CN102491936B - 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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- 0 C*c1c[s]cc1 Chemical compound C*c1c[s]cc1 0.000 description 8
- HEVRPTFPKKCNTM-UHFFFAOYSA-N CCCN(C(c(c1c2CCc3c4)c(CCc5cc(Br)c(C)cc5-5)c-5c2-c3cc(OC)c4Br)=O)C1=O Chemical compound CCCN(C(c(c1c2CCc3c4)c(CCc5cc(Br)c(C)cc5-5)c-5c2-c3cc(OC)c4Br)=O)C1=O HEVRPTFPKKCNTM-UHFFFAOYSA-N 0.000 description 1
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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 with yellow-green fluorescence and preparation method thereof and application.
Background technology
Luminous organic material is because it has very high using value in field of photovoltaic materials such as photochemistry device, organic electroluminescence device (ELD) and solar cells (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, the representative De perylene diimide analog derivative (P.Wang that glows that mainly contains, 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); Coumarin derivatives (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 (such as perylene, helicene etc.) and push-pull effect (as tonka bean camphor, rhodamine etc.) be important Consideration in the design of fluorescent material is synthetic, so be the new focus of research at present in conjunction with the molecule of push-and-pull electronic effect in conjugative effect and molecule.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 with photoluminescent property and preparation method thereof.
Conjugated compound provided by the present invention, its general structure is suc as formula shown in I:
In described formula I general structure, Ar is selected from the phenyl of phenyl, replacement and any one in heterocyclic radical; R is n-propyl or dodecyl; R ' is methyl.
Described heterocyclic radical specifically can be the 3-thienyl.
The phenyl of described replacement specifically can be following any one: 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-formyl radical phenyl and 4-chloro-phenyl-.
The method of conjugated compound shown in preparation formula I comprises the steps:
1) with 7,7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1,1 '-naphthyl naphthalene and MALEIC ANHYDRIDE are carried out back flow reaction in organic solvent, obtain the acid anhydrides adduct A shown in formula II;
2) gained acid anhydrides adduct A is dissolved in methylene dichloride, and the acetic acid solution that drips wherein bromine reacts, obtain the oxidation adduct B shown in formula III;
3) gained oxidation adduct B and Tri N-Propyl Amine or dodecyl amine are reacted in organic solvent, obtain the lactim C shown in formula IV;
The definition cotype I of R in formula IV;
4) under the condition of catalyzer triphenyl phosphorus palladium and alkali existence, the fragrant boric acid shown in described lactim C and formula V is reacted in organic solvent, obtain the conjugated compound shown in formula I;
Ar-B(OH)
2
(formula V)
The definition cotype I of Ar in formula V.
Wherein, step 1) MALEIC ANHYDRIDE and 7 described in, 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; Described organic solvent specifically can be dimethylbenzene; In described 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, described adduct A and bromine mol ratio are 1: 4-8 specifically can be 1: 5; The reaction times of described reaction is 8-12 hour, specifically can be 10-12 hour, and temperature of reaction is room temperature, specifically can be 15-18 ℃; Described acetic acid and bromine volume ratio 5: 1-10: 1, specifically can be 8: 1-9: 1.
Step 3) in, described organic solvent is dimethyl formamide (DMF) or toluene, preferred DMF; Described reaction needs to carry out under argon shield;
When described oxidation adduct B and Tri N-Propyl Amine reacted, the mol ratio of described oxidation adduct B and Tri N-Propyl Amine was 1: 5-1: 10, specifically can be 1: 8; The reaction times of described reaction is 12-24 hour, specifically can be 20-24 hour, and temperature of reaction is 30-70 ℃, specifically can be 40-60 ℃;
When described oxidation adduct B and dodecyl amine reacted, the mol ratio of described oxidation adduct B and dodecyl amine was 1: 1-1: 3, specifically can be 1: 1; The reaction times of described reaction is 12-24 hour, specifically can be 20-24 hour, and temperature of reaction is 90-110 ℃, specifically can be 95-100 ℃.
