CN102491936A - Conjugated compound with yellow-green fluorescence and preparation method and use thereof - Google Patents
Conjugated compound with yellow-green fluorescence and preparation method and use thereof Download PDFInfo
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Abstract
The invention discloses a conjugated compound with yellow-green fluorescence and a preparation method and use thereof. The general structural formula of the conjugated compound is shown by a formula I. The skeleton of the compound is a conjugated system consisting of five aromatic rings fixed by two methylenes, so the compound has a larger delocalized system; the fixation function of the methylenes provides the system with spiral chirality; and because the electron-donating and electron-withdrawing effects of methoxy and substituted aryl or heterocyclic ring and the electron-donating effect of imide make the excitation of ground state electrons easier and promote fluorescence emission, the compound has a longer excitation wavelength and a longer emission wavelength, for example if the Ar is phenyl, the excitation wavelength in methylbenzene is 420 nanometers and the emission wavelength in methylbenzene is 474 nanometers. The compound has a bright yellow-green color in solution. The method disclosed by the invention for preparing the conjugated compound has the characteristics of cheap raw material, simple synthesis, high product yield and easy derivatization; and the obtained compound is tested by an instrument to have correct structure and high stability and therefore has a good application prospect in field of photoelectric materials.
Description
Technical field
The present invention relates to a kind of conjugated compound and preparation method thereof and application with yellow-green fluorescence.
Background technology
Luminous organic material is because it has very high using value in photochemistry device, organic electroluminescence device (ELD) and solar cell field of photovoltaic materials such as (OPV); So the research of organic photoelectrical material is the focus of numerous scientist's researchs, and red-green-blue enjoys researchist's favor for a long time as the basis of fluorescent material research always.
At present in this field, representative mainly containing glow De perylene diimide analog derivative (P.Wang, H.L.Zhang; L.Zhang; Synthesis and characterization of perylene diimides new style red light-emitting material, Chemical Industry and Engineering Progress, 2008; 27,460-463); Coumarins verivate (the H.Tang of green light; X.R.Wang, Y.Li, Green organic light-emitting diodes with improved stability and efficiency utilizing a wide band gap material as the host; DISPLAYS; 2008,29,502-505); Pyrazoline derivative (the C.Hao of blue light-emitting; Xu.Xing, Y.H.Gang, Novel fluorine carzazole based conjugated containing pyrazoline and benzothiazole segments for blue light-emitting materials; Chin.Chem.Lett.; 2007,18,1496-1500) etc.
Conjugative effect ianthone such as perylene, helicene etc.) and push-pull effect (like tonka bean camphor, rhodamine etc.) in the design of fluorescent material is synthetic, be important consideration, be the new focus of studying at present so combine the conjugative effect and the molecule of intramolecularly push-and-pull electronic effect.Therefore the conjugated compound with photoluminescent property of synthesizing new has very high scientific research value and using value.
Summary of the invention
The object of the present invention is to provide a kind of conjugated compound and preparation method thereof with photoluminescent property.
Conjugated compound provided by the present invention, its general structure is suc as formula shown in the I:
In the said formula I general structure, Ar is selected from any one in phenyl, substituted phenyl and the heterocyclic radical; R is n-propyl or dodecyl; R ' is a methyl.
Said heterocyclic radical specifically can be the 3-thienyl.
Said substituted phenyl specifically can be following any one: 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-formyl radical phenyl and 4-chloro-phenyl-.
Prepare the method for conjugated compound shown in the formula I, comprise the steps:
1) with 7,7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1,1 '-naphthyl naphthalene and MALEIC ANHYDRIDE carry out back flow reaction in organic solvent, obtain the acid anhydrides adduct A shown in the formula II;
2) gained acid anhydrides adduct A is dissolved in the methylene dichloride, and reacts, obtain the oxidation adduct B shown in the formula III to the acetic acid soln of dropping liquid bromine wherein;
3) gained oxidation adduct B and Tri N-Propyl Amine or dodecyl amine are reacted in organic solvent, obtain the lactin C shown in the formula IV;
The definition cotype I of R among the formula IV;
4) under the condition of catalyzer triphenyl phosphorus palladium and alkali existence, the fragrant boric acid shown in said lactin C and the formula V is reacted in organic solvent, obtain the conjugated compound shown in the formula I;
Ar-B(OH)
2
(formula V)
The definition cotype I of Ar among the formula V.
