CN105017264A - Organic small molecular photoelectric functional material, and preparation method thereof - Google Patents
Organic small molecular photoelectric functional material, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic small molecular photoelectric functional material. The organic small molecular photoelectric functional material containing porphyrin units and different dye units is prepared via selection of a plurality of dyes, and taking acetylenic bonds or aromatic ring or heterocyclic aromatic as bridges. According to a preparation method, the organic small molecular photoelectric functional material is prepared via Suzuki coupling reaction or Sonogashira coupling reaction. The organic small molecular photoelectric functional material possesses excellent processability, and appropriate energy band structures, and is high in energy conversion efficiency.
Description
Technical field
The present invention relates to organic photoelectrical material field, particularly a kind of organic molecule photoelectric functional material and preparation method thereof.
Background technology
Sun power has the features such as clean, resource is extensive, is considered to the preferred resources of alternative fossil resources, the exploitation of sun power is more and more received to the concern of the mankind.But the energy density of sun power is low, not easily directly utilize, needing to change into other energy could utilize better.In effective utilization of sun power, utilize photocell to convert solar energy into electrical energy to be one of research field with fastest developing speed, most active in the last few years.
The organic solar batteries of solution processable has low cost, be easy to process (as can spin coating, spray ink Printing etc.), be suitable for preparing the potential advantage such as large area flexible device, not only can simplify the preparation process of device, also can greatly reduce preparation cost, thus receive and pay close attention to widely.Donor material in battery active material can be divided into conjugated polymers and organic molecule according to the size of molecular weight, the easy film forming of polymkeric substance, but product is not easy to purify, molecular weight distribution is wide, and every batch of product be synthesized causes the efficiency of solar cell usually to there is larger difference because molecular weight and distribution thereof there are differences, and organic molecule does not exist these problems, therefore there is the advantage of its uniqueness in organic molecule in organic solar batteries.Photosynthesis be green plants by after Chlorophyll absorption light, carry out photochemical reaction and carry out storage power, thus provide food and the energy etc. for the mankind.The structure of porphyrin is similar with chlorophyll, there is large pi-conjugated system and high molar absorptivity, electronics can transfer to acceptor to body rapidly, easily change its physicochemical property by the modification of peripheral groups and cavity metal, Porphyrin and its derivative is the earliest by as one of light active material material being applied to organic solar batteries.But the photoelectric transformation efficiency based on Porphyrin and its derivative organic solar batteries is but very low.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the present invention is to provide a kind of organic molecule photoelectric functional material, have good processing characteristics, suitable energy band structure, effciency of energy transfer is high.
Object of the present invention is achieved through the following technical solutions:
A kind of organic molecule photoelectric functional material, its chemical structure is as follows:
Wherein: A is for being substituted or unsubstituted aromatic nucleus conjugated bridge; B is end group dye groups, and M is metal ion or protium; Ar is substituted or unsubstituted aromatic group; M is 0 or 1.
Described Ar is the aromatic nucleus be made up of ethene support group, acetylene support group, hydrocarbon atom; The aromatic heterocycle be made up of carbon nitrogen hydrogen atom, the aromatic heterocycle be made up of carbon nitrogen oxygen hydrogen atom; The aromatic heterocycle be made up of carbon sulphur hydrogen atom; The aromatic heterocycle be made up of carbon silicon hydrogen atom; The aromatic heterocycle be made up of carbon nitrogen sulphur hydrogen atom; More than one in the aromatic heterocycle be made up of carbon silicon sulphur hydrogen atom.
Described A is the conjugation emigrant that more than one aromatic heterocycles in the aromatic heterocycle that forms of the aromatic heterocycle that forms of aromatic heterocycle, carbon nitrogen sulphur hydrogen atom that aromatic heterocycle, carbon silicon hydrogen atom that aromatic heterocycle, carbon sulphur hydrogen atom that aromatic heterocycle, carbon nitrogen oxygen hydrogen atom that aromatic nucleus, the carbon nitrogen hydrogen atom be made up of hydrocarbon atom is formed are formed are formed are formed and carbon silicon sulphur hydrogen atom are formed, and the number of elementary entitles of structure conjugation emigrant is 0,1,2,3 or 4.
In the aromatic group be substituted, substituted radical is more than one in alkyl, fluoro-alkyl, alkoxyl group, ester group, carbonyl.
