CN101993392B - Multi-cyano substituted triphenylamine derivatives and synthesis method and use thereof - Google Patents
Multi-cyano substituted triphenylamine derivatives and synthesis method and use thereof Download PDFInfo
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- CN101993392B CN101993392B CN200910091417.2A CN200910091417A CN101993392B CN 101993392 B CN101993392 B CN 101993392B CN 200910091417 A CN200910091417 A CN 200910091417A CN 101993392 B CN101993392 B CN 101993392B
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Abstract
The invention belongs to the field of organic light-sensitive and/or electron transport materials in organic solar cell devices, in particular to multi-cyano substituted triphenylamine derivatives for organic light-sensitive and/or electron transport materials, a synthesis method thereof, and use of the multi-cyano substituted triphenylamine derivative materials as organic solar cell devices. Through molecular design, triphenylamine is taken as a main framework and multi-cyano groups with high electron withdrawing ability are introduced, so that charge transfer in molecules is strong. Therefore, the energy gap is reduced, and the aims that the light absorption range is wide and a light absorption peak value is positioned at a long wavelength are fulfilled. Meanwhile, the molecules have high electron-capturing capacity and can be applied to the organic light-sensitive layer and/or electron transport layer materials for organic solar cells. The multi-cyano substituted triphenylamine derivatives have the structure shown in the description.
Description
Technical field
The invention belongs to the organic photosensitive in organic solar batteries device and/or electron transport material field, replace triphenylamine derivative and synthetic method thereof in particular to the many cyano group of a class for organic photosensitive and/or Organic Electron Transport Material, and replace the purposes of triphenylamine derivative material as aspects such as the organic photosensitive layer of organic solar batteries device and/or electron transport layer materials with such many cyano group.
Background technology
The world today is along with the fast development of economy, and energy problem more and more causes the attention of people.The energy dilemma that mineral fuel exhaustion causes, the Greenhouse effect that burning mineral fuel causes make the living environment of the mankind face significant challenge.The sun power taking up an area ball total energy more than 99% progresses into the visual field of people, and the distribution that sun the subject of knowledge and the object of knowledge has is wide obtains favor that is convenient, that harmless free from environmental pollution, the inexhaustible advantage of people is subject to numerous scientist.But the solar cell materials such as the silicon used at present, because cost is too high, can only in some special occasions as used, so current solar electrical energy generation amount is only equivalent to 0.04% of global gross generation for power satellite or side area communication tower.Make solar electrical energy generation obtain large-scale promotion, just must reduce the cost of solar cell material, or find more cheap solar cell material.
Traditional solar cell needs a large amount of high-quality inorganic semiconductor materials, as silicon, gallium arsenide, makes cost very high.Although the application of polysilicon and amorphous silicon is more much lower than silicon single crystal cost, the not high and cost of efficiency remain high remain solar cell cannot the significant obstacle of spread.The research and development of organic solar batteries makes solar cell cost degradation become possibility.The energy conversion efficiency of the best organic solar batteries of current report is close to the efficiency (4% ~ 8%) of business-like amorphous si solar cells.
Organic solar batteries promises to be big area and cheap photovoltaic system.Its major advantage be preparation easily, low, the raw material of processing temperature and processing technology cost low, flexible device may be produced on the plastic substrate simultaneously.But the efficiency of organic solar batteries is always very low for a long time, the basic physical process of this and it is inseparable.When solar irradiation is mapped on inorganic semiconductor, inorganic semiconductor directly can produce unbound electron, the effect of the built in field that these current carriers are formed between doping content or the different semi-conductor of doping type issue estranged from, form electric current at external circuit.When in illumination to organic semiconductor, produce exciton (electron-hole pair) in organic semiconductor, exciton splits at different organic layer (heterojunction) interface usually, otherwise these excitons will by radiation or radiationless mode inactivation.It is new for body or acceptor molecule that nearest research work mainly concentrates on synthesis, the charge mobility improving organic compound makes electronic energy avoid being captured at organic layer to increase electron diffusion length, improves the photoabsorption of photosensitive molecular in sunlight spectral range to improve the external quantum efficiency of device.
Summary of the invention
The object of the invention is to overcome Problems existing in above-mentioned organic photosensitive and/or electron transport material, provide the many cyano group of a class to replace organic photosensitive and/or the electron transport material of triphenylamine derivative; By molecular designing, take triphenylamine as main skeleton, introduce and there are the many cyano groups haling electronic capability, make it have Intramolecular electron transfer strongly, thus reduce energy gap, reach the object that light absorption range is wide, extinction peak value is positioned at long wave strong point; Meanwhile, molecule has very strong captures electronic capability, and organic photosensitive layer and/or the electron transport layer materials that can be applied to organic solar batteries use.
Another object of the present invention is to provide the synthetic method of a class many cyano group replacements triphenylamine derivative of object one.
The many cyano group of a class that an also object of the present invention is to provide object one replaces the purposes of triphenylamine derivative as aspects such as the organic photosensitive layer of organic solar batteries device and/or electron transport layer materials.