Wherein, MALEIC ANHYDRIDE described in the step 1) and 7,7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1, the mol ratio of 1 '-naphthyl naphthalene is 1: 1-1.5: 1, specifically can be 1: 1; Said organic solvent specifically can be YLENE; In the said back flow reaction, the reaction times is 6-10 hour, specifically can be 8-10 hour, and temperature of reaction is 130-160 ℃, specifically can be 140-150 ℃.
Step 2) in, said adduct A and liquid bromine mol ratio are 1: 4-8 specifically can be 1: 5; The reaction times of said reaction is 8-12 hour, specifically can be 10-12 hour, and temperature of reaction is a room temperature, specifically can be 15-18 ℃; Said acetate and liquid bromine volume ratio 5: 1-10: 1, specifically can be 8: 1-9: 1.
In the step 3), said organic solvent is N (DMF) or toluene, preferred DMF; Said reaction needs is carried out under argon shield;
When said oxidation adduct B and Tri N-Propyl Amine reacted, the mol ratio of said oxidation adduct B and Tri N-Propyl Amine was 1: 5-1: 10, specifically can be 1: 8; The reaction times of said reaction is 12-24 hour, specifically can be 20-24 hour, and temperature of reaction is 30-70 ℃, specifically can be 40-60 ℃;
When said oxidation adduct B and dodecyl amine reacted, the mol ratio of said oxidation adduct B and dodecyl amine was 1: 1-1: 3, specifically can be 1: 1; The reaction times of said reaction is 12-24 hour, specifically can be 20-24 hour, and temperature of reaction is 90-110 ℃, specifically can be 95-100 ℃.
In the step 4), said alkali specifically can be salt of wormwood; Said organic solvent is selected from any one in following two kinds of mixed solutions: 1) toluene, ethanol and the water mixed solvent that mixes to obtain according to volume ratio 8-5: 4-3: 3-1,2) YLENE, ethanol mixes the mixed solvent that obtains with water according to volume ratio 8-5: 4-3: 3-1; Said reaction needs is carried out under argon shield;
The mol ratio of said triphenyl phosphorus palladium, lactin C and fragrant boric acid is 0.02-0.1: 1: 2-3 specifically can be 0.043: 1: 3; The reaction times of said reaction is 16-24 hour, specifically can be 20-24 hour, and temperature of reaction is 90-110 ℃, specifically can be 95-100 ℃; Said reaction needed argon shield.
A further object of the present invention provides the application of above-mentioned fluorescent conjugated compound in preparation luminous organic material or organic fluorescent dye.
Conjugated compound provided by the invention; Because the conjugated system that this compound is made up of 5 aromatic nucleus of two methylene radical fixed; Thereby have bigger delocalization system, and because the fixed action of methylene radical makes this system have spiral chirality, simultaneously because methoxyl group and substituted aromatic base or heterocyclic push-and-pull electronic effect and the imido electronic effect of drawing make that the ground state electronics is more easy excitated; Can promote fluorescent emission, thereby have long excitation wavelength and emission wavelength.With Ar=phenyl among the formula I is example, and its excitation wavelength in toluene is 420nm, and emission wavelength is 474nm.In solution, demonstrate bright-coloured yellow-green colour.The method of the above-mentioned conjugated compound of preparation provided by the invention, low in raw material cost, synthetic simple, the product productive rate is high, is prone to derivatize, and correct through instrument detecting gained compound structure, good stability has good application prospects in field of photovoltaic materials.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of embodiment 1 preparation gained conjugated compound.
Fig. 2 is the nuclear-magnetism carbon spectrum of embodiment 1 preparation gained conjugated compound.
Fig. 3 is the single crystal structure of embodiment 1 preparation gained conjugated compound.
Fig. 4 is the excitation spectrum of embodiment 1 preparation gained conjugated compound.
Fig. 5 is the emmission spectrum of embodiment 1 preparation gained conjugated compound.