In the aromatic nucleus conjugated bridge be substituted, substituted radical is more than one in alkyl, fluoro-alkyl, alkoxyl group, ester group, carbonyl.
Described M is zine ion, cupric ion, magnesium ion or nickel ion.
Described B is the one in following structure:
The preparation method of described organic molecule photoelectric functional material, comprises the following steps:
Adopt the preparation of Suzuki linked reaction: by 5 under argon gas atmosphere protection, the two boric acid ester porphyrin of 10-and bromide are dissolved in and fill 1, in the reaction flask of 2-glycol dimethyl ether, add four (triphenyl phosphorus) and close palladium, two days two nights of stirring reaction under 95 ~ 105 DEG C of heating conditions, be cooled to room temperature, with chloroform extraction, be spin-dried for solvent, by silica gel column chromatography and GPC HPLC purifying, be finally spin-dried for solvent, again recrystallization, product is dry under vacuo, obtains organic molecule photoelectric functional material;
The mol ratio of described 5,10-two boric acid ester porphyrins and bromide is 1:(2.5 ~ 3.5); The molar weight of described 1,2-glycol dimethyl ether is 90 ~ 110 times of the two boric acid ester porphyrin of 5,10-and bromide integral molar quantity; The molar weight that described four (triphenyl phosphorus) close palladium is 9% ~ 11% of the two boric acid ester porphyrin of 5,10-and bromide integral molar quantity.
The preparation method of described organic molecule photoelectric functional material, comprises the following steps:
Adopt the preparation of Sonogashira linked reaction: under an argon atmosphere by 5, the two ethynyl porphyrins of 10-, bromide are dissolved in the reaction flask filling toluene and triethylamine, add four (triphenyl phosphorus) and close palladium, cuprous iodide, at 75 ~ 85 DEG C, heated and stirred reacts three days three nights, is cooled to room temperature, with chloroform extraction, be spin-dried for solvent, by silica gel column chromatography and GPC, HPLC purifying, be finally spin-dried for solvent, recrystallization again, product is dry under vacuo;
The mol ratio of described 5,10-two ethynyl porphyrins and bromide is 1:(2.5 ~ 3.5); The molar weight of described toluene is 90 ~ 110 times of the two ethynyl porphyrins of 5,10-and bromide integral molar quantity; The molar weight of described triethylamine is 40 ~ 60 times of the two ethynyl porphyrins of 5,10-and bromide integral molar quantity; The molar weight that described four (triphenyl phosphorus) close palladium is, 9% ~ 11% of the two ethynyl porphyrins of 10-and bromide integral molar quantity; The molar weight of described cuprous iodide is, 9% ~ 11% of the two ethynyl porphyrins of 10-and bromide integral molar quantity.
Organic molecule photoelectric functional material of the present invention has following characteristics:
(1) by the connection of conjugated bridge, reach effective conjugation in whole molecule, thus can promote intramolecular effective charge transfer (ICT), molecule has very wide absorption;
(2) by introducing different dyestuff end groups, ICT effect can be made stronger, then absorb meeting red shift more, in addition some dyestuff self has good absorption, then absorbing can be stronger, thus be applied in organic photovoltaic, device can be made to catch more photon, thus can short-circuit current be increased;
(3) after introducing and inhaling electrical dyestuff, can the HOMO energy level of effective drawing molecule, widening on the basis absorbed, the Porphyrin Molecule of structure can also made as small molecules donor material, there is larger open circuit voltage in the devices.Some molecule can obtain less power loss value (numerical difference of optical band gap and open circuit voltage) like this;
(4) by introducing different fragrance (mixing) rings to porphyrin two meso positions, the frontier orbit of Porphyrin Molecule can effectively be regulated, and can by modifying the solvability changing molecule;
(5) by the side chain modification to fragrance (mix) ring, end group dyestuff, conjugated bridge, the while of can effectively improving deliquescent, also can the frontier orbit of effective Molecular regulator;
