CN102153733B - Supermolecular polymer photoelectric material and application thereof - Google Patents
Supermolecular polymer photoelectric material and application thereof Download PDFInfo
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- CN102153733B CN102153733B CN 201110030281 CN201110030281A CN102153733B CN 102153733 B CN102153733 B CN 102153733B CN 201110030281 CN201110030281 CN 201110030281 CN 201110030281 A CN201110030281 A CN 201110030281A CN 102153733 B CN102153733 B CN 102153733B
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Abstract
The invention provides a supermolecular polymer photoelectric material and application thereof to a photoelectric device. The supermolecular polymer photoelectric material comprises an A1 unit, an A2 unit, a functional group B and a functional group C, wherein the functional group B and the functional group C are connected with the A1 unit and the A2 unit respectively; the A1 unit and the A2 unit are oligomers containing conjugation units or small molecular components containing conjugation units; the functional group B is crown ether; the functional group C is a secondary ammonium salt; the functional groups B and C are connected with each other through a hydrogen bond; and the crown ether and a secondary ammonium salt material have very strong coaction in reagents such as chloroform/acetonitrile, toluene/acetonitrile, chlorobenzene, o-dichlorohenzene and the like, so that a supermolecular polymer can be formed. The supermolecular polymer has the characteristics of determination of a small molecular structure, easy purification, multiple functions, solution processability and the like. The defects of the need of vapor deposition processing, unstable polymer structure, difficulty in purifying and the like existing in the conventional small molecular photoelectric material are overcome. The supermolecular polymer photoelectric material can be applied to an organic photoelectric device as a novel supermolecular polymer photoelectric material.
Description
Technical field
The present invention relates to the organic photoelectrical material technical field, be specifically related to supermolecule polymer photovaltaic material that the interaction of one type of crown ether and secondary ammonium salt forms and the application in organic electro-optic device thereof.
Background technology
Organic Light Emitting Diode is because its brightness is high, and in light weight, WV is low, and thickness of detector is thinner, and can be with a wide range of applications in fields such as FPD and organic illuminations through the characteristics such as method preparation of wet processes such as spin coating or spray ink Printing.From Deng's high official position study group of Kodak [Tang, C.W. in 1987; Van Slyke S.A.et.al; Appl.Phys.Lett.1987,51,913.] invented the organic molecule membrane electro luminescent device of sandwich device architecture, the nineteen ninety R.H.Friend of univ cambridge uk study group [Burroughes, J.H.; Bradley, D.D.C., Friend, R.H; Holmes, A.B.et al; Nature 1990,347,539.] report the phenomenon of polymer electroluminescence under low voltage, opened the frontier of polymer electroluminescence research.Recent two decades, organic flat panel display is obtained huge progress, has stepped into the industrialization stage at present, becomes the next-generation that replaces liquid-crystal display.
The photovaltaic material of report mainly concentrates on organic molecule and the polymkeric substance at present, but never causes concern yet form the supermolecule polymer material through host-guest interaction.Because having possessed small molecule structure simultaneously, supermolecule polymer confirms, is prone to purifying and characteristics such as polymkeric substance multifunctionality, solution processable; Also having overcome traditional micromolecular photoelectric material must be through vapor deposition processing with polymer architecture be indefinite, the shortcoming of difficult purification etc., so supermolecule polymer is applied to photovaltaic material and has great application prospect.
Summary of the invention
The present invention provides supermolecule polymer photovaltaic material and application thereof.The supermolecule polymer photovaltaic material is to be functional group with crown ether and secondary ammonium salt; The middle conjugation oligopolymer of introducing; The interaction of hydrogen bond of the Subjective and Objective through crown ether and secondary ammonium salt forms supermolecule polymer, is applied to obtain preferable performance in the Organic Light Emitting Diode.The material that contains crown ether and secondary ammonium salt has very strong host-guest interaction to form supermolecule polymer in organic reagents such as chloroform/acetonitrile, toluene/acetonitrile, chlorobenzene, orthodichlorobenzene; Can be used as luminous issuance of materials or transport material and be applied in the organic electro-optic device (Organic Light Emitting Diode for example; Organic solar batteries, organic field effect tube).
Supermolecule polymer photovaltaic material provided by the invention has following structure:
A
1And A
2Be oligopolymer that contains conjugate unit or the small molecule component that contains conjugate unit; The B of functional group is the crown ether structure, and the C of functional group is a secondary ammonium salt structure; Link to each other with interaction of hydrogen bond between B of functional group and the C of functional group.
Above-mentioned A
1And A
2Have more than one of following structure, but be not limited thereto:
Wherein R is an alkyl chain.
Above-mentioned R is straight chained alkyl, branched-chain alkyl or the cyclic alkyl chain of C1～C20; Wherein one or more carbon atoms can be replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro, and Wasserstoffatoms can be replaced by fluorine atom, Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro.
The B of functional group has a kind of in the following structure:
Above-mentioned R
1Be Wasserstoffatoms or alkyl chain; R
1Straight chained alkyl, branched-chain alkyl or cyclic alkyl chain for C1～C20; Wherein one or more carbon atoms can be replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro, and Wasserstoffatoms can be replaced by fluorine atom, Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro.
