CN110041337A - A kind of pyrrolopyrrole class organic semiconducting materials containing free radical, preparation method and applications - Google Patents
A kind of pyrrolopyrrole class organic semiconducting materials containing free radical, preparation method and applications Download PDFInfo
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Abstract
The pyrrolopyrrole class organic semiconducting materials that the invention discloses a kind of containing free radical, preparation method and applications, belong to optoelectronic materials technology.Preparation method of the invention includes: to mix pyrrolopyrrole halo derivatives with monomer I, or pyrrolopyrrole organo-tin compound is mixed with monomer I ', obtains pyrrolopyrrole class organic semiconducting materials；Pyrrolopyrrole class organic semiconducting materials and oxidant reaction are obtained into the pyrrolopyrrole class organic semiconducting materials containing free radical.Preparation method synthetic route of the invention is simple, is readily synthesized.Pyrrolopyrrole class organic semiconducting materials prepared by the present invention containing free radical, its electron mobility is high, stability of molecule is good, absorption intensity is high and it is narrow to absorb wavestrip, its absorbing wavelength reaches near infrared band, can be used for the free sill of the devices such as near-infrared, narrowband photodetector, organic field-effect tube.
Description
Technical field
The present invention relates to optoelectronic materials technologies, and in particular to a kind of pyrrolopyrrole class containing free radical is organic partly to be led
Body material, preparation method and applications.
Background technique
Optical detector technology can be realized precisely to be detected from ultraviolet visible light region to infrared light district, usually be applied to industrial production,
The fields such as military research, photoelectronics.With social development, people to optical detector technology increasingly higher demands, therefore in addition to
To widening outside the research of detectable wave band, the development for paying attention to detecting narrowband is also needed.Narrowband detector is also referred to as wave band and distinguishes spy
Device is surveyed, there is wavelength sensitivity characteristic, the light of detection specific band is merely able to, is played in terms of bio-imaging and security monitoring important
Effect.
Currently, what is be often used in optical detection is the inorganic semiconductor photoelectric material of Si, GaN or InGaAs, wave is responded
Section is wider, and also needs to realize narrowband response by optical filter or prism-coupled in use, and complex manufacturing process is cumbersome, and detects
As a result often there is error.Also, inorganic semiconductor photoelectric material prepares the entire complex process of light-detecting device, at high cost.
Currently, natural limit of the size of inorganic thin film field-effect tube already close to miniaturization, to further increase
Circuit level needs separately to ward off new diameter, and the manufacturing cost of inorganic thin film field-effect tube is high, monocrystalline is difficult to prepare, needs high temperature
Technique and substrate are hard material.In face of these problems, in recent years with the development of organic polymer, organic field-effect tube
(OFET) just more and more paid attention to by people, compared with traditional inorganic field effect pipe, OFET has many incomparable
A little:
(1) film technique of organic film is more, update, the size of device can accomplish smaller (point in size), thus
Integrated level can be improved so that the operation power of integrated circuit reduces, arithmetic speed faster；
(2) can be appropriately modified by organic molecular structure to improve its electrical property, can also by adulterate come
Reach identical purpose, so that the performance of OFET be made to be improved；
(3) it can be achieved larger in area；
(4) organic material is from a wealth of sources is easily obtained；
(5) there is better flexibility by the organic field-effect tube of organic material preparation, bending appropriate is carried out to device
It will not influence the electrical characteristics of device.
However, the organic semiconducting materials for being used as organic field effect tube not only need to have stable electrochemistry spy
Property, should also have a π-conjugated systems of towering key, the axial direction of pi bond overlapping should shortest distance direction one as far as possible between source-drain electrode
It causes, to be conducive to the transmission of carrier.Thus one, in order to make growth and the orientation of crystal reach optimal pattern, also one
Determine to limit the application of most of organic materials in degree, and film preparation condition is also put forward higher requirements.It is existing
Preparation of the technology for the organic semiconducting materials as organic field effect tube, the process is more complicated, and obtain
Organic semiconducting materials electron mobility is lower.
Summary of the invention
The pyrrolopyrrole class organic semiconducting materials that the purpose of the present invention is to provide a kind of containing free radical, preparation method
And its application, with wider, the complex manufacturing process that solves inorganic semiconductor photoelectric material response wave band in existing narrowband Detection Techniques
It is cumbersome, and there is error in detection result.