(6) different metal ion is inserted, because different metal ions has different outer charge distribution, and after inserting different metal ion also can there is slight change in the configuration of Porphyrin Molecule, this all can make final Porphyrin Molecule have different frontier orbits, never can affect the absorption of Porphyrin Molecule.Finally can affect short-circuit current, the open circuit voltage of resulting devices.So, the metal be applicable to can be sought, obtain and there is high efficiency Porphyrin Molecule;
(7) can be come by the frontier orbit of final molecule selected suitable for (be subject to) body, make this molecule can as being subject to of organic thin film solar cell (to) body material.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) organic photovoltaic devices adopting organic molecule photoelectric functional material of the present invention to prepare can have wide absorption and high open circuit voltage simultaneously, namely can have less power loss numerical value (numerical difference of band gap and open circuit voltage);
(2) organic molecule photoelectric functional material of the present invention has good processing characteristics, and film-forming properties is superior;
(3) the dark absorption of organic molecule photoelectric functional material of the present invention makes it have potentiality as infrared eye.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The synthesis of embodiment 1C16TPTRD
The synthesis of two (5-(the 2-hexyl decyl) thiophene) porphyrin of step 1:15,15-
In 1000mL two mouthfuls of round-bottomed flasks, add 5-(2-hexyl decyl) thiophene-2-formaldehyde (1.632g, 4.86mmol), dipyrromethane (700mg, 4.86mmol) and the methylene dichloride of 500mL, ventilate 30 minutes with nitrogen, then the trifluoroacetic acid of 0.25mL is added, at room temperature stirring reaction 12 hours, then add 1.8g 2,3-bis-chloro-5,6-dicyano-1,4-benzoquinones (DDQ), continues stirring reaction 12 hours, after add the triethylamine cancellation reaction of 5mL.After reaction terminates, with silica gel/(methylene dichloride is eluent) column chromatography, obtain crude product after being spin-dried for, then use chloroform/methanol recrystallization, obtain dark red solid.
1H NMR(300MHz,CDCl
3)δ10.27(s,2H),9.35(q,8H),7.74(d,2H),7.20(d,2H),3.09(d,4H),1.93(m,2H),1.61-1.25(m,48H),0.95-0.82(m,12H),-2.96(s,2H)。
The synthesis of two (5-(the 2-hexyl decyl) thiophene) zinc protoporphyrin of step 2:5,15-two bromo-10,20-
By 5, two (5-(the 2-hexyl decyl) thiophene) porphyrin (688mg of 15-, 0.7mmol) be dissolved in the chloroform of 700mL, add the pyridine of 35mL, lucifuge, then add bromo-succinimide (NBS) (274mg, 1.54mmol), 0 DEG C of reaction 30 minutes, after at room temperature continue reaction 4 hours, finally with acetone cancellation reaction.React complete, add water, with chloroform extraction, anhydrous sodium sulfate drying, is dissolved in after being spin-dried for solvent in the chloroformic solution of 50mL, after add the zinc acetate methanol solution (243mg of 12mL, the zinc acetate of 1.2mmol is dissolved in the methanol solvate of 12mL), lucifuge refluxes 2 hours.React complete, washing, and with anhydrous sodium sulfate drying, be spin-dried for solvent, after using purification by silica gel column chromatography, obtain the solid of shiny red.
1H NMR(600MHz,CDCl
3)δ9.00(d,4H),8.51(d,4H),7.79(d,2H),7.23(d,2H),3.03(d,4H),1.85(m,2H),1.63-1.19(m,48H),1.01-0.79(m,12H)。
The synthesis of step 3,5,15-two (trimethylsilyl acetylene)-10,20-pairs of (5-(2-hexyl decyl) thiophene) zinc protoporphyrins
In two mouthfuls of round-bottomed flasks of 100mL, add 5,15-two bromo-10, two (5-(the 2-hexyl decyl) thiophene) zinc protoporphyrin (570mg of 20-, 0.5mmol), 25mL tetrahydrofuran (THF) and 12.5mL triethylamine, logical nitrogen 30 minutes, then two (triphenylphosphine) palladium chloride (17.5mg, 0.025mmol) is added, cuprous iodide (CuI) (5mg, 0.025mmol) with trimethylsilyl acetylene (200mg, 2mmol), lucifuge, reacts at room temperature stirring reaction three days.React complete, washing, with dichloromethane extraction, with anhydrous sodium sulfate drying, recycle silicon glue/(methylene dichloride/sherwood oil=1:1 is eluent) column chromatography, is spin-dried for and obtains green solid.