Step 4) in, described alkali specifically can be salt of wormwood; Described organic solvent is selected from any one in following two kinds of mixed solutions: the 1) mixed solvent that is mixed to get according to volume ratio 8-5: 4-3: 3-1 of toluene, ethanol and water, 2) mixed solvent that is mixed to get according to volume ratio 8-5: 4-3: 3-1 of dimethylbenzene, ethanol and water; Described reaction needs to carry out under argon shield;
The mol ratio of described triphenyl phosphorus palladium, lactim C and fragrant boric acid is 0.02-0.1: 1: 2-3 specifically can be 0.043: 1: 3; The reaction times of described reaction is 16-24 hour, specifically can be 20-24 hour, and temperature of reaction is 90-110 ℃, specifically can be 95-100 ℃; Described reaction needed argon shield.
A further object of the present invention is to provide the application of above-mentioned fluorescent conjugated compound in preparation luminous organic material or organic fluorescent dye.
Conjugated compound provided by the invention, due to this compound by 5 fixing conjugated systems that aromatic nucleus forms of two methylene radical, thereby has a larger delocalization system, and because the fixed action of methylene radical makes this system have spiral chirality, simultaneously make the ground state electronics more easy excitated due to the aromatic base of methoxyl group and replacement or push-and-pull electronic effect and the imido electronic effect of drawing of heterocycle, can promote fluorescent emission, thereby have long excitation wavelength and emission wavelength.The Ar=phenyl is as example in the formula I, and its excitation wavelength in toluene is 420nm, and emission wavelength is 474nm.Present bright-coloured yellow-green colour in solution.The method of the above-mentioned conjugated compound of preparation provided by the invention, raw material is cheap, and synthetic simple, products collection efficiency is high, and easily derivatize, detect the gained compound structure through instrument correct, and good stability has good application prospect 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 below by specific embodiment, but the present invention is not limited thereto.
Experimental technique described in following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
The formula I compound of embodiment 1, preparation Ar=phenyl, R=n-propyl, R '=methyl (is D
1)
Reaction formula is as follows:
1) add successively 159g (0.5mol) 7 in the 1000ml round-bottomed flask, 7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1,1 '-naphthyl naphthalene, 49g (0.5mol) MALEIC ANHYDRIDE and 500ml dimethylbenzene, 160 ℃ of reflux 10 hours, reaction system is removed dimethylbenzene 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) add 8.3g (0.02mol) adduct A and 40ml methylene dichloride in the 250ml round-bottomed flask, get 3ml (0.058mol) bromine and be dissolved in 50ml acetic acid, be placed in dropping funnel, slowly splash in flask under room temperature, after 12 hours, filter a small amount of washed with dichloromethane, obtain 9.1g oxidation adduct B, productive rate is 80%;
3) add 5.7g (0.01mol) oxidation adduct B and 5.9g (0.1mol) Tri N-Propyl Amine in the 250ml round-bottomed flask, be heated to 40 degree reactions after 24 hours in 100ml DMF, be spin-dried for reaction solution, a small amount of washed with dichloromethane obtains the 4.26g product C
1, productive rate 70%;
4) get 61mg (0.1mmol) C
1And 36.6mg (0.3mmol) phenylo boric acid adds in two mouthfuls of bottles of 25ml, adds 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe 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 is spin-dried for, and separates the hydrogenation helicene D that obtains phenyl substituted through column chromatography
143.6mg, productive rate 72%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, 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 as follows:
1) preparation of C1 prepares according to the method in embodiment 1;
2) get 61mg (0.1mmol) C
1And 40.8mg (0.3mmol) adds in two mouthfuls of bottles of 25ml methylphenylboronic acid, adds 5ml toluene and 3ml ethanol and 2ml 2mol/LNa with syringe 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 is spin-dried for, and separates obtaining the hydrogenation helicene D that p-methylphenyl replaces through column chromatography
247.5mg, productive rate 75%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, 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 as follows:
1) preparation of C1 prepares according to the method in embodiment 1;
2) get 61mg (0.1mmol) C
1And 45.6mg (0.3mmol) adds in two mouthfuls of bottles of 25ml methoxyphenylboronic acid, adds 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe 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 is spin-dried for, and separates obtaining the hydrogenation helicene D that p-methoxyphenyl replaces through column chromatography
353.2mg, productive rate 80%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, 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 as follows:
1) preparation of C1 prepares according to the method in embodiment 1;
2) get 61mg (0.1mmol) C
1And 46.8mg (0.3mmol) adds in two mouthfuls of bottles of 25ml chlorobenzene boric acid, adds 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe 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 is spin-dried for, and separates obtaining the hydrogenation spiral shell D that rubigan replaces through column chromatography
440.4mg, productive rate 60%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, this compound structure is correct.