The many cyano group that the present invention relates to a class tool electron withdrawing properties replace organic photosensitive and/or the electron transport material of triphenylamine derivative, this compounds has very wide spectral absorption scope (400nm ~ 800nm) and very low reduction potential (about-0.33V vs SCE), and the organic photosensitive material and/or the electron transport material that can be used for organic solar batteries device use.The molecular structure of material of the present invention is as shown in following general formula.With the organic solar batteries device prepared by material of the present invention due to spectral absorption wide ranges, the sunlight of wide range of wavelengths can be absorbed thus improve the external quantum efficiency of device, more effectively utilizing solar energy.Material of the present invention has very low reduction potential, effectively can accept electronics as electron transport material, promotes the charge separation of exciton, thus improves the performance of solar cell device.
The present invention has adopted easy method to synthesize, and a series of many cyano group of a class with efficient organic photosensitive and/or electron transport material use that can be used as replaces triphenylamine derivative.Organic solar batteries device of the present invention comprises negative electrode, anode and organic thin film layer, at least comprise organic photoactive layer in organic thin film layer between a cathode and an anode, preferred organic photoactive layer comprises general formula (I), (II) or (III) represents, and many cyano group replace triphenylamine derivatives.The molecule that the many cyano group of a class of the present invention replaces triphenylamine derivative has one of following structure:
Wherein:
R
1, R
2, R
3substituting group can be identical or not identical, the substituted or unsubstituted alkyl being selected from hydrogen, having 1 to 20 carbon atom independently, the substituted or unsubstituted cycloalkyl with 5 to 20 carbon atoms, the alkoxyl group with 1 to 20 carbon atom, the aralkyl with 6 to 60 carbon atoms, the aryl with 6 to 50 ring carbon atoms, the aryloxy with 6 to 50 annular atomses or the one had in the aromatic heterocyclic group of 5 to 50 annular atomses.
R
4the one that substituting group can be selected from hydrogen, carboxyl, fluoromethyl, cyano group, nitro or have in the ester group of 2 to 20 carbon atoms.
Described R
1, R
2, R
3in the non-substituted alkyl with 1 to 20 carbon atom be one in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl.
Described R
1, R
2, R
3in the substituted alkyl with 1 to 20 carbon atom be methylol, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1,2-dihydroxy ethyl, 1,3-dihydroxy isopropyl base, 2,3 one dihydroxyl-tertiary butyl, 1,2,3 one trihydroxy-propyl group, amino methyl, 1-amino-ethyl, 2-amino-ethyl, 2-aminoisobutyric base, 1,2-diamino ethyl, 1,3-diamino sec.-propyl, 2,3-diamino-tertiary butyl or 1, one in 2,3-triamino propyl group.
Described R
1, R
2, R
3in the unsubstituted cycloalkyl with 5 to 20 carbon atoms are one in cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, adamantyl or norborneol alkyl;
Described R
1, R
2, R
3in the alkoxyl group with 1 to 20 carbon atom be the group represented by-OR, the group that wherein R represents is alkyl, alkyl is the one in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, methylol, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyl isobutyl-or 1,2-dihydroxy ethyl.
Described R
1, R
2, R
3in there are 6 to 60 carbon atoms aralkyl be benzyl, 1-phenylethyl, 2-phenylethyl, 1-propyloxy phenyl base, 2-propyloxy phenyl base, phenyl t-butyl, Alpha-Naphthyl methyl, 1-Alpha-Naphthyl ethyl, 2-Alpha-Naphthyl ethyl, 1-Alpha-Naphthyl sec.-propyl, 2-Alpha-Naphthyl sec.-propyl, betanaphthyl methyl, 1-betanaphthyl ethyl, 2-betanaphthyl ethyl, 1-betanaphthyl sec.-propyl, 2-betanaphthyl sec.-propyl, 1-pyrrol ylmethyl, 2-(1-pyrryl) ethyl, to methyl-benzyl, between one in methyl-benzyl or adjacent methyl-benzyl.
Described R
1, R
2, R
3in there are 6 to 50 ring carbon atoms aryl be phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 9-naphthacenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-xenyl, 3-xenyl, 4-xenyl, p-terphenyl-4-base, p-terphenyl-3-base, p-terphenyl-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, p-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl, 4 '-methyl biphenyl or 4 " one in the-tertiary butyl-p-terphenyl-4-base.
Described R
1, R
2, R
3in there are 6 to 50 annular atomses aryloxy be the group represented by-OAr, the group that wherein Ar represents is aromatic group, aromatic group is phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 9-naphthacenyl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-xenyl, 3-xenyl, 4-xenyl, p-terphenyl-4-base, p-terphenyl-3-base, p-terphenyl-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, p-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl, 4 '-methyl biphenyl or 4 " one in the-tertiary butyl-p-terphenyl-4-base.
Described R
1, R
2, R
3in there are 5 to 50 annular atomses aromatic heterocyclic group be 1-pyrryl, 2-pyrryl, 3-pyrryl, pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-indyl, 2-indyl, 3-indyl, 4-indyl, 5-indyl, 6-indyl, 7-indyl, 1-pseudoindoyl, 2-pseudoindoyl, 3-pseudoindoyl, 4-pseudoindoyl, 5-pseudoindoyl, 6-pseudoindoyl, 7-pseudoindoyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl, 1-isobenzofuran-base, 3-isobenzofuran-base, 4-isobenzofuran-base, 5-isobenzofuran-base, 6-isobenzofuran-base, 7-isobenzofuran-base, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, one in 7-isoquinolyl or 8-isoquinolyl.