Fig. 6 is the nucleus magnetic hydrogen spectrum of embodiment 2 preparation gained conjugated compounds.
Fig. 7 is the nuclear-magnetism carbon spectrum of embodiment 2 preparation gained conjugated compounds.
Fig. 8 is the excitation spectrum of embodiment 2 preparation gained conjugated compounds.
Fig. 9 is the emmission spectrum of embodiment 2 preparation gained conjugated compounds.
Figure 10 is the nucleus magnetic hydrogen spectrum of embodiment 3 preparation gained conjugated compounds.
Figure 11 is the nuclear-magnetism carbon spectrum of embodiment 3 preparation gained conjugated compounds.
Figure 12 is the single crystal structure of embodiment 3 preparation gained conjugated compounds.
Figure 13 is the excitation spectrum of embodiment 3 preparation gained conjugated compounds.
Figure 14 is the emmission spectrum of embodiment 3 preparation gained conjugated compounds.
Figure 15 is the nucleus magnetic hydrogen spectrum of embodiment 4 preparation gained conjugated compounds.
Figure 16 is the nuclear-magnetism carbon spectrum of embodiment 4 preparation gained conjugated compounds.
Figure 17 is the excitation spectrum of embodiment 4 preparation gained conjugated compounds.
Figure 18 is the emmission spectrum of embodiment 4 preparation gained conjugated compounds.
Figure 19 is the nucleus magnetic hydrogen spectrum of embodiment 5 preparation gained conjugated compounds.
Figure 20 is the nuclear-magnetism carbon spectrum of embodiment 5 preparation gained conjugated compounds.
Figure 21 is the excitation spectrum of embodiment 5 preparation gained conjugated compounds.
Figure 22 is the emmission spectrum of embodiment 5 preparation gained conjugated compounds.
Figure 23 is the nucleus magnetic hydrogen spectrum of embodiment 6 preparation gained conjugated compounds.
Figure 24 is the nuclear-magnetism carbon spectrum of embodiment 6 preparation gained conjugated compounds.
Figure 25 is the excitation spectrum of embodiment 6 preparation gained conjugated compounds.
Figure 26 is the emmission spectrum of embodiment 6 preparation gained conjugated compounds.
Figure 27 is the nucleus magnetic hydrogen spectrum of embodiment 7 preparation gained conjugated compounds.
Figure 28 is the nuclear-magnetism carbon spectrum of embodiment 7 preparation gained conjugated compounds.
Figure 29 is the excitation spectrum of embodiment 7 preparation gained conjugated compounds.
Figure 30 is the emmission spectrum of embodiment 7 preparation gained conjugated compounds.
Figure 31 is the nucleus magnetic hydrogen spectrum of embodiment 8 preparation gained conjugated compounds.
Figure 32 is the nuclear-magnetism carbon spectrum of embodiment 8 preparation gained conjugated compounds.
Figure 33 is the excitation spectrum of embodiment 8 preparation gained conjugated compounds.
Figure 34 is the emmission spectrum of embodiment 8 preparation gained conjugated compounds.
Figure 35 is the nucleus magnetic hydrogen spectrum of embodiment 9 preparation gained conjugated compounds.
Figure 36 is the nuclear-magnetism carbon spectrum of embodiment 9 preparation gained conjugated compounds.
Figure 37 is the excitation spectrum of embodiment 9 preparation gained conjugated compounds.
Figure 38 is the emmission spectrum of embodiment 9 preparation gained conjugated compounds.
Embodiment
The present invention will be described through specific embodiment below, but the present invention is not limited thereto.
Experimental technique described in the following embodiment like no specified otherwise, is ordinary method; Said reagent and material like no specified otherwise, all can obtain from commercial sources.
