CN109593049A - A kind of dinaphthalene phenols solid fluorescent material - Google Patents
A kind of dinaphthalene phenols solid fluorescent material Download PDFInfo
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- CN109593049A CN109593049A CN201811549686.4A CN201811549686A CN109593049A CN 109593049 A CN109593049 A CN 109593049A CN 201811549686 A CN201811549686 A CN 201811549686A CN 109593049 A CN109593049 A CN 109593049A
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- bis
- fluorescent material
- fluorescent
- dinaphthalene
- solid
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- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000007787 solid Substances 0.000 title claims abstract description 19
- 150000002989 phenols Chemical class 0.000 title claims abstract description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000000976 ink Substances 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 44
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000005284 excitation Effects 0.000 description 9
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 238000010189 synthetic method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- -1 methoxymethoxy Chemical group 0.000 description 6
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- OBXSGRKNCOCTTM-UHFFFAOYSA-N benzyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCC1=CC=CC=C1 OBXSGRKNCOCTTM-UHFFFAOYSA-N 0.000 description 3
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 3
- 230000003760 hair shine Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000006505 p-cyanobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C#N)C([H])([H])* 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008359 benzonitriles Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
- C07C255/43—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms the carbon skeleton being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of dinaphthalene phenols solid fluorescent materials and preparation method thereof, belong to field of functional materials.Heretofore described dinaphthalene phenolic compound has simple molecular structure, and the regulation of its fluorescence emission wavelengths can be realized by function dough, and launch wavelength range can cover the visible-range from blue light to feux rouges, has potential application in photoelectric field.Such fluorescent material has solvatochromism.With the increase of solvent polarity, the emission peak of such fluorescent molecule can gradually red shift.In addition, such material also has changing color resulting from acid property, there is potential application in fields such as secrecy inks.
Description
[technical field]
The present invention relates to fluorescent material technical fields, more particularly to a kind of dinaphthalene phenols solid fluorescent material.
[background technique]
Luminous organic material has in Organic Light Emitting Diode (OLED), the fields such as organic light emitting display and photoelectric device
Wide application value.Traditional luminous organic material has stronger fluorescence in the solution, but shines in the solid state
Weaken and do not shine even, reason is aggregation inducing fluorescent quenching caused by intermolecular π-π interaction.In modern technologies
In, fluorescent material generally requires to exist with state of aggregation, and fluorescent quenching problem caused by assembling is with regard to inevitable.Which has limited
Application of the conventional fluorescent material in practical field.In 2001, Tang Benzhong seminar developed a series of with aggregation inducing
The fluorescent molecule of the characteristics of luminescence.The fluorescence of this kind of molecule in the solution is very weak, but the strong light under coherent condition or solid-state
It spends very high.This special luminosity causes the extensive research interest of people.When developing fluorescent organic solid material, in addition to
Consider outside the fluorescence quantum yield under solid-state, it is also contemplated that launch wavelength whether can it is easy regulate and control, this is also and actually answers
With closely related major issue.But since most of fluorescent organic solid material skeleton structures are complicated, its fluorescence hair is adjusted
Optical wavelength often has very big difficulty, and the adjustable fluorescent organic solid material that shines for capableing of covering visible light range still compares
It is few.Since the application fields such as photoelectric material have a large amount of demand for organic solid luminescent material, design synthesizing new tool
There is the adjustable organic solid luminescent material that shines of simple molecules skeleton to have a very important significance.
[summary of the invention]
Technical problem to be solved by the present invention lies in provide a kind of dinaphthalene phenols solid fluorescent material.
The present invention is achieved through the following technical solutions:
A kind of dinaphthalene phenols solid fluorescent material, molecular structural formula are shown in formula I:
R in formula1For hydrogen, aryl or cyano；R2For hydrogen, aryl or cyano；R3For alkyl or alkoxyalkyl；R4For alkyl
Or aryl.