Described R
4middle fluoromethyl is the one in the methyl of a fluorine, difluoro or trifluoro replacement.
Described R
4in there are 2 to 20 carbon atoms ester group be one in methoxycarbonyl, ethoxycarbonyl, propyl ester base, isopropyl ester group, positive butyl ester base, Zhong Ding ester group, isobutyl ester group, n-pentyl ester base, just own ester group, positive heptyl ester base or n-octyl base.
The synthetic method that the many cyano group of a class of the present invention replaces triphenylamine derivative comprises the following steps:
(1). under protection of inert gas, will with substituent R
1, R
2and R
3to iodine triphenylamine with substituent R
4acetylene mixing, wherein, with substituent R
1, R
2and R
3to iodine triphenylamine with substituent R
4the mol ratio of acetylene be 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with organic solvent, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography or recrystallization, obtain alkynyl triphenylamine;
(2). under protection of inert gas; alkynyl triphenylamine step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE; then mixture is stirred in methylene dichloride; through silica gel column chromatography or recrystallization, obtain many cyano group triphenylamine derivative with said structure.
Wherein: R
1, R
2, R
3, R
4definition replace R in the molecular structure of triphenylamine derivative with the many cyano group of above-mentioned definition one class
1, R
2, R
3, R
4.
Described organic solvent is diethylamine, triethylamine, Isopropylamine, quadrol or TERTIARY BUTYL AMINE.
The many cyano group of a class of the present invention replaces organic photosensitive layer and/or the electron transport layer materials that triphenylamine derivative material can be used as organic solar batteries device, for the preparation of organic solar batteries device.
The many cyano group of a class of the present invention replaces the organic electron transport layer material that triphenylamine derivative material also can be used as organic electro-optic device.
The structure of organic solar batteries device of the present invention can be: anode/organic cavity transmission layer/organic photosensitive layer/organic electron transport layer/negative electrode.Above-mentioned each organic layer can adopt the method for the various deposition organic membrane such as vacuum-evaporation, spraying, spin coating or printing to prepare.
Negative electrode, anode and organic thin film layer is comprised at above-mentioned organic solar batteries device, at least comprise organic photoactive layer in organic thin film layer between a cathode and an anode, and in organic photosensitive layer, comprise a class of the present invention many cyano group replacements triphenylamine derivative material.
Described organic electro-optic device can be used in organic field effect tube, organic integrated circuits, organic solar batteries, organic laser or organic sensor.
The preferred implementation of fabricate devices:
The typical structure of organic solar batteries device is: substrate/anode/organic cavity transmission layer (HTL)/organic photosensitive layer/organic electron transport layer (ETL)/organic hole blocking layer/negative electrode.
Substrate is transparent, can be glass or flexible substrate, and flexible substrate adopts a kind of material in polyester, poly-phthalimide compounds; Anode layer can adopt inorganic materials or organic conductive polymer, inorganic materials is generally the higher metal of the work functions such as metal oxide or gold, copper, silver such as tin indium oxide (hereinafter referred to as ITO), zinc oxide, zinc tin oxide, the optimized ITO that is chosen as; Organic conductive polymer is preferably a kind of material in Polyglycolic acid fibre/polyvinylbenzenesulfonic acid sodium (hereinafter referred to as PEDOT:PSS), polyaniline (hereinafter referred to as PANI).Cathode layer generally adopts metal that the work functions such as lithium, magnesium, calcium, strontium, aluminium or indium are lower or a kind of and copper, gold or silver-colored alloy in them, or the electrode layer that above-mentioned metal or alloy and metal fluoride are alternately formed, and the present invention is preferably metallic aluminium; Organic cavity transmission layer generally adopts phthalocyanine, and the present invention is preferably CuPc (CuPc), Phthalocyanine Zinc (ZnPc) or CuPc doped F 4-TCNQ; Organic photosensitive layer is responsible for the absorption of light and is produced current carrier, and the preferred many cyano group triphenylamine derivative of the present invention of the present invention is as organic photosensitive layer; Organic electron transport layer generally adopts soccerballene (C60) or bisbenzimidazole generation-3,4,9,10-tetra-Suo Ji perylene (PTCBI), and the preferred many cyano group of the present invention of the present invention replaces triphenylamine derivative as organic electron transport layer; Organic hole blocking layer is responsible for blocking hole and is transferred to negative electrode, and the present invention is preferably 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP).
A series of organic solar batteries device of the present invention can be prepared in accordance with the following methods:
(1) divide the cleaning of a few step with the glass substrate of anode by clean-out system, deionized water and organic solution;
(2) by the organic cavity transmission layer of the method evaporation device of vacuum-evaporation;
(3) the organic photosensitive layer of evaporation device is continued again;
(4) organic electron transport layer of evaporation device is continued;
(5) organic hole blocking layer of evaporation device is continued;
(6) metallic cathode is prepared by the method for evaporation or sputtering again.