The technical scheme to solve the above technical problems is that
A kind of pyrrolopyrrole class organic semiconducting materials containing free radical, molecular structure is as shown in formula I:
Wherein, R1For tert-butyl, aromatic radical or heterocyclic aromatic base；R2For tert-butyl, aromatic radical or heterocyclic aromatic base；R3For
Oxygen atom or sulphur atom；R4For H atom, the straight chained alkyl or branched alkyl of C1-C60；R5For oxygen atom, sulphur atom or imido grpup；
R6For furans, and two furans, union II furans, three furans, tetrad furans, thiophene, 1,4-Dithiapentalene, union II thiophene, terthienyl,
Four bithiophenes, 3,4- ethene dioxythiophene, selenophen and two selenophens, union II selenophen, three selenophens, tetrad selenophen, aromatic radical, nitrile
Base, nitro-derivative, fluorine-containing thiophene, fluorine-containing furans, fluorine-containing selenophen, phenyl, 1- naphthalene or 2- naphthalene.
It should be noted that the furans of the above-mentioned meaning of the present invention, refer to 1 oxygen-containing five member ring heterocyclic compound, and two furans,
Union II furans, three furans and tetrad furans refer respectively to 2,2,3,4 oxygen-containing five-ring heterocycles.
Furans C4H4O (English: Furan), structural formula are as follows:
And two furans C6H4O2(English: Furo [3,2-b] furan), structural formula are as follows:
Union II furans C8H6O2(English: 2,2'-Bifuran), structural formula are as follows:
Three furans C12H8O3(English: 2,2':5', 2 "-Terfuran), structural formula are as follows:
Tetrad furans C16H10O4(English: 2,2':5', 2 ": 5 ", 2 " '-Quaterfuran), structural formula are as follows:
Similarly, the signified thiophene of the present invention, 1,4-Dithiapentalene, union II thiophene, terthienyl, four bithiophenes；And selenophen, simultaneously
Two selenophens, union II selenophen, three selenophens, tetrad selenophen are also in this way, increasing separately the ring number of thiophene, selenophen.Divide below
Molecular formula and structural formula are not provided.
Thiophene C4H4S (English: Thiophene), structural formula are as follows:
1,4-Dithiapentalene C6H4S2(English: Thieno [3,2-b] thiophene), structural formula are as follows:
Union II thiophene C8H6S2(English: 2,2'-Bithiophene), structural formula are as follows:
Terthienyl C12H8S3(English: 2,2':5', 2 "-Terthiophene), structural formula are as follows:
Four bithiophene C16H10S4(English: 2,2':5', 2 ": 5 ", 2 " '-Quaterthiophene), structural formula are as follows:
To simplify description, selenophen, simultaneously two selenophens, union II selenophen, three selenophens and tetrad selenophen no longer provide one by one, tie
Structure formula is that above-mentioned O atom or S atom are replaced with Se atom.
A kind of preparation method of the pyrrolopyrrole class organic semiconducting materials containing free radical, comprising:
(1) pyrrolopyrrole halides and its derivative are mixed with monomer I, or by pyrrolopyrrole organo-tin compound
It is mixed with monomer I ', obtains pyrrolopyrrole class organic semiconducting materials；
I structure of monomer is as shown in formula II:
Wherein, R1For tert-butyl, aromatic radical or heterocyclic aromatic base；R2For tert-butyl, aromatic radical or heterocyclic aromatic base；R3For
Hydroxyl or sulfydryl；R7For fragrant ylboronic acid, ene boric acid, aromatic radical borate or ene boric acid ester；
I ' structure of monomer such as formula II ' is shown:
Wherein, R1For tert-butyl, aromatic radical or heterocyclic aromatic base；R2For tert-butyl, aromatic radical or heterocyclic aromatic base；R3For
Hydroxyl or sulfydryl；R7' it is halogen；
(2) oxidant mixing is added into pyrrolopyrrole class organic semiconducting materials, obtains the pyrrolo- containing free radical
Pyroles organic semiconducting materials.
Further, in preferred embodiments of the present invention, prepare that pyrrolopyrrole class is organic partly to be led in above-mentioned steps (1)
The detailed process of body material are as follows: pyrrolopyrrole halides are added and its derivative, monomer I, palladium catalyst, Phosphine ligands, alkali are solid
Body and water, it is cold in the solvent of toluene or dioxane under 90 DEG C~120 DEG C reaction temperatures in inert gas atmosphere protection
Solidifying back flow reaction 10h~14h；
Wherein, rubbing between pyrrolopyrrole halides and its derivative, monomer I, palladium catalyst, Phosphine ligands and alkali solid
You are than being 1:(2.2~4): (0.05~0.1): (0.15~0.4): (3~4), the additional amount of water are pyrrolopyrrole halides
And its 0.2wt%~0.4wt% of derivative；Alkali solid includes tetrabutylammonium hydroxide, potassium carbonate or cesium carbonate.