Between embodiment 5, preparation Ar=, the formula I compound of thienyl, R=n-propyl, R '=methyl (is D
1)
Reaction formula is as follows:
1) preparation of C1 prepares according to the method in embodiment 1;
2) get 61mg (0.1mmol) C
1And between 38.4mg (0.3mmol), thienyl boric acid adds in two mouthfuls of bottles of 25ml, adds 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe 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 is spin-dried for, and separates obtaining the hydrogenation helicene D that thiophene replaces through column chromatography
545.7mg, productive rate 74%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, 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 as follows:
1) preparation of B prepares according to the method in embodiment 1;
2) add 5.7g (0.01mol) oxidation adduct B and 18.5g (0.1mol) dodecyl in the 250ml round-bottomed flask, be heated to 100 degree reactions after 24 hours in 100ml DMF, be spin-dried for reaction solution, 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, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe 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 is spin-dried for, and separates the hydrogenation helicene D that obtains phenyl substituted through column chromatography
658.5mg, productive rate 80%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, 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 as follows:
1) C
2Preparation prepare according to the method in embodiment 6;
2) get 74mg C
2(0.1mmol) and 45mg (0.3mmol) formylphenylboronic acid is added in two mouthfuls of bottles of 25ml, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe 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 is spin-dried for, and separates the hydrogenation helicene D that obtains the formyl radical phenyl substituted through column chromatography
723.6mg, productive rate 43%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, 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 as follows:
1) C
2Preparation prepare according to the method in 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, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe 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 is spin-dried for, and separates obtaining the hydrogenation helicene D that p-methoxyphenyl replaces through column chromatography
865.7mg, productive rate 83%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, 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 as follows:
1) C
2Preparation prepare according to the method in 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, add 5ml toluene and 3ml ethanol and 2ml 2mol/L K with syringe 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 is spin-dried for, and separates obtaining the hydrogenation helicene D that rubigan replaces through column chromatography
951.2mg, productive rate 64%.
The structure detection result of this compound is as follows:
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
+)。
By above-mentioned detected result as can be known, this compound structure is correct.
Determinand does with toluene the mensuration that solvent carries out uv-visible absorption spectra and fluorescence spectrum, obtains table 1 data.
Table 1, embodiment 1-9 prepare the optical property list of gained conjugated compound
In table 1, excitation wavelength and the emission wavelength of the conjugated compound of embodiment 1-9 preparation are all measured in toluene solvant.This series compound also has fluorescence under solid-state, fluorescence also exists when this series compound is made organic film, and this provides the foundation for the application of this quasi-molecule on luminescent material.
The conjugated compound of embodiment 1-9 preparation all presents yellow-green colour in toluene solvant.
Claims (9)
1. general structure is suc as formula the conjugated compound shown in I:
In described formula I, Ar is selected from any one in phenyl, 3-thienyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-formyl radical phenyl and 4-chloro-phenyl-; R is n-propyl or dodecyl; R ' is methyl.