Preferably, R in the structural formula1For at least one of hydrogen, phenyl, 4- cyano-phenyl, cyano.
Preferably, R in the structural formula2For at least one of hydrogen, phenyl, 4- cyano-phenyl, cyano.
Preferably, R in the structural formula3For at least one of methyl, methoxy.
Preferably, R in the structural formula4For methyl.
Above-mentioned dinaphthalene phenols solid fluorescent material to prepare reaction equation as follows:
Specifically includes the following steps:
(1) by 7,7 '-two amido dinaphthols -3,3 '-dialdehyde of methyl protection and methyltriphenylphosphonium bromide in alkaline item
Under part, compound DB-1 is obtained after reacting 1-24 hours at -20-80 DEG C；
(2) by methoxy protection 7,7 '-two amido dinaphthols -3,3 '-dialdehyde and benzyl diethyl phosphate or
4- cyanobenzyls diethyl phosphate under alkaline condition, obtained after being reacted 1-48 hours at -20-80 DEG C compound DB-2 or
DB-3；
(3) 7,7 '-two amido dinaphthols -3,3 '-dialdehyde that methoxy is protected is existed with benzene acetonitrile or malononitrile
Under alkaline condition, compound DB-4 or DB-5 are obtained after reacting 1-48 hours at -20-80 DEG C；
The launch wavelength of solid fluorescent material provided by the invention can cover the visible-range from blue light to feux rouges；With molten
Agent polarity increases, and the fluorescence emission wavelengths of fluorescent dye are mobile to long wave direction, has solvatochromism；Compound DB-4 and
DB-5 has aggregation-induced emission performance；Such fluorescent material also has changing color resulting from acid property, can be applied to the neck such as secrecy ink
Domain.
[Detailed description of the invention]
Fig. 1 is the fluorescence emission spectrum of DB-1, DB-2, DB-3, DB-4 and DB-5 in the solid state.
Fig. 2A is fluorescence emission spectrum of the DB-1 in toluene, methylene chloride, tetrahydrofuran, acetonitrile, DMSO.Excitation wavelength
For 370nm.
Fig. 2 B is fluorescence emission spectrum of the DB-2 in toluene, methylene chloride, tetrahydrofuran, acetonitrile, DMSO.Excitation wavelength
For 350nm.
Fig. 2 C is fluorescence emission spectrum of the DB-3 in toluene, methylene chloride, tetrahydrofuran, acetonitrile, DMSO.Excitation wavelength
For 410nm.
Fig. 2 D is fluorescence emission spectrum of the DB-4 in toluene, methylene chloride, tetrahydrofuran, acetonitrile, DMSO.Excitation wavelength
For 410nm.
Fig. 2 E is fluorescence emission spectrum of the DB-5 in toluene, methylene chloride, tetrahydrofuran, acetonitrile, DMSO.Excitation wavelength
For 480nm.
Fig. 3 A is DB-4 in the MeCN/H in different water contents (vol%)2Fluorescence emission spectrum in O solvent.Concentration is
10 μM, excitation wavelength 410nm.
Fig. 3 B is the I/I of DB-40With the correlogram in system between water content, I0For DB-4 in pure acetonitrile most
Big fluorescent emission intensity, concentration are 10 μM, excitation wavelength 410nm.
Fig. 3 C is DB-5 in the MeCN/H in different water contents (vol%)2Fluorescence emission spectrum in O solvent.Concentration is
10 μM, excitation wavelength 480nm.
Fig. 3 D is the I/I of DB-50With the correlogram in system between water content, I0For DB-5 in pure acetonitrile most
Big fluorescent emission intensity, concentration are 10 μM, excitation wavelength 480nm.
Fig. 4 A is that the uv absorption spectra after trifluoroacetic acid is added in the dichloromethane solution of DB-5.
Fig. 4 B is that the fluorescence emission spectrogram of compound after trifluoroacetic acid is added in the dichloromethane solution of DB-5, and concentration is 10 μM, is swashed
Hair wavelength is 460nm.