Preferably, such as 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C or 120 DEG C of above-mentioned reaction temperature.It returns
Flow reaction time such as 10h, 11h, 12h, 13h or 14h.Pyrrolopyrrole halides and its derivative, monomer I, palladium catalyst,
Molar ratio such as 1:2.2:0.15:3,1:2.6:0.075:0.2:3.5,1:3:0.075:0.3 between Phosphine ligands and alkali solid:
3.5 or 1:4:0.1:0.4:4.The additional amount of water be pyrrolopyrrole halides and its derivative 0.2wt%, 0.25wt%,
0.3wt%, 0.35wt% or 0.4wt%.In the present invention, pyrrolopyrrole halides and its derivative refer to pyrrolopyrrole
Halides or pyrrolopyrrole halo derivatives.Preferably, palladium catalyst includes tetrakis triphenylphosphine palladium or three (dibenzylidenes third
Ketone) two palladiums.
Preferably, Phosphine ligands include three (o-methyl-phenyl) phosphines.
Further, in preferred embodiments of the present invention, above-mentioned pyrrolopyrrole halides and its derivant structure are such as
Shown in formula III:
Wherein, R4For H atom, the straight chained alkyl or branched alkyl of C1-C60；R5For oxygen, sulphur or imido grpup；R6For furans,
And two furans, union II furans, three furans, tetrad furans, thiophene, 1,4-Dithiapentalene, union II thiophene, terthienyl, four bithiophenes,
3,4- ethene dioxythiophene, selenophen and two selenophens, union II selenophen, three selenophens, tetrad selenophen, aromatic radical, itrile group, nitro spread out
Biological, fluorine-containing thiophene, fluorine-containing furans, fluorine-containing selenophen, phenyl, 1- naphthalene or 2- naphthalene；X is halogen.
Further, in preferred embodiments of the present invention, prepare that pyrrolopyrrole class is organic partly to be led in above-mentioned steps (1)
The detailed process of body material are as follows: pyrrolopyrrole organo-tin compound, monomer I ', palladium catalyst and Phosphine ligands are added, in inertia
It is condensed in dry and the toluene of deoxygenation or the solvent of tetrahydrofuran under 80 DEG C~120 DEG C reaction temperatures in gas atmosphere protection
Back flow reaction 6h~10h；
Wherein, the molar ratio between pyrrolopyrrole organo-tin compound, monomer I ', palladium catalyst and Phosphine ligands is 1:(2
~3): (0.05~0.1): (0.15~0.4).
Preferably, such as 80 DEG C of above-mentioned reaction temperature, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C
Or 120 DEG C.Reflux time such as 6h, 7h, 8h, 9h or 10h.Pyrrolopyrrole organo-tin compound, monomer I ', palladium chtalyst
Molar ratio such as 1:2:0.05:0.15,1:2.6:0.075:0.2,1:2.6:0.75:0.3 or 1 between agent and triphenylphosphine:
3:0.1:0.4.
Preferably, palladium catalyst includes: tetrakis triphenylphosphine palladium, bis- (triphenylphosphine) palladium chlorides or bis- (acetonitrile) dichlorides
Palladium.
Preferably, Phosphine ligands include triphenylphosphine or tri-tert-butylphosphine.
Further, in preferred embodiments of the present invention, above-mentioned pyrrolopyrrole organo-tin compound structure such as formula IV
It is shown:
Wherein, R4For H atom, the straight chained alkyl or branched alkyl of C1-C60；R5For oxygen atom, sulphur atom or imido grpup；R6
For furans and two furans, union II furans, three furans, tetrad furans, thiophene, 1,4-Dithiapentalene, union II thiophene, terthienyl, four
Bithiophene, 3,4- ethene dioxythiophene, selenophen, and two selenophens, union II selenophen, three selenophens, tetrad selenophen, aromatic radical, itrile group,
Nitro-derivative, fluorine-containing thiophene, fluorine-containing furans, fluorine-containing selenophen, phenyl, 1- naphthalene or 2- naphthalene；R8For 3 methyl or 3 fourths
Base.
Further, in preferred embodiments of the present invention, the detailed process of above-mentioned steps (2) are as follows: under room temperature, will
Oxidant is added after the dissolution of pyrrolopyrrole class organic semiconducting materials, reacts 10min~20min；Wherein, pyrrolopyrrole class
The molar ratio of organic semiconducting materials and oxidant is 1:(50~70).
Preferably, the above-mentioned reaction time is 10min, 12min, 14min, 15min, 16min, 18min or 20min.Pyrroles
And the molar ratio of pyroles organic semiconducting materials and oxidant such as 1:50,1:55,1:60,1:65 or 1:70.
Preferably, oxidant includes brown lead oxide, sodium bismuthate, periodic acid, cobalt trifluoride or Na2Fe04.
The above-mentioned pyrrolopyrrole class organic semiconducting materials containing free radical are preparing answering in narrowband photodetector
With.