2. prepare the method for conjugated compound shown in claim 1 Chinese style I, comprise the steps:
1) with 7,7 '-dimethoxy-3,4,3 ', 4 '-tetrahydrochysene-1,1 '-naphthyl naphthalene and MALEIC ANHYDRIDE are carried 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 methylene dichloride, and the acetic acid solution that drips wherein bromine reacts, obtain the compound shown in the formula III;
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 in the formula IV;
4) under the condition of catalyzer triphenyl phosphorus palladium and alkali existence, the fragrant boric acid shown in the compound shown in the formula IV and formula V is reacted in organic solvent, obtain the conjugated compound shown in formula I;
Ar-B(OH)
2
(formula V)
The definition cotype I of Ar in the formula V.
3. method according to claim 2 is characterized in that: in step 1), and described 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; Described organic solvent is dimethylbenzene; In described back flow reaction, the reaction times is 6-10 hour, and temperature of reaction is 130-160 ℃.
4. method according to claim 2, is characterized in that: step 2) in, the compound shown in described formula II and bromine mol ratio are 1:4-8; The reaction times of described reaction is 8-12 hour, and temperature of reaction is room temperature; Described acetic acid and bromine volume ratio 5:1 – 10:1.
5. method according to claim 2, it is characterized in that: in step 3), described organic solvent is dimethyl formamide or toluene; Described reaction needs to carry out under argon shield.
6. method according to claim 2, it is characterized in that: in step 3), compound and Tri N-Propyl Amine shown in described formula III react, and the mol ratio of the compound shown in described formula III and Tri N-Propyl Amine is 1:5-1:10; The reaction times of described reaction is 12-24 hour, and temperature of reaction is 30-70 ℃.
7. method according to claim 2, it is characterized in that: in step 3), the compound shown in described formula III and dodecyl amine react, and the mol ratio of the compound shown in described formula III and dodecyl amine is 1:1-1:3; The reaction times of described reaction is 12-24 hour, and temperature of reaction is 90-110 ℃.
8. the described method of any one according to claim 2-7, it is characterized in that: in step 4), described alkali is salt of wormwood; Described organic solvent is selected from any one in following two kinds of mixed solutions: the 1) mixed solvent that is mixed to get according to volume ratio 8-5:4-3:3-1 of toluene, ethanol and water, 2) mixed solvent that is mixed to get according to volume ratio 8-5:4-3:3-1 of dimethylbenzene, ethanol and water; Described reaction needs to carry out under argon shield;
The mol ratio of the fragrant boric acid shown in the compound shown in described triphenyl phosphorus palladium, formula IV and formula V is 0.02-0.1:1:2-3; The reaction times of described reaction is 16-24 hour, and temperature of reaction is 90-110 ℃.
9. the application of conjugated compound claimed in claim 1 in preparation luminous organic material or organic fluorescent dye.
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| CN106008318B (en) * | 2016-05-19 | 2018-10-09 | 中国科学院化学研究所 | A kind of chiral organic dye molecule and the preparation method and application thereof with circular polarised luminescence property |
| CN113149999B (en) * | 2021-02-05 | 2022-09-13 | 中国科学院化学研究所 | Heteroatom-bridged fluorescent conjugated aromatic band and preparation method and application thereof |
| CN113801057B (en) * | 2021-08-13 | 2023-04-18 | 浙江大学 | chrysene-base 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 |
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| WO2011018144A2 (en) * | 2009-08-12 | 2011-02-17 | Merck Patent Gmbh | Phenanthro[1,10,9,8-c,d,e,f,g]carbazole polymers and their use as organic semiconductors |
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| WO2011018144A2 (en) * | 2009-08-12 | 2011-02-17 | Merck Patent Gmbh | Phenanthro[1,10,9,8-c,d,e,f,g]carbazole polymers and their use as organic semiconductors |
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