[specific embodiment]
The present invention is further explained in the light of specific embodiments, but the present invention is not limited to following embodiments.
Embodiment 1: synthesis compound DB-1
Structural formula:
Chinese: 2,2'- dimethoxy-N7,N7,N7',N7'Tetramethyl -3,3'- divinyl-[1,1'- union II
Naphthalene] -7,7'- diamines
English name: 2,2'-dimethoxy-N7,N7,N7',N7'-tetramethyl-3,3'-divinyl-[1,1'-
binaphthal ene]-7,7'-diamine
Synthetic method: under nitrogen atmosphere, methyltriphenylphosphonium bromide (648mg, 1.8mmol) is dissolved in the anhydrous tetrahydro of 20mL
In furans and it is cooled to 0 DEG C.The hexane solution (1mL, 1.6mmol) of 2.5M n-BuLi is added dropwise into above-mentioned solution.
After stirring 30 minutes at 0 DEG C, bis- (dimethylamino) -2,2'- dimethoxys-of 7,7'- [1,1'- binaphthalene] -3,3'- bis- is added
Aldehyde (227mg, 0.5mmol).Ice bath is removed, reaction solution is stirred at room temperature 6 hours.After reaction, saturation chlorination is added
Ammonium salt solution, organic phase are extracted with ethyl acetate twice.Organic phase after merging is washed with saturated sodium chloride solution, then with anhydrous
Sodium sulphate is dry.Organic solvent is removed in rotation, and gained crude product crosses silica gel column chromatography, is eluted with petrol ether/ethyl acetate (V/V=10:1)
Obtain yellow solid product 153mg, yield 67%.1H NMR(500MHz,CDCl3) δ 7.97 (s, 2H), 7.72 (d, J=
9.1Hz, 2H), 7.17 (dd, J=17.7,11.0Hz, 2H), 7.04 (dd, J=9.0,1.8Hz, 2H), 6.23 (d, J=
1.0Hz, 2H), 5.91 (dt, J=11.7,5.8Hz, 2H), 5.45-5.09 (m, 2H), 3.37 (s, 6H), 2.71 (s, 12H)13C
NMR(126MHz,DMSO)δ154.64,148.66,135.31,132.66,129.56,126.32,126.05,123.88,
123.58,115.58,114.32,103.84,60.95,40.23.HRMS(ESI)calcd.for C30H33O2N2 +:
453.25365,found:453.25345.
Embodiment 2: synthesis compound DB-2
Structural formula:
Chinese: bis- (the methoxymethoxy)-N of 2,2'-7,N7,N7',N7'((the E)-styrene of tetramethyl -3,3'- two
Base)-[1,1'- binaphthalene] -7,7'- diamines
English name: 2,2'-bis (methoxymethoxy)-N7,N7,N7',N7'-tetramethyl-3,3'-di
((E)-sty ryl)-[1,1'-binaphthalene]-7,7'-diamine
Synthetic method: benzyl diethyl phosphate (501mg, 2.2mmol) is dissolved in 20mL anhydrous tetrahydro furan and is cooled down
To 0 DEG C.NaH (100mg, 60%, 2.5mmol) is added into above-mentioned solution.After stirring 1 hour at 0 DEG C, it is bis- that 7,7'- is added
(dimethylamino) -2,2'- bis- (methoxymethoxies)-[1,1'- binaphthalene] -3,3'- dialdehyde (516mg, 1mmol).Remove ice
Bath, reaction solution are stirred at room temperature 12 hours.After reaction, ice water is added, organic phase is extracted with ethyl acetate twice.It closes
Organic phase after and is washed with saturated sodium chloride solution, then dry with anhydrous sodium sulfate.Organic solvent, gained crude product mistake are gone in rotation
Silica gel column chromatography affords yellow solid product 290mg, yield 45% with petrol ether/ethyl acetate (V/V=12:1).1H
NMR(500MHz,CDCl3) δ 8.11 (s, 2H), 7.74 (dd, J=23.0,12.7Hz, 4H), 7.57 (d, J=7.5Hz, 4H),
7.36 (t, J=7.4Hz, 4H), 7.25 (d, J=16.0Hz, 4H), 7.08 (d, J=7.6Hz, 2H), 6.33 (s, 2H), 4.70
(d, J=5.7Hz, 2H), 4.54 (d, J=5.5Hz, 2H), 2.89 (s, 6H), 2.74 (s, 12H)13C NMR(126MHz,
DMSO)δ151.59,148.30,137.62,134.54,129.16,128.80,127.94,127.33,126.18,126.05,
125.28,123.97,123.61,123.37,115.38,103.63,99.50,98.34,56.20,39.76.HRMS(ESI)
calcd.for C44H45O4N2 +:665.33738,found:665.33624.