The formula I compound of embodiment 1, preparation Ar=phenyl, R=n-propyl, R '=methyl (is D
1)
Reaction formula is following:
1) in the 1000ml round-bottomed flask, adds 159g (0.5mol) 7,7 '-dimethoxy-3,4 successively; 3 ', 4 '-tetrahydrochysene-1,1 '-naphthyl naphthalene, 49g (0.5mol) MALEIC ANHYDRIDE and 500ml YLENE; 160 ℃ of reflux 10 hours, reaction system is removed YLENE with wet distillation, after the remaining solid drying; With 500ml diacetyl oxide recrystallization, filter and obtain 87.8g acid anhydrides adduct A, productive rate is 82%;
2) in the 250ml round-bottomed flask, add 8.3g (0.02mol) adduct A and 40ml methylene dichloride, get 3ml (0.058mol) liquid bromine and be dissolved in 50ml acetate, place tap funnel; Slowly splash in the flask under the room temperature; After 12 hours, filter a small amount of washed with dichloromethane; Obtain 9.1g oxidation adduct B, productive rate is 80%;
3) in the 250ml round-bottomed flask, add 5.7g (0.01mol) oxidation adduct B and 5.9g (0.1mol) Tri N-Propyl Amine, in 100ml DMF, be heated to 40 degree reactions after 24 hours, revolve dry reaction liquid, a small amount of washed with dichloromethane obtains the 4.26g product C
1, productive rate 70%;
4) get 61mg (0.1mmol) C
1And in two mouthfuls of bottles of 36.6mg (0.3mmol) phenylo boric acid adding 25ml, under argon shield, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation helicene of phenyl D through column chromatography
143.6mg, productive rate 72%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ7.52(d，J＝7.1Hz，4H)，7.41(t，J＝7.3Hz，4H)，7.36-7.26(m，4H)，6.87(s，2H)，4.17(d，J＝15.9Hz，2H)，3.67(dd，J＝8.4，5.9Hz，2H)，3.33(s，6H)，2.93-2.89(m，4H)，2.65-2.49(m，2H)，1.70-1.77(m，2H)，0.98(t，J＝7.4Hz，3H).
MALDI-TOF?MS：605(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
The formula I compound of embodiment 2, preparation Ar=p-methylphenyl, R=n-propyl, R '=methyl (is D
2)
Reaction formula is following:
1) preparation of C1 prepares according to the method among the embodiment 1;
2) get 61mg (0.1mmol) C
1And 40.8mg (0.3mmol) adds 5ml toluene and 3ml ethanol and 2ml 2mol/LNa with syringe in two mouthfuls of bottles of methylphenylboronic acid adding 25ml under argon shield
2CO
3K
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation helicene of p-methylphenyl D through column chromatography
247.5mg, productive rate 75%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ7.42(d，J＝8.0Hz，4H)，7.27(s，2H)，7.22(d，J＝7.9Hz，4H)，6.85(s，2H)，4.16(d，J＝15.9Hz，2H)，3.66(t，J＝7.1Hz，2H)，3.31(s，6H)，2.98-2.80(m，4H)，2.65-2.50(m，2H)，2.39(s，6H)，1.70-1.77(m，2H)，0.98(t，J＝7.4Hz，3H).
MALDI-TOF?MS：633(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
The formula I compound of embodiment 3, preparation Ar=p-methoxyphenyl, R=n-propyl, R '=methyl (is D
3)
Reaction formula is following:
1) preparation of C1 prepares according to the method among the embodiment 1;
2) get 61mg (0.1mmol) C
1And 45.6mg (0.3mmol) adds 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe in two mouthfuls of bottles of methoxyphenylboronic acid adding 25ml under argon shield
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation helicene of p-methoxyphenyl D through column chromatography
353.2mg, productive rate 80%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ7.47(d，J＝8.2Hz，4H)，6.95(d，J＝8.2Hz，4H)，6.85(s，2H)，4.16(d，J＝16.0Hz，2H)，3.85(s，6H)，3.73-3.59(m，2H)，3.32(s，6H)，2.86-2.91(m，4H)，2.69-2.45(m，2H)，1.79-1.68(m，2H)，0.98(t，J＝7.2Hz，3H).