1H NMR(600MHz,CDCl
3)δ9.61(d,4H),9.12(d,4H),7.67(d,2H),7.15(d,2H),3.05(d,4H),1.87(m,2H),1.61-1.18(m,48H),0.93-0.87(m,12H),0.61(s,18H)。
The synthesis of step 4,5,15-two (acetylene)-10,20-pairs of (5-(2-hexyl decyl) thiophene) zinc protoporphyrins
By 5, two (trimethylsilyl acetylene)-10 of 15-, two (5-(the 2-hexyl decyl) thiophene) zinc protoporphyrin (411mg of 20-, 0.35mmol) be dissolved in the tetrahydrofuran solution of 20mL, add tetrabutyl ammonium fluoride (0.72mL, 1M inTHF), at room temperature stirring reaction 5 minutes, the cancellation that adds water is reacted.With chloroform extraction, anhydrous sodium sulfate drying, be spin-dried for, with silica gel/(methylene dichloride/sherwood oil=1:1 is eluent) column chromatography, be spin-dried for and obtain green solid.
1H NMR(300MHz,CDCl
3)δ9.65(d,4H),9.18(d,4H),7.68(d,2H),7.16(d,2H),4.11(s,2H),3.08(d,4H),1.92(m,2H),1.57-1.22(m,48H),0.94-0.88(m,12H)。
The synthesis of step 5,5-bromothiophene-2-(3-ethyl) rhodanine
By 5-bromothiophene-2-formaldehyde (546.7mg, 2.862mmol), 3-ethyl rhodanine (506.9mg, 3.1485mmol) be dissolved in the Glacial acetic acid of 40mL, add ammonium acetate (485mg, 6.3mmol), return stirring spends the night, and the cancellation that adds water is reacted.With dichloromethane extraction, anhydrous sodium sulfate drying, be spin-dried for, with silica gel/(methylene dichloride/sherwood oil=1:2 is eluent) column chromatography, be spin-dried for and obtain bright yellow solid.1H NMR(300MHz,CDCl3)δ7.75(s,1H),7.16(d,2H),4.18(q,2H),1.29(t,3H)。
The synthesis of step 6,4-bromobenzene-2-(3-ethyl) rhodanine
By 4-bromobenzene-2-formaldehyde (526.5mg, 2.862mmol), 3-ethyl rhodanine (506.9mg, 3.1485mmol) be dissolved in the Glacial acetic acid of 40mL, add ammonium acetate (485mg, 6.3mmol), return stirring spends the night, and the cancellation that adds water is reacted.With dichloromethane extraction, anhydrous sodium sulfate drying, be spin-dried for, with silica gel/(methylene dichloride/sherwood oil=1:2 is eluent) column chromatography, be spin-dried for and obtain yellow solid.Mass(MALDI-TOF):Obs.327.7；Calcd.for C
12H
10BrNO
2S,328.2。
The synthesis of step 7:C16TPTRD
Under the protection of argon gas; 5 are added in two mouthfuls of round-bottomed flasks of 50mL; two (acetylene)-10 of 15-; 20-two (3; two (dodecyloxy) benzene of 5-) zinc protoporphyrin (262mg; 0.2mmol), 5-bromothiophene-2-(3-ethyl) rhodanine (199.74mg, 0.6mmol); dry toluene (10mL); triethylamine (5mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium (24mg; 0; 02mmol), lucifuge, stirring reaction three days at 80 DEG C.React complete, be cooled to room temperature, washing, with toluene extraction, anhydrous sodium sulfate drying, is spin-dried for, and crosses post, obtains atropurpureus solid.Mass(MALDI-TOF):Obs.1818.2；Calcd.forC
104H
103N
6O
6S
6Zn,1817.9。
The synthesis of embodiment 2 C16TPPRD
Under the protection of argon gas; 5 are added in two mouthfuls of round-bottomed flasks of 50mL; two (acetylene)-10 of 15-; 20-two (3; two (dodecyloxy) benzene of 5-) zinc protoporphyrin (262mg; 0.2mmol), 4-bromobenzene-2-(3-ethyl) rhodanine (196.2mg, 0.6mmol); dry toluene (10mL); triethylamine (5mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium (24mg; 0; 02mmol), lucifuge, stirring reaction three days at 80 DEG C.React complete, be cooled to room temperature, washing, with toluene extraction, anhydrous sodium sulfate drying, is spin-dried for, and crosses post, obtains atropurpureus solid.Mass(MALDI-TOF):Obs.1806.3；Calcd.forC
108H
134N
6O
6S
4Zn,1805.9。
The synthesis of embodiment 3PorEFDPP