Embodiment 3: synthesis compound DB-3
Structural formula:
Chinese: 4,4'- ((1E, 1'E)-(bis- (the dimethylamino) -2,2'- of 7,7'- bis- (methoxymethoxies)-[1,
1'- binaphthalene] -3,3'- diyl) bis- (ethylene -2,1- diyls)) two benzonitriles
English name: 4,4'- ((1E, 1'E)-(7,7'-bis (dimethylamino) -2,2'-bis
(methoxymethoxy)-[1,1'-binaphthalene]-3,3'-diyl)bis(ethene-2,1-diyl))
dibenzonitrile
Synthetic method: it is similar with the synthetic method of DB-2, the difference is that using 4- cyanobenzyls diethyl phosphate generation
For benzyl diethyl phosphate.The substance being added when reaction is 4- cyanobenzyls diethyl phosphate (556mg, 2.2mmol), NaH
Bis- (the dimethylamino) -2,2'- of (100mg, 60%, 2.5mmol) and 7,7'- bis- (methoxymethoxies)-[1,1'- binaphthalene] -
3,3'- dialdehyde (516mg, 1mmol) obtain brown product 377mg, yield 49%.1H NMR(500MHz,CDCl3)δ8.12(s,
2H), 7.80 (dd, J=31.6,12.8Hz, 2H), 7.62 (s, 8H), 7.27 (d, J=7.1Hz, 2H), 7.09 (d, J=
9.1Hz, 2H), 6.28 (s, 2H), 4.66 (d, J=5.7Hz, 2H), 4.51 (d, J=5.7Hz, 2H), 2.94 (s, 6H), 2.75
(s,12H).13C NMR(126MHz,DMSO)δ151.77,148.57,142.41,134.99,132.69,129.40,127.89,
126.81,126.22,126.14,125.33,123.44,123.31,119.07,115.44,109.06,103.43,98.50,
56.24.HRMS(ESI)calcd.for C46H43O4N4 +:715.32788,found:715.32666.