The present invention adopts easy method to synthesize the many cyano group of a class to replace triphenylamine derivative, and replaces triphenylamine derivative with this many cyano group and make organic photosensitive and/or electron transport material has made organic solar batteries device.This type of many cyano group replaces the absorption spectrum responding range (400nm ~ 800nm) that triphenylamine derivative has Gao Bingkuan, and has and high capture electronic capability, is organic photosensitive material and/or electron transport material that a class has high photosensitizing ability.
In order to understand content of the present invention better, technical scheme of the present invention will be further illustrated by specific embodiment below, but being not limited thereto.
Embodiment
Embodiment 1. 2-(4-(hexichol amido) phenyl)-1, Isosorbide-5-Nitrae, the preparation of 4-four cyano-1,3-butadiene (MTCBD)
(1). under nitrogen protection, will mix iodine triphenylamine with acetylene, wherein, be 2: 3 to the mol ratio of iodine triphenylamine and acetylene; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain ethynyl triphenylamine, productive rate is about 90%;
(2). under nitrogen protection; what step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE ethynyl triphenylamine; then by mixture stirring at normal temperature 16 hours in methylene dichloride; through its hexane solution recrystallization; obtain target product, productive rate is about 95%.
m/z：397.13(100.0％)，398.14(28.3％)，399.14(3.9％)，398.13(1.8％)。
The solar cell device preparation of compound MTCBD
The ito glass substrate cleaned up prepares solar cell.ITO thickness is about 150nm.During evaporation organic materials, (CuPc, MTCBD, C60 and BCP) vacuum is about 1 × 10
-5pa, vacuum during evaporation negative electrode is about 1 × 10
-4pa.When preparing solar cell, ITO substrate is room temperature, and the evaporation rate of CuPc, C60 and MTCBD is about 0.1nm/s, and the evaporation rate of BCP is about 0.05nm/s, and the evaporation rate of aluminium is about 0.2nm/s.The thickness of device architecture and corresponding each layer is:
ITO/CuPc(44nm)/MTCBD(10nm)/C60(40nm)/BCP(10nm)/Al(100nm)。
Device performance is as follows:
Open circuit voltage: 0.52V; Short-circuit current: 0.67mA; Packing factor: 0.55; Effciency of energy transfer: 2.5%.
Embodiment 2. 2-(4-(hexichol amido) phenyl)-1,1,3,4,4-pentacyano-1,3-butadiene (MPCBD)
(1). under nitrogen protection, mixed by iodo-for 4-triphenylamine with cyanoacetylene, wherein, the mol ratio of the iodo-triphenylamine of 4-and cyanoacetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through its petroleum ether solution recrystallization, obtain target product, productive rate is about 80%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 20 hours in methylene dichloride, first through silica gel column chromatography; obtain target product, productive rate is about 85%.
m/z：422.13(100.0％)，423.13(31.6％)，424.13(4.8％)。
The solar cell device preparation of compound MPCBD
The ito glass substrate cleaned up prepares solar cell.ITO thickness is about 150nm.During evaporation organic materials, (CuPc, MPCBD, C60 and BCP) vacuum is about 1 × 10
-5pa, vacuum during evaporation negative electrode is about 1 × 10
-4pa.When preparing solar cell, ITO substrate is room temperature, and the evaporation rate of CuPc, C60 and MPCBD is about 0.1nm/s, and the evaporation rate of BCP is about 0.05nm/s, and the evaporation rate of aluminium is about 0.2nm/s.The thickness of device architecture and corresponding each layer is:
ITO/CuPc(44nm)/MPCBD(10nm)/C60(40nm)/BCP(10nm)/Al(100nm)
Device performance is as follows:
Open circuit voltage: 0.60V; Short-circuit current: 0.72mA; Packing factor: 0.56; Effciency of energy transfer: 3.1%.
Embodiment 3. 2-(4-(two para-totuidine bases) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DTMTCBD)
(1). under nitrogen protection, mixed by iodo-for 4-N, N-bis-pairs of toluene aniline with acetylene, wherein, the mol ratio of 4-iodo-N, N-bis-pairs of toluene aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 83%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 18 hours in methylene dichloride, through its hexane solution recrystallization; obtain target product, productive rate is about 80%.
m/z：425.16(100.0％)，426.17(30.5％)，427.17(4.5％)，426.16(1.8％)。
Embodiment 4. 2-(4-(biphenyl amido) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DBMTCBD)
(1). under nitrogen protection, mixed by iodo-for 4-N, N-biphenyl aniline with acetylene, wherein, the mol ratio of 4-iodo-N, N-biphenyl aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 70%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 70%.
m/z：549.20(100.0％)，550.20(41.4％)，551.20(9.1％)，550.19(1.8％)。
The solar cell device preparation of Compound D BMTCBD
The ito glass substrate cleaned up prepares solar cell.ITO thickness is about 150nm.During evaporation organic materials, (CuPc, DBMTCBD, C60 and BCP) vacuum is about 1 × 10
-5pa, vacuum during evaporation negative electrode is about 1 × 10
-4pa.When preparing solar cell, ITO substrate is room temperature, and the evaporation rate of CuPc, C60 and DBMTCBD is about 0.1nm/s, and the evaporation rate of BCP is about 0.05nm/s, and the evaporation rate of aluminium is about 0.2nm/s.The thickness of device architecture and corresponding each layer is:
ITO/CuPc(15nm)/DBMTCBD(20nm)/C60(30nm)/BCP(10nm)/Al(100nm)
Device performance is as follows:
Open circuit voltage: 0.50V; Short-circuit current: 0.61mA; Packing factor: 0.52; Effciency of energy transfer: 2.1%.