The C of functional group has a kind of in the following structure:
X
-Be F
-, Cl
-, Br
-, I
-, PF
6 -, OTf
-, BF
4 -,
CF
3SO
3 -, CH
3SO
3 -, ClO
4 -Or NO
3 -
Above-mentioned R
2Be Wasserstoffatoms or alkyl chain; R
2For C1～C20 straight chain, side chain or cyclic alkyl chain; Wherein one or more carbon atoms can be replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro, and Wasserstoffatoms can be replaced by fluorine atom, Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro.
The C of functional group of the B of functional group of crown ether structure and secondary ammonium salt structure has very strong interaction to form the supermolecule polymer photovaltaic material in organic reagents such as chloroform/acetonitrile, toluene/acetonitrile, chlorobenzene, orthodichlorobenzene.
Electroluminescent device of the present invention comprises glass, the hole transmission layer that closes attached to Conducting Glass layer (PEDOT) on glass, with the Conducting Glass laminating, the luminescent layer of fitting with hole transmission layer, the cathode layer of fitting with luminescent layer.Luminescent layer is made up of synthetic supermolecule polymer photovaltaic material of the present invention.With analysis means such as nucleus magnetic resonance, mass spectrum, ultimate analysis, DTA the supermolecule polymer photovaltaic material is characterized, to carrying out performance characterization with above-mentioned supermolecule polymer photovaltaic material electroluminescent device.
Compared with prior art, the present invention has the following advantages:
(1) supermolecule polymer photovaltaic material structure provided by the invention is confirmed, is synthesized simply, is prone to a large amount of preparations.
(2) the present invention is through introducing the oligopolymer of difference in functionalityization, the application of having expanded the supermolecule polymer photovaltaic material.
(3) supermolecule polymer photovaltaic material of the present invention has utilized small molecule structure to confirm, be prone to purifying and characteristics such as polymkeric substance multifunctionality, solution processable; Also overcome the processing conditions waste starting material and the shortcomings such as polymer architecture is indefinite, difficult purification of small molecules vapor deposition, thereby made the supermolecule polymer photovaltaic material that very big commercial promise arranged.
Description of drawings
Fig. 1 is embodiment 1 a crown ether monomer I, the structural representation of secondary ammonium salt monomer II and different shape supermolecule polymer III;
Fig. 2 is that embodiment 1 dislikes the crown ether monomer I, under secondary ammonium salt monomer II and the different solubility supermolecule polymer III at deuterochloroform and deuterium for the proton magnetic spectrum figure in the acetonitrile mixed solvent;
Fig. 3 is embodiment 1 a crown ether monomer I, the differential scanning calorimetric thermogram of the supermolecule polymer III of secondary ammonium salt monomer II and solid state powder;
Fig. 4 is the viscosity variation diagram of supermolecule polymer III under different solubility of embodiment 1;
Fig. 5 is embodiment 1 a crown ether monomer I, the abosrption spectrogram of the supermolecule polymer III of secondary ammonium salt monomer II and solid state powder;
Fig. 6 is embodiment 1 a crown ether monomer I, the emmission spectrum figure of the supermolecule polymer III of secondary ammonium salt monomer II and solid state powder;
Fig. 7 is the supermolecule polymer III of embodiment 1 solid state powder and the emmission spectrum figure after Ir (ppy) 3 (1%) blend.
Embodiment
Through specific embodiment the present invention is further described below; Its purpose is to help better to understand content of the present invention; Comprise that specifically monomeric synthetic, the supermolecule polymer performance characterization of crown ether monomer, secondary ammonium salt prepares with organic electro-optic device, but the protection domain that these specific embodiments do not limit the present invention in any way.
Raw material 4-bromo-dibenzo 24-hat-8 is pressed the method preparation of document [Pierre Mobian, et al.Org.Biomol.Chem, 2006,4,224-231], 2; 7-two bromo-9, the 9-dioctyl fluorene, 2,7-two (4,4; 5,5-tetramethyl--1,3,2-dioxa borine-2-yl)-9, the 9-dioctyl fluorene is pressed document [Qiong Hou; Qingmei Zhou, Yong Cao.et al.Macromolecules, 2004,37 (17): 6299-6305] preparation, p-bromobenzaldehyde reagent directly foreignizes source company from peace and orders.
Synthetic route is following:
(1) preparation of 4-(4,4,5,5-tetramethyl--1,3,2-dioxa borine-2-yl)-dibenzo 24-hat-8 (a)
With 4-bromo-dibenzo 24-hat 8 (5.27g; 10mmol), duplex pinacol boric acid ester (3.81g; 15mmol), Potassium ethanoate 4.0g; 40mmol) join in two mouthfuls of flasks of 150mL with two (diphenylphosphine) (ferrocene) palladium chlorides (150mg) of 1 ' 1-, the Ar gas shiled adds 100mL1,4-dioxane down.Reflux, reaction 36h.Reaction solution is poured in the icy salt solution, stirred adding methylene dichloride down, extraction, organic layer merges organic phase with washing.After dried over mgso, remove organic solvent again, obtain light yellow sticky solid (a).