Under the protection of argon gas; 5 are added in two mouthfuls of round-bottomed flasks of 50mL; two (acetylene)-10 of 15-; 20-two (3; two (dodecyloxy) benzene of 5-) zinc protoporphyrin (262mg; 0.2mmol), single bromo Coumarin pyrrolo-pyrrole-dione (342mg, 0.6mmol); dry toluene (10mL); triethylamine (5mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium (24mg; 0; 02mmol), lucifuge, stirring reaction three days at 80 DEG C.React complete, be cooled to room temperature, washing, with toluene extraction, anhydrous sodium sulfate drying, is spin-dried for, and crosses post, obtains atropurpureus solid.Mass(MALDI-TOF):Obs.2013.6；Calcd.forC
124H
156N
8O
8S
2Zn,2013.2。
The synthesis of embodiment 4, PorESeDPP
Under the protection of argon gas; 5 are added in two mouthfuls of round-bottomed flasks of 50mL; two (acetylene)-10 of 15-; 20-two (3; two (dodecyloxy) benzene of 5-) zinc protoporphyrin (262mg; 0.2mmol), two selenium phenol pyrrolo-pyrrole-dione (418mg, 0.6mmol) of single bromo; dry toluene (30mL); triethylamine (15mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium (24mg; 0; 02mmol), lucifuge, stirring reaction three days at 80 DEG C.React complete, be cooled to room temperature, washing, with toluene extraction, anhydrous sodium sulfate drying, is spin-dried for, and crosses post, obtains atropurpureus solid.Mass(MALDI-TOF):Obs.2268.3；Calcd.forC
124H
156N
8O
4S
2Se
4Zn,2268.8。
The synthesis of embodiment 5, PorETzDPP
Under the protection of argon gas; 5 are added in two mouthfuls of round-bottomed flasks of 50mL; two (acetylene)-10 of 15-; 20-two (3; two (dodecyloxy) benzene of 5-) zinc protoporphyrin (262mg; 0.2mmol), single bromo double thiazole pyrrolo-pyrrole-dione (362mg, 0.6mmol); dry toluene (30mL); triethylamine (15mL), cuprous iodide (8mg, 0.04mmol) and tetrakis triphenylphosphine palladium (24mg; 0; 02mmol), lucifuge, stirring reaction three days at 80 DEG C.React complete, be cooled to room temperature, washing, with toluene extraction, anhydrous sodium sulfate drying, is spin-dried for, and crosses post, obtains atropurpureus solid.Mass(MALDI-TOF):Obs.2081.2；Calcd.forC
120H
152N
12O
4S
6Zn,2080.9。
Embodiment 6:
Take metallic aluminium as preparation and the performance of the organic photovoltaic battery device of negative electrode
Taking metallic aluminium as the structure of the organic photovoltaic battery device of negative electrode is: ITO/PEDOT:PSS (40nm)/active layer/PFN (10nm)/Al.Device fabrication processes is: with the ito glass cleaned in advance for anode, the water-soluble polymers PEDOT:PSS of spin coating 40 nanometer on ito glass, C16TPTRD and PC prepared by the embodiment 1 continuing spin coating 80 nanometer after drying on different slice, thin piece separately
61c16TPPRD and the PC of BM, embodiment 2 preparation
61porEFDPP and the PC of BM, embodiment 3 preparation
61porESeDPP and the PC of BM, embodiment 4 preparation
61porETzDPP and the PC of BM, embodiment 5 preparation
61bM as photovoltaic active layers, the PFN of then spin coating 10nm after dry, the Al metallic cathode of last vacuum evaporation 90 nanometer.Positive bias is applied between ITO and Al metal electrode, its battery behavior is measured under the irradiation of the AM1.5 simulated solar irradiation of 100 milliwatt every square centimeter, the open circuit voltage of this battery device is respectively 0.93,0.90,0.80,0.73 and 0.69 volt, short-circuit current is respectively 11.4,10.6,7.6,6.5 and 5.7 milliamperes every square centimeter, packing factor difference 44.2%, 41%, 37%, 35%, 32%, effciency of energy transfer is respectively 4.69%, 3.9%, 2.2%, 1.6%, 1.26%.