Embodiment 4: synthesis compound DB-4
Structural formula:
Chinese: (2Z, 2'Z) -3,3'- (bis- (the dimethylamino) -2,2'- of 7,7'- bis- (methoxymethoxies)-[1,
1'- binaphthalene] -3,3'- diyl) bis- (2- phenyl acrylonitriles)
English name: (2Z, 2'Z) -3,3'- (7,7'-bis (dimethylamino) -2,2'-bis
(methoxymethoxy)-[1,1'-binaphthalene]-3,3'-diyl)bis(2-phenylacrylonitrile)
Synthetic method: by bis- (the dimethylamino) -2,2'- of 7,7'- bis- (methoxymethoxies)-[1,1'- binaphthalene] -3,
3'- dialdehyde (258mg, 0.5mmol) and benzene acetonitrile (146mg 1.25mmol) are dissolved in 20mL dehydrated alcohol, and piperidines is added
(25mg, 0.29mmol).Reaction solution is heated to flowing back, is stirred 18 hours.After reaction, reaction solution is cooled to room
Wen Houyou Precipitation, filtering, precipitated silica gel column chromatography for gained, was eluted with petroleum ether/methylene chloride (V/V=4:1)
To orange solid product 296mg, yield 83%.1H NMR(500MHz,CDCl3)δ8.80(s,1H),8.23(s,1H),7.87
(d, J=9.8Hz, 2H), 7.75 (d, J=7.4Hz, 2H), 7.54-7.40 (m, 5H), 7.39-7.24 (m, 5H), 7.10 (d, J
=8.8Hz, 2H), 6.27 (d, J=32.5Hz, 2H), 4.66 (d, J=26.3Hz, 4H), 2.98 (s, 6H), 2.81 (s, 12H)
.13C NMR(126MHz,DMSO)δ152.12,149.43,139.17,136.02,134.15,130.15,129.30,129.06,
129.01,128.71,128.51,125.52,122.86,122.81,122.57,118.22,115.57,109.68,102.91,
98.91,56.35.HRMS(ESI)calcd.for C46H43O4N4 +:715.32788,found:715.32660.
Embodiment 5: synthesis compound DB-5
Structural formula:
Chinese: 2,2'- ((bis- (methoxymethoxy)-[the 1,1'- union IIs of bis- (the dimethylamino) -2,2'- of 7,7'-
Naphthalene] -3,3'- diyl) bis- (methylene)) two malononitrile
English name: 2,2'- ((7,7'-bis (dimethylamino) -2,2'-bis (methoxymethoxy)-[1,
1'-bina phthalene]-3,3'-diyl)bis(methanylylidene))dimalononitrile
Synthetic method: it is similar with the synthetic method of DB-4, the difference is that replacing benzene acetonitrile using malononitrile.When reaction
The substance of addition is bis- (the dimethylamino) -2,2'- of 7,7'- bis- (methoxymethoxies)-[1,1'- binaphthalene] -3,3'- dialdehyde
(258mg, 0.5mmol), malononitrile (72.6mg 1.1mmol) and piperidines (25mg, 0.29mmol), obtain red product
270mg, yield 90%.1H NMR(500MHz,CDCl3) δ 8.88 (s, 2H), 8.36 (s, 2H), 7.85 (d, J=9.2Hz, 2H),
7.09 (dd, J=9.2,1.9Hz, 2H), 6.08 (s, 2H), 4.51 (q, J=6.3Hz, 4H), 3.19 (s, 6H), 2.86 (s,
12H).13C NMR(126MHz,DMSO)δ156.16,152.35,150.83,138.13,131.63,130.74,122.14,
122.05,119.96,116.04,115.11,114.18,102.29,99.54,77.35,56.53,39.47.HRMS(ESI)
calcd.for C36H33O4N6 +:613.25578,found:613.25488.
Embodiment 6: molten mutagens color is carried out to DB-1, DB-2, DB-3, DB-4 and the DB-5 of embodiment 1-5 preparation, aggregation lures
Lead the research of the optical properties such as luminous and changing color resulting from acid.
The fluorescence emission wavelengths of compound DB-1, DB-2, DB-3, DB-4 and DB-5 in the solid state be respectively 464nm,
515nm, 538nm, 567nm and 618nm, launch wavelength range cover the visible-range from blue light to feux rouges, as shown in Figure 1.
Solid state fluorescence quantum yield according to integrating sphere technology, DB-1, DB-2, DB-3, DB-4 and DB-5 luminescent material is respectively
16.3%, 4.4%, 2.2%, 3.3% and 4.2%.Such luminescent material is dissolved in ordinary organic solvents, including toluene, dichloromethane
Alkane, THF, acetonitrile and DMSO, it is not soluble in water.
As shown in Fig. 2A, 2B, 2C, 2D and 2E, compound DB-1, DB-2, DB-3, DB-4 and DB-5 have apparent molten cause
Change colour property.In low polar solvent such as toluene, fluorescence emission wavelengths are shorter；With the increase of solvent polarity, fluorescent emission
Wavelength gradually red shift.In big polar solvent such as DMSO, fluorescence emission wavelengths reach maximum.