(2) with 4-(4,4,5,5-tetramethyl--1; 3,2-dioxa borine-2-yl)-dibenzo 24-hat-8 (4.02g, 7mmol); 2,7-two bromo-9,9-dioctyl fluorene (1.65g; 3mmol), four close triphenyl phosphorus palladium (60mg) and join in the two-mouth bottle of 100mL, the Ar gas shiled adds 40mL toluene, 20mL THF and 6mL organic bases down.Reflux 36h.Reaction solution is poured in the icy salt solution, stirred adding methylene dichloride down, extraction, organic layer merges organic phase with washing.After the dried over mgso, remove and desolvate.The gained solid is that 5: 5: 1 sherwood oil, ETHYLE ACETATE and methylene dichloride mixed solvent carries out wash-out through volume ratio again, crosses post through neutral aluminium sesquioxide then, obtains faint yellow semisolid (I) 1.2g, and yield is 32%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：7.72(d，J＝7.8Hz，2H)，7.52～7.48(m，4H)，7.22～7.19(m，4H)，6.95(d，J＝8.5Hz，2H)，6.92～6.85(m，8H)，4.27(t，J＝4.6Hz，4H)，4.29～4.26(m，4H)，4.23～4.20(m，4H)，4.18～4.15(m，8H)，3.98～3.92(m，16H)，3.86(s，16H)，2.04～1.98(m，4H)，1.18～1.05(m，20H)，0.78(t，J＝7.0Hz，6H)，0.71-0.70(m，4H)。
13C?NMR(CDCl
3，75MHz)δ(ppm)：151.1，148.7，148.5，148.2，139.2，139.1，134.8，125.2，121.0，120.6，119.7，119.3，113.9，113.8，113.3，70.8，69.5，69.3，69.1，68.9，54.7，39.9，31.2，29.5，28.7，23.3，22.1，13.5。Mass spectrum (Madi-Tof): theoretical value 1282.7, actual value (M)
+1282.5, (M+Na)
+1305.5, (M+K)
+1321.5.Ultimate analysis theoretical value C
77H
102O
16(%): C 72.05, and H 8.01. actual value (%): C 71.45, and H 8.34.
Secondary ammonium salt monomer N, the preparation of N '-[(9,9-dioctyl fluorene-2,7-yl)-two (1, the 4-phenyl)]-dimethylene dibenzyl ammonium hexafluorophosphate (II)
(1) 2,7-two (phenyl aldehyde-4-yl)-9, the preparation of 9-dioctyl fluorene (b)
With 2,7-two (4,4,5; 5-tetramethyl--1,3,2-dioxa borine-2-yl)-9; The 9-dioctyl fluorene (3.2g, 5mmol), 4-bromo-phenyl aldehyde (2.0g, 11mmol), yellow soda ash (4.24g; 40mmol) close triphenyl phosphorus palladium (175mg) and join in the two-mouth bottle of 150mL, saturated 20mL water, the 80mL toluene of adding down of Ar with four.Reflux 24h.Reaction solution is poured in the icy salt solution, stirs adding methylene dichloride down, extraction, organic layer merges organic phase with washing.Wash three times, organic layer with anhydrous magnesium sulfate drying after, remove organic solvent.The gained solid is that 5: 1 petrol ether/ethyl acetate mixed solvent carries out wash-out through volume ratio again, crosses post through neutral aluminium sesquioxide then, obtains light yellow solid (b) 2.7g, yield 90.0%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：10.0(s，2H)，7.99(dd，J＝1.7，6.6Hz，4H)，7.84(dd，J＝1.9，8.7Hz，6H)，7.66(dd，J＝1.7，7.89Hz，2H)，7.62(d，J＝1.2Hz，2H)，2.10～2.05(m，4H)，1.18～1.07(m，20H)，0.78(t，J＝7.0Hz，6H)，0.71-0.70(m，4H)。
13C?NMR(CDCl
3，100MHz)δ(ppm)：191.8，152.0，147.5，140.9，138.9，135.1，130.3，127.7，126.5，121.7，120.5，55.5，40.3，31.7，29.9，29.1，23.8，22.5，14.0。Mass spectrum (ESI): theoretical value 598.4, actual value (M+1)
+599.3.Ultimate analysis theoretical value C
43H
50O
2(%): C 86.24, and H 8.42.Actual value (%): C 85.82, and H 8.51.