Preferably, the pyrrolopyrrole class organic semiconducting materials containing free radical are in organic field effect tube, You Jitai
Application on the photoelectric devices such as positive energy battery.
The invention has the following advantages:
1, the aromatic radical or heteroaryl perfume base of the invention by pyrrolopyrrole chemical structure replaces with five yuan containing O, S or Se
Heterocycle, and pyrrolopyrrole class organic semiconducting materials are generated by reacting with monomer I or monomer I ' containing phenol or benzenethiol,
Under the action of oxidant by pyrrolopyrrole class organic semiconducting materials chemical structure containing the hydroxyl on phenol or benzenethiol
Base or sulfhydryl oxidase are at benzene oxygen radical or benzene Thiyl Radical, to obtain the pyrrolopyrrole class organic semiconductor containing free radical
Material.This pyrrolopyrrole class organic semiconducting materials containing free radical has the advantages that performance is stable, and pyrrolopyrrole class
After organic semiconducting materials are by being oxidized to free radical, red shift occurs for spectrum, and molecule molar absorption coefficient improves a lot；
And it is absorbed by force and absorption wavestrip is narrow, and absorbing wavelength can be used for other devices such as narrowband photodetector up near infrared band
Part.
2, the present invention introduces phenylol or benzenethiol group by monomer I or monomer I ' in pyrrolopyrrole structure,
The phenyl ring wherein introduced extends the conjugated system of its total, and the electron motion range on free radical expands, entire molecule
Energy tends towards stability.Overlapped between track, electronics is transported on the entire molecular skeleton that the multiple atoms for participating in bonding are formed
It is dynamic, pi bond is formed, additionally due to the extension of conjugate length, π-π interorbital energy difference can be reduced, and so as to spaced reduction, be caused
Red shift occurs for the increase of absorption spectrum wavelength when electron transition, absorption spectrum.In addition, in I ' chemical structure of monomer I or monomer
R1And R2Phenoxy group can also be rolled into a ball or protection is played the role of by thiophenyl group, to also improve the pyrrolopyrrole containing free radical
The stability of class organic semiconducting materials.
3, the present invention also introduces the five-ring heterocycles containing O, S or Se in pyrrolopyrrole chemical structure, thus in preparation
O, S or Se atom are introduced in pyrrolopyrrole class organic semiconducting materials containing free radical, due to the work between O, S or Se atom
With, so that it is conducive to packing of molecules under solid states, to improve the pyrrolopyrrole class organic semiconductor containing free radical
The electronic transmission performance of material.
4, comprising opening shell state and closed shell in the pyrrolopyrrole class organic semiconducting materials prepared by the present invention containing free radical
State, the pyrrolopyrrole class organic semiconducting materials structure of closed shell state is as shown in formula V:
It can be calculated according to density functional theory (DFT), the ratio for opening shell state is 33%~37%, and surplus is closed shell
State.Wherein open that shell state proportion is small (being less than 50%), the suction of the pyrrolopyrrole class organic semiconducting materials containing free radical
Receiving spectrum can reach near infrared band；And it is small due to opening shell state proportion, the pyrrolopyrrole class containing free radical is organic partly to be led
Body stability of material is higher.There is unpaired electron to deposit on the free radical of pyrrolopyrrole class organic semiconducting materials containing free radical
It is being more advantageous to electric current transmission, the sensitivity of detection can be improved.The generation of closed shell state is organic due to being located at pyrrolopyrrole class
Two electronics at both ends move on entire molecular skeleton in semiconductor material structures, can form the knot of entirety conjugation
Structure.It is closed shell state with a conjugated structure and free-radical contents to open that shell state is not high, so that the pyrrolo- pyrrole that the present invention obtains
The energy for coughing up class organic semiconducting materials totally tends towards stability, therefore the stability of pyrrolopyrrole class organic semiconducting materials is very
It is good.And the closed shell state that diradical pyrrolopyrrole class organic semiconducting materials of the invention are formed, efficiently avoids list
Only one electronics of free sill and the case where without closed shell state；Additionally due to the organic semiconducting materials free radical of single free radical
Content is relatively high, and there is also the problems of stability difference.