Compound DB-4 and DB-5 have aggregation-induced emission property.As shown in figs.3 a and 3b, in pure acetonitrile solution, change
The emission wavelength for closing object DB-4 is 551nm, when the water content of acetonitrile/water mixed solvent is more than 60%, with water content after
Continuous to increase, luminous intensity starts rapid increase.When water content reaches 90%, luminous intensity reaches maximum value, is that pure acetonitrile is molten
11 times in liquid.As illustrated in figures 3 c and 3d, emission wavelength of the compound DB-5 in pure acetonitrile solution is 578nm, works as acetonitrile/water
When the water content of mixed solvent is more than 70%, continue to increase with water content, luminous intensity starts to be gradually increasing.Work as water content
When reaching 90%, luminous intensity reaches maximum value, is 4 times in pure acetonitrile solution.
Compound DB-1, DB-2, DB-3, DB-4 and DB-5 have changing color resulting from acid property.To the dichloro of such fluorescent molecule
After being gradually added into trifluoroacetic acid in dichloromethane, different degrees of blue shift also occurs for maximum absorption band, at maximum emission wavelength
Fluorescence intensity be also gradually reduced.As illustrated in figures 4 a and 4b, trifluoro is gradually added into the dichloromethane solution of compound DB-5
Acetic acid is detected by ultra-violet absorption spectrum and finds that its absorbance at 475nm gradually decreases, and at 280nm and 375nm
There are two new absorption peaks.With the increase of trifluoroacetic acid concentration, fluorescence intensity of the compound DB-5 at 575nm wavelength is gradually
Reduce.The dichloromethane solution priming color of compound DB-5 be it is orange, be added trifluoroacetic acid after, orange gradually to take off, solution
It becomes colorless.This fluorescent molecule can be applied to the fields such as secrecy ink.
The above description is only a preferred embodiment of the present invention, for the purpose of the present invention, is merely illustrative, and not restrictive
's；The understanding of those of ordinary skill in the art requires to carry out many in limited range to it and change in the invention patent
Change, modification or even equivalent change, but fall within protection scope of the present invention.
Claims (5)
1. a kind of dinaphthalene phenols solid fluorescent material, it is characterised in that the structural formula of the fluorescent material is as follows:
In Formulas I, R1For hydrogen, aryl or cyano；R2For hydrogen, aryl or cyano；R3For alkyl or alkoxyalkyl；R4For alkyl or virtue
Base.
2. dinaphthalene phenols solid fluorescent material according to claim 1, it is characterised in that: R in the structural formula1For hydrogen,
Phenyl, 4- cyano-phenyl, any one in cyano.
3. dinaphthalene phenols solid fluorescent material according to claim 1, it is characterised in that: R in the structural formula2For hydrogen,
Phenyl, 4- cyano-phenyl, any one in cyano.
4. dinaphthalene phenols solid fluorescent material according to claim 1, it is characterised in that: R in the structural formula3For first
Any one in base, methoxy.
5. dinaphthalene phenols solid fluorescent material according to claim 1, it is characterised in that: R in the structural formula4For first
Any one in base, phenyl.
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Cited By (2)
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| CN114957179A (en) * | 2022-06-22 | 2022-08-30 | 四川大学 | Compound for distinguishing organic liquids with similar structures and preparation method and application thereof |
| CN116478067A (en) * | 2023-04-23 | 2023-07-25 | 曲阜师范大学 | Cyano-olefin solid luminescent material based on chiral binaphthyl skeleton, and preparation method and application thereof |
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| CN116478067A (en) * | 2023-04-23 | 2023-07-25 | 曲阜师范大学 | Cyano-olefin solid luminescent material based on chiral binaphthyl skeleton, and preparation method and application thereof |
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