MALDI-TOF?MS：665(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
The formula I compound of embodiment 4, preparation Ar=rubigan, R=n-propyl, R '=methyl (is D
4)
Reaction formula is following:
1) preparation of C1 prepares according to the method among the embodiment 1;
2) get 61mg (0.1mmol) C
1And 46.8mg (0.3mmol) adds 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe in two mouthfuls of bottles of chlorobenzene boric acid adding 25ml under argon shield
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation spiral shell of rubigan D through column chromatography
440.4mg, productive rate 60%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ7.46(d，J＝8.3Hz，4H)，7.37(d，J＝8.3Hz，4H)，7.26(s，2H)，6.84(s，2H)，4.16(d，J＝15.9Hz，2H)，3.66(td，J＝6.9，1.9Hz，2H)，3.35(s，6H)，2.98-2.81(m，4H)，2.63-2.49(m，2H)，1.69-1.77(m，2H)，0.98(t，J＝7.4Hz，3H).
MALDI-TOF?MS：674(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
The formula I compound of thienyl, R=n-propyl, R '=methyl (is D between embodiment 5, preparation Ar=
1)
Reaction formula is following:
1) preparation of C1 prepares according to the method among the embodiment 1;
2) get 61mg (0.1mmol) C
1And thienyl boric acid adds in two mouthfuls of bottles of 25ml between 38.4mg (0.3mmol), under argon shield, adds 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation helicene of thiophene D through column chromatography
545.7mg, productive rate 74%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ7.66(dd，J＝2.9，1.0Hz，2H)，7.50-7.42(m，4H)，7.35(dd，J＝5.0，3.0Hz，2H)，6.86(s，2H)，4.16(d，J＝15.9Hz，2H)，3.66(td，J＝6.9，1.9Hz，2H)，3.35(s，6H)，2.98-2.81(m，4H)，2.63-2.49(m，2H)，1.69-1.77(m，2H)，0.98(t，J＝7.4Hz，3H).
MALDI-TOF?MS：617(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
The formula I compound of embodiment 6, preparation Ar=phenyl, R=dodecyl, R '=methyl (is D
6)
Reaction formula is following:
1) preparation of B prepares according to the method among the embodiment 1;
2) in the 250ml round-bottomed flask, add 5.7g (0.01mol) oxidation adduct B and 18.5g (0.1mol) dodecyl, in 100ml DMF, be heated to 100 degree reactions after 24 hours, revolve dry reaction liquid, a small amount of washed with dichloromethane obtains the 6.26g product C
2, productive rate 85%;
3) get 74mg C
2(0.1mmol) and 36.6mg (0.3mmol) phenylo boric acid add in two mouthfuls of bottles of 25ml, under argon shield, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation helicene of phenyl D through column chromatography
658.5mg, productive rate 80%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ7.53(d，J＝7.5Hz，4H)，7.41(t，J＝7.3Hz，4H)，7.37-7.27(m，4H)，6.87(s，2H)，4.17(d，J＝15.7Hz，2H)，3.69(t，J＝6.8Hz，2H)，3.33(s，6H)，2.88-2.92(m，4H)，2.55-2.64(m，2H)，1.68-1.70(m，2H)，1.29-1.35(m，19H)，0.88(t，J＝5.6Hz，3H).
MALDI-TOF?MS：731(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
Embodiment 7, preparation Ar=(are D to the formula I compound of formyl radical phenyl, R=dodecyl, R '=methyl
7)
Reaction formula is following:
1) C
2Preparation prepare according to the method among the embodiment 6;
2) get 74mg C
2(0.1mmol) and 45mg (0.3mmol) formylphenylboronic acid is added in two mouthfuls of bottles of 25ml, under argon shield, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation helicene of formyl radical phenyl D through column chromatography
723.6mg, productive rate 43%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ10.05(s，2H)，7.92(d，J＝8.2Hz，4H)，7.71(d，J＝8.1Hz，4H)，7.34(s，2H)，6.88(s，2H)，4.19(d，J＝15.9Hz，2H)，3.69(t，J＝6.6Hz，2H)，3.35(s，6H)，3.02-2.83(m，4H)，2.66-2.45(m，2H)，1.77-1.64(m，2H)，1.26-1.34(m，18H)，0.88(t，J＝6.6Hz，3H).