5, the pyrrolopyrrole class organic semiconducting materials prepared by the present invention containing free radical, electron mobility is high, divides
Sub- stability is good, absorption intensity is high and absorption wavestrip is narrow, and absorbing wavelength reaches near infrared band, can be used for near-infrared, narrow band light
The free sill of the devices such as electric explorer, organic field-effect tube.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the embodiment of the present invention 1；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the embodiment of the present invention 2；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of the embodiment of the present invention 3；
Fig. 4 is the uv-visible absorption spectroscopy figure of the embodiment of the present invention 1,2 and 3；
Fig. 5 is the variation diagram of the UV absorption intensity under the 400w illumination of the embodiment of the present invention 1,2 and 3；
Fig. 6 is the uv-visible absorption spectroscopy figure after the embodiment of the present invention 1 is placed 16 weeks；
Fig. 7 is the uv-visible absorption spectroscopy figure after the embodiment of the present invention 2 is placed 16 weeks；
Fig. 8 is the uv-visible absorption spectroscopy figure after the embodiment of the present invention 3 is placed 16 weeks；
Fig. 9 be the embodiment of the present invention 2 prepare photoelectric detector at 650nm photoresponse current graph；
Figure 10 be the embodiment of the present invention 2 prepare photoelectric detector at 780nm photoresponse current graph；
Figure 11 be the embodiment of the present invention 2 prepare photoelectric detector at 808nm photoresponse current graph；
Figure 12 is the mobility test chart of the embodiment of the present invention 2；
Figure 13 is the channel current-source-drain voltage change curve of the embodiment of the present invention 2.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
The present invention is will to mix pyrrolopyrrole halides and its derivative with monomer I, or pyrrolopyrrole is organic
Tin compound is mixed with monomer I ', obtains pyrrolopyrrole class organic semiconducting materials, then to pyrrolopyrrole class organic half
Oxidant mixing is added in conductor material, obtains the pyrrolopyrrole class organic semiconducting materials containing free radical.Pyrrolopyrrole
Halides and its derivative and monomer I and pyrrolopyrrole organo-tin compound and monomer I ' finally obtain the pyrrole containing free radical
Simultaneously pyroles organic semiconducting materials are coughed up, reaction process is respectively as shown in reaction route I and II:
React route I:
React route II:
Embodiment 1
The preparation method of the present embodiment is carried out according to above-mentioned reaction route I, the pyrrolopyrrole halo derivatives knot of use
In structure formula, R4For 2- octane dodecyl；R5For oxygen atom, R6For furans；X is Br.In I structural formula of monomer, R1For tert-butyl；R2
For tert-butyl；R3For hydroxyl；R7It is 1,3,2- dioxane, penta boron, 4,4,5,5- tetramethyls.
The preparation method of the pyrrolopyrrole class organic semiconducting materials containing free radical of the present embodiment, comprising:
(1) pyrrolopyrrole halo derivatives, monomer I, tetrakis triphenylphosphine palladium, three (o-methyl-phenyl) phosphines, four are added
Butyl ammonium hydroxide and water are condensed back in toluene solvant under 120 DEG C of reaction temperatures anti-in inert gas atmosphere protection
12h is answered, pyrrolopyrrole class organic semiconducting materials are obtained.Wherein, pyrrolopyrrole halo derivatives, monomer I, four (triphens
Base phosphine) palladium, molar ratio of three (o-methyl-phenyls) between phosphine and tetrabutylammonium hydroxide be 1:2.6:0.075:0.2, water plus
Enter the 0.3wt% that amount is pyrrolopyrrole halo derivatives.
(2) under room temperature, dioxy is added after pyrrolopyrrole class organic semiconducting materials being dissolved in methylene chloride
Change lead and react 15min, obtains the pyrrolopyrrole class organic semiconducting materials containing free radical.Wherein, pyrrolopyrrole class is organic
The molar ratio of semiconductor material and brown lead oxide is 1:60.
Embodiment 2
The preparation method of the present embodiment is carried out according to above-mentioned reaction route I, the pyrrolopyrrole halo derivatives knot of use
R in structure formula4For 2- octane dodecyl；R5For oxygen atom；R6For thiophene；X is Br.In I structural formula of monomer, R1For tert-butyl；R2
For tert-butyl；R3For hydroxyl；R7It is 1,3,2- dioxane, penta boron, 4,4,5,5- tetramethyls.
The preparation method of the pyrrolopyrrole class organic semiconducting materials containing free radical of the present embodiment, comprising:
(1) pyrrolopyrrole halo derivatives, monomer I, tetrakis triphenylphosphine palladium, three (o-methyl-phenyl) phosphines, four are added
Butyl ammonium hydroxide and water are condensed back in toluene solvant under 120 DEG C of reaction temperatures anti-in inert gas atmosphere protection
12h is answered, pyrrolopyrrole class organic semiconducting materials are obtained.Wherein, pyrrolopyrrole class organic semiconducting materials, monomer I, four
(triphenylphosphine) palladium, molar ratio of three (o-methyl-phenyls) between phosphine and tetrabutylammonium hydroxide are 1:2.6:0.075:0.2, water
Additional amount be pyrrolopyrrole class organic semiconducting materials 0.3wt%.