The preparation of (2) two-{ [(9,9-dioctyl fluorene-2,7-yl)-two (1, the 4-phenyl)]-two methyl }-two benzylamino formic acid tertiary butyl ester (c)
With 2,7-two (phenyl aldehyde-4)-9, the 9-dioctyl fluorene (1.5g, 2.5mmol) and benzylamine (1.07g 10mmol) joins in two mouthfuls of flasks of 100mL, and the Ar gas shiled adds down 50mL toluene, reflux 20h.Reaction solution is revolved dried.Solid is dissolved in two mouthfuls of flasks that join 100mL in the 20mL THF, add again 50mL methyl alcohol and Peng Qinghuana (0.49g, 10mmol), reflux 8h.Reaction heat is poured in the icy salt solution, added sodium hydrogencarbonate, dichloromethane extraction.Anhydrous magnesium sulfate drying revolves dried.Solid is dissolved in the 50mL exsiccant methylene dichloride, joins in two mouthfuls of flasks of 100mL, add again tert-Butyl dicarbonate (1.43g, 6.5mmol) with the 4-Dimethylamino pyridine of catalytic amount, reflux 12h.Stopped reaction revolves dried.The gained solid is that 5: 1 petrol ether/ethyl acetate mixed solvent carries out wash-out through volume ratio, crosses post through neutral aluminium sesquioxide again, white sticky solid (c) 1.84g, yield 77%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：7.77(d，J＝7.9Hz，2H)，7.64(d，J＝8.2Hz，4H)，7.60～7.56(m，4H)，7.38～7.25(m，14H)，4.48(s，4H)，4.40(s，4H)，2.06～2.01(m，4H)，1.53(s，18H)，1.19～1.06(m，20H)，0.79(t，J＝6.6Hz，6H)，0.73～0.72(m，4H)。
13C?NMR(CDCl
3，75MHz)δ(ppm)：156.0，151.7，1240.7，139.7，138.1，136.9，128.5，128.3，127.9，127.7，127.6，127.4，127.3，125.9，121.5，121.4，120.0，80.1，55.3，55.3，49.1，48.9，40.4，31.7，30.0，29.1，28.5，23.8，22.5，14.0。Mass spectrum (ESI): theoretical value 980.6, actual value (M+1)
+981.8.Ultimate analysis theoretical value C
67H
84N
2O
4(%): C 82.00, and H 8.63, and N 2.85.Actual value (%): C 81.01, and H 8.32, and N 2.89.
(3) (1.42g 1.5mmol) joins in two mouthfuls of flasks of 100mL, in reaction flask, adds 30mL CH again with two-{ [(9,9-dioctyl fluorene-2,7-yl)-two (1, the 4-phenyl)]-two methyl }-two benzylamino formic acid tertiary butyl ester
2Cl
2, the Ar gas shiled adds 3mL CF down
3COOH reacts 12h under the room temperature.In reaction solution, add saturated NH
4PF
6The aqueous solution revolves dried organic solvent, and solid is separated out, suction filtration.Solid is dissolved in acetonitrile, joins NH
4PF
6Aqueous solution recrystallization, suction filtration, drying obtains light yellow solid and is secondary ammonium salt monomer (II) 1.45g, and yield is 90%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：7.84(d，J＝7.9Hz，2H)，7.73(d，J＝8.3Hz，4H)，7.70(d，J＝1.2Hz，2H)，7.66(dd，J＝1.6，7.9Hz，2H)，7.49(t，J＝8.3Hz，4H)，7.43～7.37(m，5H)，4.03(s，4H)，4.00(s，4H)，2.13～2.07(m，4H)，1.33～1.00(m，20H)，0.74(t，J＝6.7Hz，6H)，0.56～0.55(m，4H)。
13C?NMR(DMSO，100MHz)δ(ppm)：156.7，146.3，145.1，143.6，136.9，135.8，135.7，135.2，134.3，134.0，132.1，131.0，126.3，125.7，60.3，55.2，54.9，36.2，34.2，33.5，33.4，28.5，27.1，19.0。Mass spectrum (Madi-Tof): theoretical value 1072.5, actual value (M-2PF
6 -)
+780.5.Ultimate analysis theoretical value C
57H
70F
12N
2P
2(%): C 63.80, and H 6.57, and N 2.61.Actual value (%): C 63.03, and H 6.84, and N 2.80.
Fig. 1 is the crown ether monomer I, and secondary ammonium salt monomer II and crown ether monomer I and secondary ammonium salt monomer II form the structural representation of supermolecule polymer III through the interaction of hydrogen bond between the Subjective and Objective.Positively charged ion in the secondary ammonium salt monomer II can be through the cavity of crown ether monomer I, and hydrogen bound to nitrogen in the secondary ammonium salt monomer II and the ether chain Sauerstoffatom in the crown ether monomer I form supermolecule polymer III through the interaction of hydrogen bond of Subjective and Objective at this moment.Secondary ammonium salt monomer II and crown ether monomer I have very strong interaction to form supermolecule polymer in organic reagents such as chloroform/acetonitrile, toluene/acetonitrile, chlorobenzene, orthodichlorobenzene.