Embodiment 5. 2-(4-(hexichol amido) phenyl)-3-(trifluoromethyl)-1, Isosorbide-5-Nitrae, 4-four cyano
(1). under nitrogen protection, mixed by iodo-for 4-triphenylamine with trifluoropropyne, wherein, the mol ratio of the iodo-triphenylamine of 4-and trifluoropropyne is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through its petroleum ether solution recrystallization, obtain target product, productive rate is about 75%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 22 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 70%.
m/z：465.12(100.0％)，466.12(31.0％)，467.13(4.2％)。
Embodiment 6. 2-(4-bis-(4-tertiary-butyl anilino) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DTBTCBD)
(1). under nitrogen protection, mixed by iodo-for 4-N, N-bis-pairs of tert.-butylbenzene aniline with acetylene, wherein, the mol ratio of 4-iodo-N, N-bis-pairs of tert.-butylbenzene aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 85%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 84%.
m/z：509.26(100.0％)，510.26(37.1％)，511.26(7.2％)，510.25(1.8％)。
Embodiment 7. 2-(4-(two-beta-naphthylamine base) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DNTCBD)
(1). under nitrogen protection, mixed by iodo-for 4-N, N-dinaphthyl aniline with acetylene, wherein, the mol ratio of 4-iodo-N, N-dinaphthyl aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 80%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 85%.
m/z：497.16(100.0％)，498.17(37.0％)，499.17(6.6％)，498.16(1.8％)。
The solar cell device preparation of Compound D NTCBD
The ito glass substrate cleaned up prepares solar cell.ITO thickness is about 150nm.During evaporation organic materials, (CuPc, DNTCBD, C60 and BCP) vacuum is about 1 × 10
-5pa, vacuum during evaporation negative electrode is about 1 × 10
-4pa.When preparing solar cell, ITO substrate is room temperature, and the evaporation rate of CuPc, C60 and DNTCBD is about 0.1nm/s, and the evaporation rate of BCP is about 0.05nm/s, and the evaporation rate of aluminium is about 0.2nm/s.The thickness of device architecture and corresponding each layer is:
ITO/CuPc(15nm)/DNTCBD(20nm)/C60(30nm)/BCP(10nm)/Al(100nm)
Device performance is as follows:
Open circuit voltage: 0.50V; Short-circuit current: 0.66mA; Packing factor: 0.57; Effciency of energy transfer: 2.1%.
Embodiment 8. 2-(4-(di-p-methoxy anilino) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DMOTCBD)
(1). under nitrogen protection, mixed by iodo-for 4-N, N-di-p-methoxy phenylaniline with acetylene, wherein, the mol ratio of 4-iodo-N, N-di-p-methoxy phenylaniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 87%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 85%.
m/z：457.16(100.0％)，458.17(37.0％)，459.17(4.9％)，458.16(1.8％)。
Embodiment 9. 2-(4-(two pairs of hexanaphthene anilinos) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DCHTCBD)
(1). under nitrogen protection, mixed by iodo-for 4-N, N-bis-pairs of hexanaphthene phenylanilines with acetylene, wherein, the mol ratio of 4-iodo-N, N-bis-pairs of hexanaphthene phenylanilines and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 77%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 75%.
m/z：561.26(100.0％)，562.29(42.9％)，563.30(8.4％)，564.30(1.1％)。
Embodiment 10. 2-(4-(two pairs of hydroxymethyl aniline bases) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DHMTCBD)
(1). under nitrogen protection, mixed by iodo-for 4-N, N-bis-pairs of hydroxymethyl phenyl aniline with acetylene, wherein, the mol ratio of 4-iodo-N, N-bis-pairs of hydroxymethyl phenyl aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 67%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 65%.
m/z：457.15(100.0％)，458.16(30.6％)，459.16(4.9％)，458.15(1.8％)。
Embodiment 10. 2-(4-(two-2-pyridyl anilinos) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DHMTCBD)
(1). under nitrogen protection, by iodo-for 4-N, N-bis--2-pyridinylphenyl aniline mix with acetylene, wherein, 4-iodo-N, N-bis-the mol ratio of-2-pyridyl aniline and acetylene be 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 87%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 12 hours in methylene dichloride, through its hexane solution recrystallization; obtain target product, productive rate is about 85%.
m/z：551.15(100.0％)，552.16(39.6％)，553.16(8.9％)，552.15(2.8％)。
Embodiment 11. 4,4-dicyano-2-dicyano ethylene group-3-(4-hexichol aminocarbonyl phenyl) ethyl butyrate (EATCBD)
(1). under nitrogen protection, mixed by iodo-for 4-N, N-phenylbenzene aniline with ethyl propiolate, wherein, the mol ratio of 4-iodo-N, N-phenylbenzene aniline and ethyl propiolate is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 85%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 82%.