MALDI-TOF?MS：787(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
The formula I compound of embodiment 8, preparation Ar=p-methoxyphenyl, R=dodecyl, R '=methyl (is D
8)
Reaction formula is following:
1) C
2Preparation prepare according to the method among the embodiment 6;
2) get 74mg C
2(0.1mmol) and 45.6mg (0.3mmol) methoxyphenylboronic acid is added in two mouthfuls of bottles of 25ml, under argon shield, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation helicene of p-methoxyphenyl D through column chromatography
865.7mg, productive rate 83%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ7.47(d，J＝8.7Hz，4H)，7.26(s，2H)，6.95(d，J＝8.7Hz，4H)，6.85(s，2H)，4.15(d，J＝15.8Hz，2H)，3.85(s，6H)，3.68(t，J＝6.4Hz，2H)，3.32(s，6H)，2.98-2.76(m，4H)，2.66-2.45(m，2H)，1.75-1.61(m，2H)，1.26-1.34(m，18H)，0.87(t，J＝6.6Hz，3H).
MALDI-TOF?MS：791(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
The formula I compound of embodiment 9, preparation Ar=rubigan, R=dodecyl, R '=methyl (is D
9)
Reaction formula is following:
1) C
2Preparation prepare according to the method among the embodiment 6;
2) get 74mg C
2(0.1mmol) and 46.8mg (0.3mmol) chlorobenzene boric acid is added in two mouthfuls of bottles of 25ml, under argon shield, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe
2CO
3The aqueous solution, ventilating adds catalyzer triphenylphosphine palladium 5mg (0.004mmol) after 5 minutes, refluxed 12 hours, gets organic layer, MgSO
4Drying is filtered, and revolves driedly, separates to obtain the substituted hydrogenation helicene of rubigan D through column chromatography
951.2mg, productive rate 64%.
The structure detection result of this compound is following:
1H?NMR(300MHz，CDCl
3)δ7.46(d，J＝8.3Hz，4H)，7.37(d，J＝8.3Hz，4H)，7.26(s，2H)，6.84(s，2H)，4.17(d，J＝16.1Hz，2H)，3.68(t，J＝6.2Hz，2H)，3.31(s，6H)，2.92-2.87(m，4H)，2.67-2.47(m，2H)，1.76-1.62(m，2H)，1.25-1.34(m，18H)，0.87(t，J＝5.9Hz，3H).
MALDI-TOF?MS：800(M
+)。
Can know that by above-mentioned detected result this compound structure is correct.
Determinand is done the mensuration that solvent carries out uv-visible absorption spectra and fluorescence spectrum with toluene, obtains table 1 data.
Table 1, embodiment 1-9 prepare the optical property tabulation of gained conjugated compound
The excitation wavelength and the emission wavelength of the conjugated compound of embodiment 1-9 preparation are all measured in toluene solvant in the table 1.This series compound also has fluorescence down solid-state, and fluorescence also exists when making organic film to this series compound, and this provides the foundation for the application of this quasi-molecule on luminescent material.
The conjugated compound of embodiment 1-9 preparation all demonstrates yellow-green colour in toluene solvant.
Claims (10)
1. general structure is suc as formula the conjugated compound shown in the I:
Among the said formula I, Ar is selected from any one in phenyl, substituted phenyl and the heterocyclic radical; R is n-propyl or dodecyl; R ' is a methyl.
2. conjugated compound according to claim 1 is characterized in that: said heterocyclic radical is the 3-thienyl;
Said substituted phenyl be following any one: 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-formyl radical phenyl and 4-chloro-phenyl-.
3. prepare the method for conjugated compound shown in the formula I, comprise the steps:
1) with 7,7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1,1 '-naphthyl naphthalene and MALEIC ANHYDRIDE carry out back flow reaction in organic solvent, obtain the compound shown in the formula II;
2) compound shown in the formula II is dissolved in the methylene dichloride, and reacts, obtain the compound shown in the formula III to the acetic acid soln of dropping liquid bromine wherein;
3) compound shown in the formula III and Tri N-Propyl Amine or dodecyl amine are reacted in organic solvent, obtain the compound shown in the formula IV;
The definition cotype I of R among the formula IV;
4) under the condition of catalyzer triphenyl phosphorus palladium and alkali existence, the fragrant boric acid shown in compound shown in the formula IV and the formula V is reacted in organic solvent, obtain the conjugated compound shown in the formula I;
Ar-B(OH)
2
(formula V)
The definition cotype I of Ar among the formula V.