Foregoing PC
61bM is English " [6,6]-phenyl C
61-butyric acid methyl ester " abbreviation.
Embodiment 7:
Take ITO as preparation and the performance of the organic photovoltaic battery device of negative electrode
Taking ITO as the structure of the organic photovoltaic battery device of negative electrode is: ITO/ZnO/PEIE/active layer/MoO
3/ Al.Device fabrication processes is: with the ito glass cleaned in advance for negative electrode, ZnO and 10nmPEIE of spin coating 40nm on ito glass, continues embodiment 7 and the PC of spin coating 120 nanometer after dry
61bM, 8 and PC
61bM, 9 and PC
61bM, 10 and PC
61bM, 11 and PC
61bM as photovoltaic active layers, the MoO of vacuum evaporation afterwards 10 nanometer
3, then the Al metal anode of vacuum evaporation 90 nanometer.Negative bias is applied between ITO and Al metal electrode, its battery behavior is measured under the irradiation of the AM1.5 simulated solar irradiation of 100 milliwatt every square centimeter, the open circuit voltage of this battery device is respectively 0.92,0.91,0.81,0.72 and 0.68 volt, short-circuit current is respectively 11.8,10.9,8.1,7.6 and 6.5 milliamperes every square centimeter, packing factor is respectively 45%, 40%, 38%, 36%, 33%, effciency of energy transfer is respectively 4.9%, 4.0%, 2.5%, 2.0%, 1.4%.
Except the organic molecule photoelectric functional material in embodiment, organic molecule photoelectric functional material of the present invention also comprises the organic molecule photoelectric functional material with following chemical structure characteristic:
Wherein: A is for being substituted or unsubstituted aromatic nucleus conjugated bridge; B is end group dye groups, and M is metal ion or protium; Ar is substituted or unsubstituted aromatic group; M is 0 or 1;
Described Ar can for the aromatic nucleus be made up of ethene support group, acetylene support group, hydrocarbon atom; The aromatic heterocycle be made up of carbon nitrogen hydrogen atom, the aromatic heterocycle be made up of carbon nitrogen oxygen hydrogen atom; The aromatic heterocycle be made up of carbon sulphur hydrogen atom; The aromatic heterocycle be made up of carbon silicon hydrogen atom; The aromatic heterocycle be made up of carbon nitrogen sulphur hydrogen atom; More than one in the aromatic heterocycle be made up of carbon silicon sulphur hydrogen atom.
The conjugation emigrant that more than one aromatic heterocycles in the aromatic heterocycle that the aromatic heterocycle that the aromatic heterocycle that the aromatic heterocycle that the aromatic heterocycle that described A can be formed for aromatic nucleus, the carbon nitrogen hydrogen atom be made up of hydrocarbon atom, carbon nitrogen oxygen hydrogen atom are formed, carbon sulphur hydrogen atom are formed, carbon silicon hydrogen atom are formed, carbon nitrogen sulphur hydrogen atom are formed and the aromatic heterocycle that carbon silicon sulphur hydrogen atom is formed are formed, the number of elementary entitles of structure conjugation emigrant is 0,1,2,3 or 4;
In the aromatic group be substituted, substituted radical is more than one in alkyl, fluoro-alkyl, alkoxyl group, ester group, carbonyl.
In the aromatic nucleus conjugated bridge be substituted, substituted radical is more than one in alkyl, fluoro-alkyl, alkoxyl group, ester group, carbonyl.
Described M is zine ion, cupric ion, magnesium ion or nickel ion.
Described B is the one in following structure:
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. an organic molecule photoelectric functional material, is characterized in that, its chemical structure is as follows:
Wherein: A is for being substituted or unsubstituted aromatic nucleus conjugated bridge; B is end group dye groups, and M is metal ion or protium; Ar is substituted or unsubstituted aromatic group; M is 0 or 1.
2. organic molecule photoelectric functional material according to claim 1, is characterized in that, described Ar is the aromatic nucleus be made up of ethene support group, acetylene support group, hydrocarbon atom; The aromatic heterocycle be made up of carbon nitrogen hydrogen atom, the aromatic heterocycle be made up of carbon nitrogen oxygen hydrogen atom; The aromatic heterocycle be made up of carbon sulphur hydrogen atom; The aromatic heterocycle be made up of carbon silicon hydrogen atom; The aromatic heterocycle be made up of carbon nitrogen sulphur hydrogen atom; More than one in the aromatic heterocycle be made up of carbon silicon sulphur hydrogen atom.