(2) under room temperature, dioxy is added after pyrrolopyrrole class organic semiconducting materials being dissolved in methylene chloride
Change lead, reacts 15min, obtain the pyrrolopyrrole class organic semiconducting materials containing free radical.Wherein, pyrrolopyrrole class is organic
The molar ratio of semiconductor material and brown lead oxide is 1:60.
Embodiment 3
The preparation method of the present embodiment is carried out according to above-mentioned reaction route I, the pyrrolopyrrole halo derivatives knot of use
In structure formula, R4For 2- octane dodecyl；R5For oxygen atom；R6For selenophen；X is Br.In I structural formula of monomer, R1For tert-butyl；R2
For tert-butyl；R3For hydroxyl；R7It is 1,3,2- dioxane, penta boron, 4,4,5,5- tetramethyls.
The preparation method of the pyrrolopyrrole class organic semiconducting materials containing free radical of the present embodiment, comprising:
(1) pyrrolopyrrole halo derivatives, monomer I, tetrakis triphenylphosphine palladium, three (o-methyl-phenyl) phosphines, four are added
Butyl ammonium hydroxide and water are condensed back in toluene solvant under 120 DEG C of reaction temperatures anti-in inert gas atmosphere protection
12h is answered, pyrrolopyrrole class organic semiconducting materials are obtained.Wherein, pyrrolopyrrole halo derivatives, monomer I, four (triphens
Base phosphine) palladium, molar ratio of three (o-methyl-phenyls) between phosphine and tetrabutylammonium hydroxide be 1:2.6:0.075:0.2, water plus
Enter the 0.3wt% that amount is pyrrolopyrrole halo derivatives.
(2) under room temperature, dioxy is added after pyrrolopyrrole class organic semiconducting materials being dissolved in methylene chloride
Change lead and react 15min, obtains the pyrrolopyrrole class organic semiconducting materials containing free radical.Wherein, pyrrolopyrrole class is organic
The molar ratio of semiconductor material and brown lead oxide is 1:60.
Embodiment 4
The preparation method of the present embodiment is carried out according to above-mentioned reaction process I, the pyrrolopyrrole halides structural formula of use
In, R4For H atom；R5For sulphur atom；R6For 3,4- difluoro thiophene；X is Br.In I structural formula of monomer, R1For phenyl ring；R2For thiophene；
R3For hydroxyl；R7For 2- allyl -4,4,5,5- tetramethyl -1,3,2- dioxaborolanes.
The preparation method of the pyrrolopyrrole class organic semiconducting materials containing free radical of the present embodiment, comprising:
(1) be added pyrrolopyrrole halides, monomer I, bis- (triphenylphosphine) palladium chlorides, tri-tert-butylphosphine, potassium carbonate and
Water is condensed back reaction 14h in toluene solvant under 90 DEG C of reaction temperatures in inert gas atmosphere protection, obtains pyrrolo-
Pyroles organic semiconducting materials.Wherein, pyrrolopyrrole halides, monomer I, bis- (triphenylphosphine) palladium chlorides, tri-tert
Molar ratio between phosphine and potassium carbonate is 1:4:0.1:0.4:4, and the additional amount of water is the 0.4wt% of pyrrolopyrrole halides.
(2) under room temperature, sodium bismuthate is added after methylene chloride dissolution in pyrrolopyrrole class organic semiconducting materials,
20min is reacted, the pyrrolopyrrole class organic semiconducting materials containing free radical are obtained.Wherein, pyrrolopyrrole class is organic partly leads
The molar ratio of body material and sodium bismuthate is 1:50.
Embodiment 5
The preparation method of the present embodiment is carried out according to above-mentioned reaction route II, the pyrrolopyrrole organo-tin compound of use
R in structural formula4For 2- butane dodecyl；R5For sulphur atom；R6For 3,4- difluoro furans；R8For 3 methyl.I ' structure of monomer
In formula, R1For thiophene；R2For furans；R3For sulfydryl；R7' it is Cl.
The preparation method of the pyrrolopyrrole class organic semiconducting materials containing free radical of the present embodiment, comprising:
(1) pyrrolopyrrole organo-tin compound, monomer I ', tetrakis triphenylphosphine palladium and triphenylphosphine is added, in inertia
It is condensed back reaction 12h in gas atmosphere protection in toluene solvant under 120 DEG C of reaction temperatures, obtaining pyrrolopyrrole class has
Machine semiconductor material.Wherein, between pyrrolopyrrole organo-tin compound, monomer I ', tetrakis triphenylphosphine palladium and triphenylphosphine
Molar ratio be 1:3:0.1:0.4.
(2) under room temperature, periodic acid is added after methylene chloride dissolution in pyrrolopyrrole class organic semiconducting materials,
10min is reacted, the pyrrolopyrrole class organic semiconducting materials containing free radical are obtained.Wherein, pyrrolopyrrole class is organic partly leads
The molar ratio of body material and periodic acid is 1:70.