4. method according to claim 3 is characterized in that: in the step 1), and said MALEIC ANHYDRIDE and 7,7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1, the mol ratio of 1 '-naphthyl naphthalene is 1: 1-1.5: 1, be specially 1: 1; Said organic solvent is a YLENE; In the said back flow reaction, the reaction times is 6-10 hour, is specially 8-10 hour, and temperature of reaction is 130-160 ℃, is specially 140-150 ℃.
5. according to claim 3 or 4 described methods, it is characterized in that: step 2) in, compound shown in the said formula II and liquid bromine mol ratio are 1: 4-8 was specially 1: 5; The reaction times of said reaction is 8-12 hour, is specially 10-12 hour, and temperature of reaction is a room temperature, is specially 15-18 ℃; Said acetate and liquid bromine volume ratio 5: 1-10: 1, be specially 8: 1-9: 1.
6. according to each described method among the claim 3-5, it is characterized in that: in the step 3), said organic solvent is N or toluene; Said reaction needs is carried out under argon shield.
7. according to each described method among the claim 3-6, it is characterized in that: in the step 3), compound shown in the said formula III and Tri N-Propyl Amine react, and the mol ratio of compound shown in the said formula III and Tri N-Propyl Amine is 1: 5-1: 10, be specially 1: 8; The reaction times of said reaction is 12-24 hour, is specially 20-24 hour, and temperature of reaction is 30-70 ℃, is specially 40-60 ℃.
8. according to each described method among the claim 3-6; It is characterized in that: in the step 3); Compound shown in the said formula III and dodecyl amine react, and the mol ratio of compound shown in the said formula III and dodecyl amine is 1: 1-1: 3, be specially 1: 1; The reaction times of said reaction is 12-24 hour, is specially 20-24 hour, and temperature of reaction is 90-110 ℃, is specially 95-100 ℃.
9. according to each described method among the claim 3-8, it is characterized in that: in the step 4), said alkali is salt of wormwood; Said organic solvent is selected from any one in following two kinds of mixed solutions: 1) toluene, ethanol and the water mixed solvent that mixes to obtain according to volume ratio 8-5: 4-3: 3-1,2) YLENE, ethanol mixes the mixed solvent that obtains with water according to volume ratio 8-5: 4-3: 3-1; Said reaction needs is carried out under argon shield;
The mol ratio of the fragrant boric acid shown in compound shown in said triphenyl phosphorus palladium, the formula IV and the formula V is 0.02-0.1: 1: 2-3 was specially 0.043: 1: 3; The reaction times of said reaction is 16-24 hour, is specially 20-24 hour, and temperature of reaction is 90-110 ℃, is specially 95-100 ℃.
10. claim 1 or 2 described conjugations are combined in the application in preparation luminous organic material or the organic fluorescent dye.
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| CN105504861A (en) * | 2015-12-24 | 2016-04-20 | 中国科学院化学研究所 | Organic dye molecules with yellow-green fluorescence and preparation method thereof |
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| CN103773060A (en) * | 2014-01-06 | 2014-05-07 | 中国科学院化学研究所 | Organic fluorochrome molecule and synthesis method and application thereof |
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| CN106008318A (en) * | 2016-05-19 | 2016-10-12 | 中国科学院化学研究所 | Chiral organic dye molecules having circularly polarized luminescence properties as well as preparation method and application of chiral organic dye molecules |
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| CN113801057A (en) * | 2021-08-13 | 2021-12-17 | 浙江大学 | chrysene radical aza [7] spiroalkene compound, preparation method and application |
| CN115894521A (en) * | 2022-10-17 | 2023-04-04 | 浙江大学杭州国际科创中心 | Fluorescent molecule based on cage-shaped oxacalixarene and preparation method and application thereof |
| CN115894521B (en) * | 2022-10-17 | 2024-07-02 | 浙江大学杭州国际科创中心 | Fluorescent molecule based on caged oxacalixarene, and preparation method and application thereof |
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