbour's carborane derivative preparation method of the present embodiment specifically comprises the following steps：
2.7g [BMIM] AuCl is added in the three-necked flask with condensation reflux unit at room temperature4It is molten with 1036mL
Agent toluene, is stirred, and 90g (0.3mol) B is added into mixed system10H12(Et2S)2With the 3 of 101.7g (0.3mol),
4-(EtCO2)2C6H3C ≡ CPhF (structural formula is as follows), then react 6h by mixture at 110 DEG C, then add 56.8mL's
Reaction is quenched in methanol, and rotation removes solvent, obtains crude product；Crude product is recrystallized with 349.5g n-hexanes as solvent, obtains chemical combination
Thing 116.6g.
Reaction principle is as follows：
By testing and calculating, the purity of gained compound (1) is 99.6%, yield 85%, MS:[M+1]:458；
Anal.Calcd for C20H27B10O4F:C 52.56, H 5.95；Found C 52.55, H 5.94.
Embodiment 2
The diaryl neighbour carborane derivative of the present embodiment has the structure as shown in formula (2)：
Diaryl neighbour's carborane derivative preparation method of the present embodiment specifically comprises the following steps：
5.4g [BMIM] AuCl is added in the three-necked flask with condensation reflux unit at room temperature4It is molten with 720mL
Agent toluene, is stirred, and 60g (0.2mol) B is added into mixed system10H12(Et2S)2With 67.8g (0.2mol) 3,4-
(EtCO2)2C6H3C ≡ CPhF (structural formula is as follows), then react 5.5h by mixture at 100 DEG C, then add 42mL first
Reaction is quenched in alcohol, and rotation removes solvent, obtains crude product；Crude product is recrystallized with 304g n-hexanes as solvent, obtains compound
76.0g。
Reaction principle is as follows：
By testing and calculating, the purity of gained compound (2) is 99.3%, yield 83%, MS:[M+1]:458；
Anal.Calcd for C20H27B10O4F:C 52.55, H 5.94；Found C 52.54, H 5.95.
Embodiment 3
The diaryl neighbour carborane derivative of the present embodiment has the structure as shown in formula (3)：
Diaryl neighbour's carborane derivative preparation method of the present embodiment specifically comprises the following steps：
8.1g [BMIM] AuCl is added in the three-necked flask with condensation reflux unit at room temperature4It is molten with 1036mL
Agent toluene, is stirred, and 90g (0.3mol) B is added into mixed system10H12(Et2S)2With 135.2g (0.3mol) 3,4-
(EtCO2)2C6H3C ≡ CPhI (structural formula is as follows), then react 8h by mixture at 105 DEG C, then add 72mL methanol
Reaction is quenched, rotation removes solvent, obtains crude product；Crude product is recrystallized with 563g n-hexanes as solvent, obtains compound
141.2g。
Reaction principle is as follows：
By testing and calculating, the purity of gained compound (3) is 99.5%, yield 83%, MS:[M+1]:566；
Anal.Calcd for C20H27B10O4I:C 42.51, H 4.81；Found C 42.50, H 4.82.
Diaryl neighbour carborane derivative and its performance in embodiment 4-15 is as shown in table 1, other reference implementation examples 1
In content.
Diaryl neighbour's carborane derivative in the embodiment 4-15 of table 1
Test example
The nonlinear optical property of compound synthesized by the various embodiments described above is characterized using second hyperpolarizabilitieof,
It is specific as follows：
Pass through the nonlinear optical property of Super-Rayleight scattering (HRS) technical research diaryl neighbour's carborane derivative.Due to
Quantitative calculating to hyperpolarizability needs the definite absworption peak wavelength value of compound, therefore successively by UV-vis and HRS to implementing
Compound in example is researched and analysed.
1) test apparatus：Shimadzu UV 101SP ultraviolet-visible spectrophotometers；Nd-YAG lasers
2) testing conditions：
In UV-vis tests：Solvent is dichloromethane, and temperature is 20 DEG C, and test sample concentration is 10-5M。
In HRS tests：Solvent is anhydrous tetrahydro furan, and fundamental laser wavelength 1064nm, pulse width 20ns are maximum
Pulse strength is 200mJ.