3. organic molecule photoelectric functional material according to claim 1, it is characterized in that, described A is the conjugation emigrant that more than one aromatic heterocycles in the aromatic heterocycle that forms of the aromatic heterocycle that forms of aromatic heterocycle, carbon nitrogen sulphur hydrogen atom that aromatic heterocycle, carbon silicon hydrogen atom that aromatic heterocycle, carbon sulphur hydrogen atom that aromatic heterocycle, carbon nitrogen oxygen hydrogen atom that aromatic nucleus, the carbon nitrogen hydrogen atom be made up of hydrocarbon atom is formed are formed are formed are formed and carbon silicon sulphur hydrogen atom are formed, and the number of elementary entitles of structure conjugation emigrant is 0,1,2,3 or 4.
4. organic molecule photoelectric functional material according to claim 2, is characterized in that, in the aromatic group be substituted, substituted radical is more than one in alkyl, fluoro-alkyl, alkoxyl group, ester group, carbonyl.
5. organic molecule photoelectric functional material according to claim 3, is characterized in that, in the aromatic nucleus conjugated bridge be substituted, substituted radical is more than one in alkyl, fluoro-alkyl, alkoxyl group, ester group, carbonyl.
6. organic molecule photoelectric functional material according to claim 1, is characterized in that, described M is zine ion, cupric ion, magnesium ion or nickel ion.
7. organic molecule photoelectric functional material according to claim 1, is characterized in that, described B is the one in following structure:
8. the preparation method of the organic molecule photoelectric functional material described in claim 1 ~ 7, is characterized in that, comprise the following steps:
Adopt the preparation of Suzuki linked reaction: by 5 under argon gas atmosphere protection, the two boric acid ester porphyrin of 10-and bromide are dissolved in and fill 1, in the reaction flask of 2-glycol dimethyl ether, add four (triphenyl phosphorus) and close palladium, two days two nights of stirring reaction under 95 ~ 105 DEG C of heating conditions, be cooled to room temperature, with chloroform extraction, be spin-dried for solvent, by silica gel column chromatography and GPC HPLC purifying, be finally spin-dried for solvent, again recrystallization, product is dry under vacuo, obtains organic molecule photoelectric functional material;
The mol ratio of described 5,10-two boric acid ester porphyrins and bromide is 1:(2.5 ~ 3.5); The molar weight of described 1,2-glycol dimethyl ether is 90 ~ 110 times of the two boric acid ester porphyrin of 5,10-and bromide integral molar quantity; The molar weight that described four (triphenyl phosphorus) close palladium is 9% ~ 11% of the two boric acid ester porphyrin of 5,10-and bromide integral molar quantity.
9. the preparation method of the organic molecule photoelectric functional material described in claim 1 ~ 7, is characterized in that, comprise the following steps:
Adopt the preparation of Sonogashira linked reaction: under an argon atmosphere by 5, the two ethynyl porphyrins of 10-, bromide are dissolved in the reaction flask filling toluene and triethylamine, add four (triphenyl phosphorus) and close palladium, cuprous iodide, at 75 ~ 85 DEG C, heated and stirred reacts three days three nights, is cooled to room temperature, with chloroform extraction, be spin-dried for solvent, by silica gel column chromatography and GPC, HPLC purifying, be finally spin-dried for solvent, recrystallization again, product is dry under vacuo;
The mol ratio of described 5,10-two ethynyl porphyrins and bromide is 1:(2.5 ~ 3.5); The molar weight of described toluene is 90 ~ 110 times of the two ethynyl porphyrins of 5,10-and bromide integral molar quantity; The molar weight of described triethylamine is 40 ~ 60 times of the two ethynyl porphyrins of 5,10-and bromide integral molar quantity; The molar weight that described four (triphenyl phosphorus) close palladium is, 9% ~ 11% of the two ethynyl porphyrins of 10-and bromide integral molar quantity; The molar weight of described cuprous iodide is, 9% ~ 11% of the two ethynyl porphyrins of 10-and bromide integral molar quantity.
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