m/z：469.15(100.0％)，470.16(31.6％)，471.16(5.9％)，470.15(1.8％)。
Embodiment 12. 2-(3-(hexichol amido) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (MMTCBD)
(1). under nitrogen protection, mixed by iodo-for 3-N, N-phenylbenzene aniline with acetylene, wherein, the mol ratio of 3-iodo-N, N-phenylbenzene aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 80%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 72%.
m/z：397.13(100.0％)，398.14(28.3％)，399.14(3.9％)，398.13(1.8％)。
Embodiment 13. 2-(3-(hexichol amido) phenyl)-1,1,3,4,4-pentacyano-1,3-butadiene (MMPCBD)
(1). under nitrogen protection, mixed by iodo-for 3-N, N-phenylbenzene aniline with cyanoacetylene, wherein, the mol ratio of 3-iodo-N, N-phenylbenzene aniline and cyanoacetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through its petroleum ether solution recrystallization, obtain target product, productive rate is about 75%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 20 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 70%.
m/z：422.13(100.0％)，423.13(31.6％)，424.13(4.8％)。
The solar cell device preparation of compound MMPCBD
The ito glass substrate cleaned up prepares solar cell.ITO thickness is about 150nm.During evaporation organic materials, (CuPc, MMPCBD, C60 and BCP) vacuum is about 1 × 10
-5pa, vacuum during evaporation negative electrode is about 1 × 10
-4pa.When preparing solar cell, ITO substrate is room temperature, and the evaporation rate of CuPc, C60 and MMPCBD is about 0.1nm/s, and the evaporation rate of BCP is about 0.05nm/s, and the evaporation rate of aluminium is about 0.2nm/s.The thickness of device architecture and corresponding each layer is:
ITO/CuPc(15nm)/MMPCBD(20nm)/C60(30nm)/BCP(10nm)/Al(100nm)
Device performance is as follows:
Open circuit voltage: 0.45V; Short-circuit current: 0.60mA; Packing factor: 0.54; Effciency of energy transfer: 1.9%.
Embodiment 14. 2-(3-bis-(p-tert-butyl-aniline base) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (DTBTCBD)
(1). under nitrogen protection, mixed by iodo-for 3-N, N-bis-pairs of tert-butyl-phenyl aniline with acetylene, wherein, the mol ratio of 3-iodo-N, N-bis-pairs of tert-butyl-phenyl aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 85%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 15 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 83%.
m/z：509.26(100.0％)，510.13(37.6％)，511.26(7.2％)，510.25(1.8％)。
Embodiment 15. 2-(3-bis-(benzidion) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (BPTCBD)
(1). under nitrogen protection, mixed by iodo-for 3-N, N-dibiphenylyl aniline with acetylene, wherein, the mol ratio of 3-iodo-N, N-dibiphenylyl aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 87%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 17 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 86%.
m/z：549.26(100.0％)，550.13(41.6％)，551.26(9.2％)，550.25(1.8％)。
Embodiment 16. 2-(3-bis-(p-2-pyridine anilino) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (BPYTCBD)
(1). under nitrogen protection, iodo-for 3-N, N-bis-(p-2-pyridine phenyl) aniline is mixed with acetylene, wherein, 3-iodo-N, N-bis-the mol ratio of (p-2-pyridine phenyl) aniline and acetylene be 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 89%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 15 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 88%.
m/z：551.26(100.0％)，552.13(39.6％)，553.26(8.2％)，552.25(2.8％)。
Embodiment 17. 2-(3-bis-(P-nethoxyaniline base) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (MMOTCBD)
(1). under nitrogen protection, mixed by iodo-for 3-N, N-di-p-methoxy phenylaniline with acetylene, wherein, the mol ratio of 3-iodo-N, N-di-p-methoxy phenylaniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 87%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 15 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 83%.
m/z：457.26(100.0％)，458.13(30.6％)，459.16(5.2％)，458.15(1.8％)。
Embodiment 18. 2-(3-(hexichol amido) phenyl)-3-Trifluoromethyl-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (MTFTCBD)
(1). under nitrogen protection, mixed by iodo-for 3-N, N-phenylbenzene aniline with trifluoropropyne, wherein, the mol ratio of 3-iodo-N, N-phenylbenzene aniline and trifluoropropyne is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through its petroleum ether solution recrystallization, obtain target product, productive rate is about 78%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 76%.
m/z：465.13(100.0％)，466.13(31.6％)，467.13(4.2％)。
Embodiment 19. 2-(3-bis-(naphthylamine base) phenyl)-1,1,3,4,4-pentacyano-1,3-butadiene (DBPPCBD)
(1). under nitrogen protection, mixed by iodo-for 3-N, N-dinaphthyl aniline with cyanoacetylene, wherein, the mol ratio of 3-iodo-N, N-dinaphthyl aniline and cyanoacetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 75%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 70%.
m/z：522.16(100.0％)，523.16(40.1％)，524.17(7.0％)。
The solar cell device preparation of Compound D BPPCBD
The ito glass substrate cleaned up prepares solar cell.ITO thickness is about 150nm.During evaporation organic materials, (CuPc, DBPPCBD, C60 and BCP) vacuum is about 1 × 10
-5pa, vacuum during evaporation negative electrode is about 1 × 10
-4pa.When preparing solar cell, ITO substrate is room temperature, and the evaporation rate of CuPc, C60 and DBPPCBD is about 0.1nm/s, and the evaporation rate of BCP is about 0.05nm/s, and the evaporation rate of aluminium is about 0.2nm/s.The thickness of device architecture and corresponding each layer is:
ITO/CuPc(15nm)/DBPPCBD(20nm)/C60(30nm)/BCP(10nm)/Al(100nm)
Device performance is as follows:
Open circuit voltage: 0.49V; Short-circuit current: 0.69mA; Packing factor: 0.53; Effciency of energy transfer: 2.5%.