3) calculate and analyze
β is calculated with internal standard method based on " two-level model "HRSValue, formula are as follows：
βHRS=β0D0(λ), D0[(the 1- λ of (λ)=1/2 max/λ2)(1-4λ2 max/λ2)]
Wherein：λ is fundamental laser wavelength (1064nm), λmaxFor compound maximum absorption wavelength, β0For static second order super
Rate.
Test result see the table below：
The nonlinear optical property analysis result of compound and adjacent carborane in the embodiment 1-15 of table 2
From the data of table 2：The synthesized more adjacent carborane of compound ultraviolet maximum absorption wavelength significantly increases, in purple
There is the good transparency in Wai Guang areas, have larger second order susceptibility β value, maximum up to 341.44 × 10-30Esu, NLO are responded,
It is adapted to turn into nonlinear optical material.
Claims (10)
1. a kind of diaryl neighbour carborane derivative, it is characterised in that there is the structure as shown in formula (Ι)：
Wherein, R1、R2、R3Separately it is selected from H, F, I, CO2Et, aminocarbazole base, carbazyl phenyl, triaryl amino or halogen
For triaryl amino.
2. diaryl neighbour carborane derivative as claimed in claim 1, it is characterised in that the triaryl amino is：
3. diaryl neighbour carborane derivative as claimed in claim 1, it is characterised in that the diaryl neighbour carborane derives
Thing is selected from：
4. a kind of preparation method of diaryl neighbour's carborane derivative as claimed in claim 1, it is characterised in that including as follows
Step：
Decaborane Lewis alkali complex compound, diaryl alkynes, catalyst are well mixed in a solvent, in 80 DEG C~140 DEG C reactions
4h~24h, add quencher to be quenched, produce.
5. the preparation method of diaryl neighbour carborane derivative as claimed in claim 4, it is characterised in that after being quenched, remove
Solvent, recrystallized with n-hexane.
6. the preparation method of diaryl neighbour carborane derivative as claimed in claim 4, it is characterised in that the catalyst is
[BMIM]AuCl4。
7. the preparation method of diaryl neighbour carborane derivative as claimed in claim 4, it is characterised in that the decaborane
Lewis alkali complex compound is B10H12(CH3CN)2、B10H12(CH3CH2=CHCN)2、B10H12(Et2S)2、B10H12(Ph3P)2、B10H12
(Ph2PN3)2、B10H12(Ph2PH)2、B10H12(Ph2POH)2、B10H12(Ph2PCl)2、B10H12(Bu3P)2In one kind.
8. the preparation method of diaryl neighbour carborane derivative as claimed in claim 4, it is characterised in that diaryl alkynes,
The mass ratio of catalyst is 1:0.01~0.05.
9. the preparation method of diaryl neighbour carborane derivative as claimed in claim 4, it is characterised in that decaborane Lewis
Alkali complex compound, the mol ratio of diaryl alkynes are 1:1~3.
A kind of 10. application of the diaryl neighbour's carborane derivative in terms of nonlinear optical material as claimed in claim 1.
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Cited By (1)
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| CN113135950A (en) * | 2020-01-19 | 2021-07-20 | 中国科学院宁波材料技术与工程研究所 | Diamine monomer and dianhydride monomer containing carborane structure as well as preparation methods and applications of diamine monomer and dianhydride monomer |
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|---|---|---|---|---|
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| CN103509043A (en) * | 2012-12-04 | 2014-01-15 | Tcl集团股份有限公司 | Dicarborane derivatives, preparation method and application thereof, and electroluminescent device |
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| CN113135950A (en) * | 2020-01-19 | 2021-07-20 | 中国科学院宁波材料技术与工程研究所 | Diamine monomer and dianhydride monomer containing carborane structure as well as preparation methods and applications of diamine monomer and dianhydride monomer |
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| CN107522725B (en) | 2019-09-27 |
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