The pyrrolopyrrole class organic semiconducting materials containing free radical through detection Examples 1 to 5 preparation, material molecule are steady
Qualitative good, absorption intensity is high and absorbs that wavestrip is narrow, and absorbing wavelength is up near infrared band.
Interpretation of result
Pyrrolopyrrole class organic semiconducting materials prepared by embodiment 1,2 and 3 are tested for the property, and are divided
Analysis.
Interpretation of result 1
Pyrrolopyrrole class organic semiconducting materials containing free radical prepared by embodiment 1,2 and 3 are black solid, will
It is configured to solution, and solution is in green.
Embodiment 1,2 and 3 prepare the pyrrolopyrrole class organic semiconducting materials containing free radical using nucleus magnetic hydrogen spectrum into
Row analysis, obtains the nucleus magnetic hydrogen spectrum figure of embodiment 1,2 and 3, as shown in Figure 1,2 and 3.
The pyrrolopyrrole class organic semiconducting materials containing free radical of embodiment 1,2 and 3 can be determined from FIG. 1 to FIG. 3
Molecular formula, may indicate that pyrrolopyrrole class organic semiconducting materials containing free radical and implement prepared by embodiment 1,2 and 3
Target product prepared by example 1,2 and 3 is consistent.
Interpretation of result 2
Pyrrolopyrrole class organic semiconducting materials containing free radical prepared by embodiment 1,2 and 3 are configured to 10-5mol/
The solution of L, and uv-visible absorption spectroscopy test is carried out, obtain the uv-visible absorption spectroscopy of embodiment 1,2 and 3
Figure, as shown in Figure 4.
From fig. 4, it can be seen that under same concentrations, the pyrrolopyrrole class containing free radical of embodiment 1,2 and 3 organic half
Conductor material λmaxRespectively 749nm, 781nm, 773nm, the absorption bands of three are between 600-800nm, absorption bands
It is narrow, and all 1000nm or so attenuation by absorption be 0.And it can be seen from the figure that embodiment 1 the pyrrolo- pyrrole containing free radical
Cough up that class organic semiconducting materials absorption intensity is most strong, the pyrrolopyrrole class organic semiconducting materials containing free radical of embodiment 2
λmaxIt is maximum.
Interpretation of result 3
The pyrrolopyrrole class organic semiconducting materials containing free radical of embodiment 1,2 and 3 are configured to 10-3Mol/L's
Solution, and drip and film is made by spin coating on the glass sheet.Under 400w light source, film is placed in and is irradiated at light source 20cm
100h observes the film of embodiment 1,2 and 3 in respective λmaxThe variation for locating UV absorption intensity, obtains embodiment 1,2 and 3
The variation diagram of UV absorption intensity under 400w illumination, as shown in Figure 5.
From fig. 5, it can be seen that embodiment 1,2 and 3 is in respective λmaxPlace irradiated through 100h after UV Change of absorption very
It is small, illustrate film good light stability made of embodiment 1,2 and 3, to also illustrate 1,2 and 3 pyrroles containing free radical of embodiment
And the good light stability of pyroles organic semiconducting materials.
Interpretation of result 4
The pyrrolopyrrole class organic semiconducting materials containing free radical of embodiment 1,2 and 3 are each configured to 10-5mol/
The solution of L, and drip and film is made by spin coating on the glass sheet.Film is placed in air, by 16 weeks later again to film
Uv-visible absorption spectroscopy test is carried out, the uv-visible absorption spectroscopy after placing embodiment 1,2 and 3 16 weeks is obtained
Figure, as shown in Fig. 6, Fig. 7 and Fig. 8.
It can be seen that the pyrrolopyrrole class organic semiconductor containing free radical of embodiment 1,2 and 3 from Fig. 6, Fig. 7 and Fig. 8
Material place in air 16 weeks after absorption spectrum compared with the absorption spectrum tested before its vary less, illustrate reality
Apply that film-air stability made of example 1,2 and 3 is good, to also illustrate pyrrolopyrrole class of the embodiment 1,2 and 3 containing free radical
The stability of organic semiconducting materials is good.
Interpretation of result 5
The pyrrolopyrrole class organic semiconducting materials containing free radical of embodiment 2 are configured to 10-5The solution of mol/L,
And by its drop coating in photoelectric detector electrode surface, after solvent volatilization completely after, respectively in 650nm, 780nm and 808nm
Its photoresponse electric current is measured under light source, the photoresponse current graph of the photoelectric detector of the preparation of embodiment 2 is obtained, such as Fig. 9, Figure 10
With shown in Figure 11.