Embodiment 20. 2-(2-bis-(anilino) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (OMTCBD)
(1). under nitrogen protection, mixed by iodo-for 2-N, N-phenylbenzene aniline with acetylene, wherein, the mol ratio of 2-iodo-N, N-phenylbenzene aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 78%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 16 hours in methylene dichloride, through its hexane solution recrystallization; obtain target product, productive rate is about 72%.
m/z：397.13(100.0％)，398.14(28.3％)，399.14(3.9％)，398.13(1.8％)。
Embodiment 21. 2-(2-bis-(anilino) phenyl)-1,1,3,4,4-pentacyano-1,3-butadiene (OMPCBD)
(1). under nitrogen protection, mixed by iodo-for 2-N, N-phenylbenzene aniline with cyanoacetylene, wherein, the mol ratio of 2-iodo-N, N-phenylbenzene aniline and cyanoacetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through its petroleum ether solution recrystallization, obtain target product, productive rate is about 70%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 18 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 62%.
m/z：422.13(100.0％)，423.13(311.6％)，424.13(4.8％)。
The solar cell device preparation of compound OMPCBD
The ito glass substrate cleaned up prepares solar cell.ITO thickness is about 150nm.During evaporation organic materials, (CuPc, OMPCBD, C60 and BCP) vacuum is about 1 × 10
-5pa, vacuum during evaporation negative electrode is about 1 × 10
-4a.When preparing solar cell, ITO substrate is room temperature, and the evaporation rate of CuPc, C60 and OMPCBD is about 0.1nm/s, and the evaporation rate of BCP is about 0.05nm/s, and the evaporation rate of aluminium is about 0.2nm/s.The thickness of device architecture and corresponding each layer is:
ITO/CuPc(15nm)/OMPCBD(20nm)/C60(30nm)/BCP(10nm)/Al(100nm)
Device performance is as follows:
Open circuit voltage: 0.43V; Short-circuit current: 0.66mA; Packing factor: 0.44; Effciency of energy transfer: 1.9%.
Embodiment 22. 2-(2-bis-(p-tert-butyl-aniline base) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (OTBTCBD)
(1). under nitrogen protection, mixed by iodo-for 2-N, N-bis-pairs of tert-butyl-phenyl aniline with acetylene, wherein, the mol ratio of 2-iodo-N, N-bis-pairs of tert-butyl-phenyl aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 69%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 20 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 62%.
m/z：509.26(100.0％)，510.26(37.1％)，511.26(7.2％)，510.25(1.8％)。
Embodiment 23. 2-(2-bis-(benzidion) phenyl)-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (ODBTCBD)
(1). under nitrogen protection, mixed by iodo-for 2-N, N-dibiphenylyl aniline with acetylene, wherein, the mol ratio of 2-iodo-N, N-dibiphenylyl aniline and acetylene is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 65%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 21 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 60%.
m/z：549.20(100.0％)，550.20(41.4％)，551.20(9.1％)，550.19(1.8％)。
Embodiment 24. 2-(2-bis-(anilino) phenyl)-3-Trifluoromethyl-1, Isosorbide-5-Nitrae, 4-four cyano-1,3-butadiene (OTFTCBD)
(1). under nitrogen protection, mixed by iodo-for 2-N, N-dibiphenylyl aniline with trifluoropropyne, wherein, the mol ratio of 2-iodo-N, N-dibiphenylyl aniline and trifluoropropyne is 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with triethylamine, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography, obtain target product, productive rate is about 75%;
(2). under nitrogen protection; product step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then by mixture stirring at normal temperature 24 hours in methylene dichloride, through silica gel column chromatography; obtain target product, productive rate is about 73%.
m/z：465.12(100.0％)，466.12(31.1％)，467.13(4.2％)。
Embodiment listed above all can be used in organic transistor, organic integrated circuits, organic solar batteries, organic laser or organic sensor.
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to above-described embodiment, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.