Fig. 2 is the crown ether monomer I, and the supermolecule polymer that I and II form under secondary ammonium salt monomer II and the different solubility is at deuterochloroform and the accumulation proton magnetic spectrum figure of deuterium for acetonitrile (volume ratio is 1: 1): a) be crown ether monomer I, b) secondary ammonium salt monomer II; Deng mole solubility crown ether monomer I and secondary ammonium salt monomer II c) 1mM, d) 2mM, e) 5mM; F) 10mM; G) 25mM, h) 50mM, i) 200mM.From proton magnetic spectrum figure can see with the ammonium positively charged ion near the Wasserstoffatoms of methylene radical tangible displacement is arranged under different solubility.Along with the increase of solubility, the interaction between crown ether monomer I and the secondary ammonium salt monomer II strengthens, and makes chemical shift draw close to 4.80.When solubility reaches 10mM, among the proton magnetic spectrum figure with ammonium root positively charged ion near the chemical shift of Wasserstoffatoms of methylene radical remain unchanged basically, the form that the supermolecule polymer that solubility forms more than 10mM is described is identical.Therefore, thus proton magnetic spectrum figure proves crown ether monomer I and secondary ammonium salt monomer II very intuitively has very strong interaction to form supermolecule polymer in the mixed solvent of chloroform and acetonitrile.Crown ether monomer I and the secondary ammonium salt monomer II interaction strength in different organic solvents is different, and binding constant changes to some extent, makes the final supermolecule polymer that forms difference to some extent on the form in solution.The crown ether monomer I is identical at the action intensity under solid-state with secondary ammonium salt monomer II, and binding constant is the same, and the form of the supermolecule polymer that obtains is the same.
Fig. 3 is the crown ether monomer I, the differential scanning calorimetric thermogram of the supermolecule polymer III of secondary ammonium salt monomer II and solid state powder.The second-order transition temperature of crown ether monomer I is 8 ℃, and the second-order transition temperature of secondary ammonium salt monomer II is 53 ℃, and the second-order transition temperature of supermolecule polymer III compares with monomer and be greatly improved, and is 110 ℃.And there is not monomeric variation in the spectrogram of supermolecule polymer III; Thereby further specify the crown ether monomer I and secondary ammonium salt monomer II has formed supermolecule polymer III through interaction; And second-order transition temperature also is improved largely, and makes supermolecule polymer have good processing characteristics.
Fig. 4 is that the viscosity under the different solubility of supermolecule polymer III changes bilogarithmic graph in chloroform and acetonitrile mixed solvent.Under low solubility, slope of a curve is 0.034, and along with the increase of solubility, slope of a curve becomes 1.758 by 0.034.Under high viscosity, supermolecule polymer III is beneficial to intermolecular self-assembly.The change solubility of slope shows the transformation of supermolecule polymer to single form greatly about 22mM.
Fig. 5 and Fig. 6 are respectively the crown ether monomer I, the film absorption spectrum of the supermolecule polymer III of secondary ammonium salt monomer II and solid state powder and emmission spectrum figure.Can find out that from absorption spectrum and emmission spectrum figure supermolecule polymer III compares with crown ether monomer I and secondary ammonium salt monomer II, keeps the position of original absorption peak and emission peak basically.The maximum absorption band of spectrogram and maximum emission peak have shown that supermolecule polymer III has possessed the characteristic of blue light material, and then are used as the blue light material of Organic Light Emitting Diode luminescent layer.
Fig. 7 is the mix film emmission spectrum figure of 1% Ir (PPy) 3 of the supermolecule polymer III of solid state powder.From the film emmission spectrum, can find out that the triplet of supermolecule polymer III is higher than Ir (PPy) 3 triplet, thereby can be used as the material of main part of Ir (PPy) 3, supermolecule polymer III is applied in the phosphorescence luminescent device.And then can obtain organic diode device efficiently.
In order further to obtain device efficiently, can increase the conjugate unit of oligopolymer.Also can obtain the device of different colours simultaneously through changing the conjugate unit of oligopolymer.In the monomer that obtains the different colours device, can obtain white light parts through the content of adjustment redgreenblue.Supermolecule polymer white light material has easy-regulating, can repeat to compare with unit molecule white light material.In case study on implementation 2, the function of above-mentioned supermolecule polymer material can be accomplished.