Claims (8)
1. the many cyano group of a class replaces triphenylamine derivative, it is characterized in that, the molecule that described many cyano group replace triphenylamine derivative has following structure:
Wherein:
R
1, R
2, R
3substituting group is identical or not identical, the substituted or unsubstituted alkyl being selected from hydrogen, having 1 to 20 carbon atom independently, the substituted or unsubstituted cycloalkyl with 5 to 20 carbon atoms, the alkoxyl group with 1 to 20 carbon atom, the aralkyl with 6 to 60 carbon atoms, the aryl with 6 to 50 ring carbon atoms, the aryloxy with 6 to 50 annular atomses or the one had in the aromatic heterocyclic group of 5 to 50 annular atomses;
R
4the one that substituting group is selected from carboxyl, fluoromethyl, cyano group or has in the ester group of 2 to 20 carbon atoms;
Described R
1, R
2, R
3in the non-substituted alkyl with 1 to 20 carbon atom be one in methyl, ethyl, propyl group, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl;
Described R
1, R
2, R
3in the substituted alkyl with 1 to 20 carbon atom be methylol, 1 one hydroxyethyls, 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1,2-dihydroxy ethyl, 1,3-dihydroxy isopropyl base, 2,3-dihydroxyl-tertiary butyl, 1,2,3-trihydroxy-propyl group, amino methyl, 1-amino-ethyl, 2-amino-ethyl, 2-aminoisobutyric base, 1,2-diamino ethyl, 1,3-diamino sec.-propyl, 2,3-diamino-tertiary butyl or 1, one in 2,3-triamino propyl group;
Described R
1, R
2, R
3in the unsubstituted cycloalkyl with 5 to 20 carbon atoms are one in cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl or norborneol alkyl;
Described R
1, R
2, R
3in the alkoxyl group with 1 to 20 carbon atom be the group represented by-OR, the group that wherein R represents is alkyl, alkyl is the one in methyl, ethyl, propyl group, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, methylol, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyl isobutyl-or 1,2-dihydroxy ethyl;
Described R
1, R
2, R
3in there are 6 to 60 carbon atoms aralkyl be benzyl, to the one in methyl-benzyl, a methyl-benzyl or adjacent methyl-benzyl;
Described R
1, R
2, R
3in there are 6 to 50 ring carbon atoms aryl be phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, a tolyl, p-methylphenyl, to the one in tert-butyl-phenyl, p-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl or 4-methyl isophthalic acid-naphthyl;
Described R
1, R
2, R
3in there are 6 to 50 annular atomses aryloxy be the group represented by-OAr, the group that wherein Ar represents is aromatic group, aromatic group be phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, a tolyl, p-methylphenyl, to the one in tert-butyl-phenyl, p-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl or 4-methyl isophthalic acid-naphthyl;
Described R
1, R
2, R
3in there are 5 to 50 annular atomses aromatic heterocyclic group be 1-pyrryl, 2-pyrryl, 3-pyrryl, pyridyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl, 1-isobenzofuran-base, 3-isobenzofuran-base, 4-isobenzofuran-base, 5-isobenzofuran-base, 6-isobenzofuran-base, 7-isobenzofuran-base, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, one in 7-isoquinolyl or 8-isoquinolyl.
2. many cyano group according to claim 1 replaces triphenylamine derivative, it is characterized in that: described R
4middle fluoromethyl is the one in the methyl of a fluorine, difluoro or trifluoro replacement;
Described R
4in there are 2 to 20 carbon atoms ester group be one in methoxycarbonyl, ethoxycarbonyl, propyl ester base, positive butyl ester base, Zhong Ding ester group, isobutyl ester group, n-pentyl ester base, just own ester group, positive heptyl ester base or n-octyl base.
3. the many cyano group according to claim 1 ~ 2 any one replace a synthetic method for triphenylamine derivative, and it is characterized in that, the method comprises the following steps:
(1). under protection of inert gas, will with substituent R
1, R
2and R
3to iodine triphenylamine with substituent R
4acetylene mixing, wherein, with substituent R
1, R
2and R
3to iodine triphenylamine with substituent R
4the mol ratio of acetylene be 2: 3; Add the bi triphenyl phosphorus palladium chloride of catalytic amount and the cuprous iodide of catalytic amount, then mixture is mixed with organic solvent, reflux under whipped state; Filter to obtain crude product, through silica gel column chromatography or recrystallization, obtain alkynyl triphenylamine;
(2). under protection of inert gas, alkynyl triphenylamine step (1) obtained mixes with the ratio that mol ratio is 1: 1 with TCNE, then mixture is stirred in methylene dichloride, through silica gel column chromatography or recrystallization, obtain described many cyano group and replace triphenylamine derivative;
Wherein: R
1, R
2, R
3, R
4definition with described in claim 1 ~ 2 any one.
4. synthetic method according to claim 3, is characterized in that: described organic solvent is diethylamine, triethylamine, Isopropylamine, quadrol or TERTIARY BUTYL AMINE.
5. the purposes of the many cyano group replacement triphenylamine derivatives according to claim 1 ~ 2 any one, it is characterized in that: described many cyano group replace triphenylamine derivative materials can as the organic photosensitive layer of organic solar batteries device and/or electron transport layer materials, for the preparation of organic solar batteries device.
6. purposes according to claim 5, it is characterized in that: described organic solar batteries device comprises negative electrode, anode and organic thin film layer, at least comprise organic photoactive layer in organic thin film layer between a cathode and an anode, and in organic photosensitive layer, comprise many cyano group replacement triphenylamine derivative material.
7. the many cyano group according to claim 1 ~ 2 any one replace a purposes for triphenylamine derivative, it is characterized in that: described many cyano group replace triphenylamine derivative material can as the organic electron transport layer material of organic electro-optic device.
8. purposes according to claim 7, is characterized in that described organic electro-optic device can be used in organic field effect tube, organic integrated circuits, organic solar batteries, organic laser or organic sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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