Case study on implementation 2 crown ether monomers 7,7 "-two (dibenzo 24-hats-8)-2,2 ': 7 ', 2 "-three (9; The 9-dioctyl fluorene) (IV), 4,7-two [7-two (dibenzo 24-hat-8)-9,9-dioctyl fluorene-2-yl]-2,1; 3-diazosulfide (V), 4,7-two [5-two (dibenzo 24-hat-8)-thiophene-2-yl]-2,1,3-diazosulfide (VI) and secondary ammonium salt N; The preparation of N '-{ [(2,2 ': 7 ', 2 "-three (9; the 9-dioctyl fluorene)-7,7 '-yl)]-two (1, the 4-phenyl) }-dimethylene dibenzyl ammonium hexafluorophosphate (VII)
Crown ether monomer 7,7 "-two (dibenzo 24-hats-8)-2,2 ': 7 ', 2 "-three (9, the 9-dioctyl fluorene) preparation (IV)
With 4-(4,4,5,5-tetramethyl--1; 3,2-dioxa borine-2-yl)-dibenzo 24-hat-8 (4.02g, 7mmol), 7,7 "-two bromo-2; 2 ': 7 ', 2 "-three (9, the 9-dioctyl fluorene) (4.0g; 3mmol), four close triphenyl phosphorus palladium (100mg) and join in the two-mouth bottle of 100mL, the Ar gas shiled adds 30mL toluene, 50mL THF and 6mL organic bases down.Reflux 36h.Reaction solution is poured in the icy salt solution, stirred adding methylene dichloride down, extraction; Organic layer merges organic phase with washing, and after dried over mgso; Removing the solid that obtains after desolvating is that 5: 10: 1 sherwood oil and ETHYLE ACETATE and methylene dichloride mixed solvent carries out wash-out through volume ratio again; Cross post through neutral aluminium sesquioxide then, obtain oyster white semisolid (IV) 1.5g, yield 24%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：7.83～7.75(m，6H)，7.72～7.60(m，8H)，7.54～7.52(m，4H)，7.24～7.21(m，4H)，6.97(d，J＝8.5Hz，2H)，6.89(s，8H)，4.30～4.29(m，4H)，4.27～4.24(m，4H)，4.23～4.15(m，8H)，3.99～3.84(m，16H)，3.83(s，16H)，2.08～2.05(m，12H)，1.25～1.09(m，60H)，0.88～0.77(m，30H)。
Crown ether monomer 4,7-two [7-two (dibenzo 24-hat-8)-9,9-dioctyl fluorene-2-yl]-2,1, the preparation of 3-diazosulfide (V)
With 4-(4,4,5,5-tetramethyl--1; 3,2-dioxa borine-2-yl)-and dibenzo 24-hat-8 (1.73g, 3mmol), 4,7-two [7-two bromo-9; 9-dioctyl fluorene-2-yl]-2,1, the 3-diazosulfide (1.3g, 1.2mmol); Four close triphenyl phosphorus palladium (40mg) joins in the two-mouth bottle of 100mL, and the Ar gas shiled adds 20mL toluene, 40mL THF and 3mL organic bases down.Reflux 36h.Reaction solution is poured in the icy salt solution, stirred adding methylene dichloride down, extraction; Organic layer merges organic phase with washing, and after dried over mgso; Removing the solid that obtains after desolvating is that petrol ether/ethyl acetate/methylene dichloride mixed solvent of 5: 10: 1 carries out wash-out through volume ratio again; Cross post through neutral aluminium sesquioxide then, obtain orange/yellow solid (V) 0.58g, yield 27%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：8.04(dd，J＝1.4，7.9Hz，2H)，7.96(s，2H)，7.88(d，J＝8.6Hz，4H)，7.80(d，J＝7.9Hz，2H)，7.54(d，J＝7.8Hz，4H)，7.24～7.21(m，4H)，6.97(d，J＝8.4Hz，2H)，6.89(s，8H)，4.30～4.27(m，4H)，4.24～4.21(m，4H)，4.24～4.22(m，4H)，4.18～4.13(m，8H)，3.99～3.94(m，16H)，3.87(s，16H)，2.09～2.05(m，4H)，1.19～1.10(m，40H)，0.88～0.76(m，20H)。
13C?NMR(CDCl
3，100MHz)δ(ppm)：154.4，152.0，151.3，149.2，149.1，148.7，141.0，140.0，139.6，136.1，133.6，128.2，127.9，125.8，124.0，121.5，121.3，120.3，120.2，119.7，114.4，114.3，113.9，71.3，70.0，69.9，69.6，69.5，55.5，40.3，31.8，30.1，29.2，24.0，22.6，14.0。Ultimate analysis theoretical value C
112H
144N
2O
16S (%): C 74.47, and H 8.03, N1.55, and S 1.78.Actual value (%): C 74.01, and H 7.34, and N 1.60, and S 1.92.
Crown ether monomer 4,7-two [5-two (dibenzo 24-hat-8)-thiophene-2-yl]-2,1, the preparation of 3-diazosulfide (VI)
With 4-(4,4,5,5-tetramethyl--1; 3,2-dioxa borine-2-yl)-and dibenzo 24-hat-8 (2.3g, 4mmol), 4; 7-two [5-two bromo-thiophene-2-yl]-2,1,3-diazosulfide (0.69g; 1.5mmol), four close triphenyl phosphorus palladium (50mg) and join in the two-mouth bottle of 100mL, the Ar gas shiled adds 20mL toluene, 40mL THF and 3mL organic bases down.Reflux 36h.Reaction solution is poured in the icy salt solution, stirred adding methylene dichloride down, extraction, organic layer is used washing, merges organic phase, and through dried over mgso, uses the methylene dichloride recrystallization except that the back gained solid that desolvates, and gets red solid (VI) 0.86g, yield 48%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：8.06(d，J＝3.3Hz，2H)，7.84(s，2H)，7.27(d，J＝3.4Hz，2H)，7.23～7.19(m，4H)，6.89(m，5H)，4.25～4.16(m，16H)，3.94～3.93(m，16H)，3.86(m，16H)。Ultimate analysis theoretical value C
62H
68N
2O
16S
3(%): C 62.40, H5.27, and N 2.35, and S 8.06.Actual value (%): C 62.01, and H 5.46, and N 2.24, and S 8.35.
Secondary ammonium salt N, the preparation of N '-{ [(2,2 ': 7 ', 2 "-three (9, the 9-dioctyl fluorene)-7,7 '-yl)]-two (1, the 4-phenyl) }-dimethylene dibenzyl ammonium hexafluorophosphate (VII)
(1) 7,7 "-two (4,4,5,5-tetramethyl--1,3,2-dioxa borine-2-yl)-2,2 ': 7 ', 2 "-three (9, the 9-dioctyl fluorene) preparation (d)
With 7,7 "-two bromo-2,2 ': 7 ', 2 " (6.0g 4.5mmol) is dissolved among the 150mLTHF, under the Ar gas shiled, dropwise adds n-BuLi (4.5mL, 2.5molL under-78 ℃ in-three (9, the 9-dioctyl fluorene)
-1), behind the reaction 2h, add 2-sec.-propyl-4,4,5,5-tetramethyl--1,3,2-dioxa borine (5mL).Rise to room temperature reaction 24h.Reaction solution is poured in the icy salt solution, stirred adding methylene dichloride down, extraction, organic layer merges organic phase, and with after the dried over mgso, removes organic solvent with washing.The gained solid is that 10: 1 sherwood oil and ETHYLE ACETATE mixed solvent carries out wash-out through volume ratio again, crosses post through neutral aluminium sesquioxide then, obtains white solid (d) 4.8g, yield 75%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：7.83(d，J＝7.7Hz，4H)，7.78(d，J＝4.0Hz，4H)，7.73(d，J＝7.6Hz，2H)，7.67(m，8H)，2.08～2.03(m，12H)，1.40(s，24H)，1.22～1.07(m，60H)，0.83～0.70(m，30H)。
13C?NMR(CDCl
3，100MHz)δ(ppm)：152.1，151.8，150.2，143.8，141.0，140.5，140.1，140.0，133.8，128.9，126.2，126.0，121.5，120.3，119.9，119.0，83.7，55.3，55.2，40.3，40.2，31.8，30.0，29.2，24.9，23.9，23.8，22.6，14.0。Ultimate analysis theoretical value C
99H1
44B
2O
4(%): C 83.75, H10.22.Actual value (%): C 83.45, and H 10.12.
(2) 7,7 "-two (phenyl aldehydes-4-yl)-2,2 ': 7 ', 2 "-three (9, the 9-dioctyl fluorene) preparation (e)
With 7,7 "-two (4,4,5,5-tetramethyl--1; 3,2-dioxa borine-2-yl)-2,2 ': 7 ', 2 "-three (9; The 9-dioctyl fluorene) (4.3g, 3mmol), 4-bromo-phenyl aldehyde (1.3g, 7mmol); (2.6g 24mmol) closes triphenyl phosphorus palladium (105mg) and joins in the two-mouth bottle of 150mL with four yellow soda ash, saturated 10mL water, the 60mL toluene of adding down of Ar.Reflux 24h.Reaction solution is poured in the icy salt solution, stirs adding methylene dichloride down, extraction, organic layer merges organic phase with washing.Wash three times, organic layer with anhydrous magnesium sulfate drying after, remove organic solvent.The gained solid is that 5: 1 sherwood oil and ETHYLE ACETATE mixed solvent carries out wash-out through volume ratio again, crosses post through neutral aluminium sesquioxide then, obtains yellow solid (e) 4.2g, yield 82.5%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：10.09(s，2H)，8.00(d，J＝8.4Hz，4H)，7.87～7.82(m，10H)，7.71～7.64(m，12H)，2.12～2.07(m，12H)，1.25～1.10(m，60H)，0.81～0.77(m，30H)。
13C?NMR(CDCl
3，75MHz)δ(ppm)：191.8，152.0，151.9，151.8，147.7，141.4，141.0，140.4，140.1，139.6，138.4，135.1，130.3，127.7，126.5，126.3，126.2，121.7，121.5，120.3，120.0，55.4，55.3，40.3，31.8，30.0，29.2，23.9，22.6，14.0。Ultimate analysis theoretical value C
101H
130O
24(%): C 88.15, and H 9.52. actual value (%): C 87.91, and H 9.13.
The preparation of (3) two-{ [(2,2 ': 7 ', 2 "-three (9, the 9-dioctyl fluorene)-7,7 '-yl)-two (1, the 4-phenyl)]-two methyl }-two benzylamino formic acid tertiary butyl ester (f)
With 7,7 "-two (phenyl aldehydes-4-yl)-2,2 ': 7 ', 2 "-three (9, the 9-dioctyl fluorene) (and 3g, 2.2mmol) and benzylamine (0.54g 5mmol) joins in two mouthfuls of flasks of 100mL, and the Ar gas shiled adds down 40mL toluene, reflux 20h.Reaction solution is revolved dried.Solid is dissolved in two mouthfuls of flasks that join 100mL in the 20mL THF, add again 60mL methyl alcohol and Peng Qinghuana (0.74g, 15mmol), reflux 8h.Reaction heat is poured in the icy salt solution, added sodium hydrogencarbonate, dichloromethane extraction.Extraction product is used anhydrous magnesium sulfate drying, revolves dried.Solid is dissolved in the 50mL exsiccant methylene dichloride, joins in two mouthfuls of flasks of 100mL, add again tert-Butyl dicarbonate (1.76g, 8mmol) with the 4-Dimethylamino pyridine of catalytic amount, reflux 12h.Stopped reaction revolves dried.The gained solid is that 10: 1 sherwood oil and ETHYLE ACETATE mixed solvent carries out wash-out through volume ratio again, crosses post through neutral aluminium sesquioxide then, yellow solid (f) 3.0g, yield 78%.
1H?NMR(CDCl
3，300MHz)δ(ppm)：7.83(d，J＝4.8Hz，2H)，7.81(s，2H)，7.80(d，J＝2.5Hz，2H)，7.70～7.67(m，6H)，7.66～7.64(m，6H)，7.62～7.59(m，4H)，7.38～7.27(m，14H)，4.48(s，4H)，4.40(s，4H)，2.11～2.06(m，12H)，1.54(s，30H)，1.20～1.10(m，60H)，0.85～0.78(m，30H)。
13C?NMR(CDCl
3，75MHz)δ(ppm)：156.1，151.8，140.7，140.6，140.5，140.1，140.0，139.9，139.7，138.0，137.0，128.6，128.0，127.5，127.3，127.2，126.2，126.0，121.5，120.0，80.1，55.3，49.0，40.4，31.8，30.0，29.2，28.5，23.9，22.6，14.0。Ultimate analysis theoretical value C
125H
164N
2O
4(%): C 85.37, and H 9.40.Actual value (%): C 85.01, and H 9.14.
(4) with two-{ [(2,2 ': 7 ', 2 "-three (9, the 9-dioctyl fluorene)-7,7 '-yl)-two (1, the 4-phenyl)]-two methyl }-(2.8g 1.6mmol) joins in two mouthfuls of flasks of 100mL two benzylamino formic acid tertiary butyl ester, in reaction flask, adds 30mLCH again
2Cl
2, the Ar gas shiled adds 3mL CF down
3COOH reacts 12h under the room temperature.In reaction solution, add saturated NH
4PF
6The aqueous solution revolves dried organic solvent, and solid is separated out, suction filtration.Solid is dissolved in acetone, joins NH
4PF
6Aqueous solution recrystallization, suction filtration, drying obtains light yellow solid (VII) 1.45g, yield 90%.
1H?NMR(DMSO，300MHz)δ(ppm)：7.97(s，2H)，7.91(d，J＝6.9Hz，6H)，7.83(d，J＝7.8Hz，4H)，7.76～7.69(m，10H)，7.60(d，J＝8.0Hz，4H)，7.50～7.47(m，10H)，4.27(s，4H)，4.21(s，4H)，2.07～2.04(m，12H)，0.96(s，60H)，0.67(s，30H)。
13C?NMR(CD
3COCD
3，100MHz)δ(ppm)：162.1，151.9，151.7，142.5，140.9，140.6，140.4，140.2，140.0，138.8，131.1，130.8，131.1，130.8，130.2，129.9，129.6，129.1，127.4，126.2，126.0，121.3，120.3，120.2，55.4，55.3，51.5，51.3，39.9，35.4，31.5，30.2，23.7，22.3，13.4。Ultimate analysis theoretical value C
115H
150F
12N
2P
2(%): C 74.65, and H 8.17, and N 1.51.Actual value (%): C 74.01, and H 8.033, and N 1.58.
Claims (4)
1. supermolecule polymer photovaltaic material is characterized in that structural formula is following:
A
1And A
2Be oligopolymer that contains conjugate unit or the small molecule component that contains conjugate unit; The B of functional group is the crown ether structure, with A
1Link to each other; The C of functional group is a secondary ammonium salt structure, with A
2Link to each other; Link to each other with interaction of hydrogen bond between B of functional group and the C of functional group; The said B of functional group has a kind of of following structure:
R wherein
1Be Wasserstoffatoms or R
1Straight chained alkyl, branched-chain alkyl or cyclic alkyl chain for C1 ~ C20; Wherein one or more carbon atoms are replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro, and Wasserstoffatoms is replaced by fluorine atom, Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro.
2. supermolecule polymer photovaltaic material according to claim 1 is characterized in that said A
1And A
2Have more than one of following structure:
Wherein R is straight chained alkyl, branched-chain alkyl or the cyclic alkyl of C1 ~ C20; Wherein one or more carbon atoms are replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro, and Wasserstoffatoms is replaced by fluorine atom, Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro.
3. supermolecule polymer photovaltaic material according to claim 1 is characterized in that the said C of functional group has a kind of in the following structure:
X wherein
-Be F
-, Cl
-, Br
-, I
-, PF
6 -, OTf
-, BF
4 -,
, CF
3SO
3 -, CH
3SO
3 -, ClO
4 -Or NO
3 -R
2Be Wasserstoffatoms or R
2Straight chained alkyl, branched-chain alkyl or cyclic alkyl chain for C1 ~ C20; Wherein one or more carbon atoms are replaced by Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro, and Wasserstoffatoms is replaced by fluorine atom, Sauerstoffatom, thiazolinyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyanic acid or nitro.
4. each described supermolecule polymer photovaltaic material application in organic electro-optic device of claim 1～3.
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