The photoelectric detector that is prepared by embodiment 2 be can be seen that from Fig. 9, Figure 10 and Figure 11 in 650nm, 780nm and
Photocurrent response can be detected under 808nm light source, measuring photoelectric current size under 650nm is about to measure photoelectricity under 17 μ a, 780nm
Stream size is that electric current has reached 35 μ a under 13 μ a, 808nm.And response wave band is relatively narrow, can be applied to precisely detect.
Interpretation of result 6
The pyrrolopyrrole class organic semiconducting materials containing free radical of embodiment 2 are configured to 10-5The solution of mol/L,
Drop coating is in transistor surface.Wherein, transistor arrangement is bottom gate bottom contact structures, on a si substrate thermally grown one layer of 285nm
SiO2As dielectric layer, 2nmCr and 30nmAu is deposited, for Au as drain-source electrodes, Cr is as adhesion layer.
Mobility test is carried out in the case where source-drain voltage is the bias of 80V, wherein grid voltage sweeps to 60V from -10V, obtains
To as shown in figure 12.And when grid voltage (Vg) is respectively 0V, 20V, 40V and 60V, channel current is changed with source-drain voltage
It is tested, obtains change curve and obtain as shown in figure 13.The pyrrolopyrrole class organic semiconductor containing free radical of embodiment 2
Material shows as N-shaped in the transistor, be fitted electron mobility be 3.36 × 10-3cm2/V·s。
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of pyrrolopyrrole class organic semiconducting materials containing free radical, which is characterized in that its molecular structure such as I institute of formula
Show:
In formula:
R1For tert-butyl, aromatic radical or heterocyclic aromatic base；
R2For tert-butyl, aromatic radical or heterocyclic aromatic base；
R3For oxygen atom or sulphur atom；
R4For H atom, the straight chained alkyl or branched alkyl of C1-C60；
R5For oxygen atom, sulphur atom or imido grpup；
R6For furans and two furans, union II furans, three furans, tetrad furans, thiophene, 1,4-Dithiapentalene, union II thiophene, three thiophenes
Pheno, four bithiophenes, 3,4- ethene dioxythiophene, selenophen, and two selenophens, union II selenophen, three selenophens, tetrad selenophen, aromatic radical,
Itrile group, nitro-derivative, fluorine-containing thiophene, fluorine-containing furans, fluorine-containing selenophen, phenyl, 1- naphthalene or 2- naphthalene.
2. a kind of preparation method of the pyrrolopyrrole class organic semiconducting materials containing free radical characterized by comprising
(1) pyrrolopyrrole halides and its derivative are mixed with monomer I, or by pyrrolopyrrole organo-tin compound and list
Body I ' mixes, and obtains pyrrolopyrrole class organic semiconducting materials；
I structure of monomer is as shown in formula II:
Wherein, R1For tert-butyl, aromatic radical or heterocyclic aromatic base；R2For tert-butyl, aromatic radical or heterocyclic aromatic base；R3For hydroxyl
Or sulfydryl；R7For fragrant ylboronic acid, ene boric acid, aromatic radical borate or ene boric acid ester；
I ' structure of monomer such as formula II ' is shown:
Wherein, R1For tert-butyl, aromatic radical or heterocyclic aromatic base；R2For tert-butyl, aromatic radical or heterocyclic aromatic base；R3For hydroxyl
Or sulfydryl；R7' it is halogen；
(2) oxidant mixing is added into pyrrolopyrrole class organic semiconducting materials, obtains the pyrrolopyrrole containing free radical
Class organic semiconducting materials.
3. the preparation method of the pyrrolopyrrole class organic semiconducting materials according to claim 2 containing free radical, special
Sign is, the detailed process of pyrrolopyrrole class organic semiconducting materials is prepared in step (1) are as follows: it is halogenated that pyrrolopyrrole is added
Object and its derivative, monomer I, palladium catalyst, Phosphine ligands, alkali solid and water, it is anti-at 90 DEG C~120 DEG C in inert gas atmosphere
Reaction 10h~14h is condensed back at a temperature of answering in the solvent of toluene or dioxane；
Wherein, the molar ratio between pyrrolopyrrole halides and its derivative, monomer I, palladium catalyst, Phosphine ligands and alkali solid
For 1:(2.2~4): (0.05~0.1): (0.15~0.4): (3~4), the additional amount of water be pyrrolopyrrole halides and its
0.2wt%~0.4wt% of derivative；Alkali solid includes tetrabutylammonium hydroxide, potassium carbonate or cesium carbonate.
4. the preparation method of the pyrrolopyrrole class organic semiconducting materials according to claim 2 containing free radical, special
Sign is that pyrrolopyrrole halides and its derivant structure are as shown in formula III:
Wherein, R4For H atom, the straight chained alkyl or branched alkyl of C1-C60；R5For oxygen atom, sulphur atom or imido grpup；R6For furan
It mutters, and two furans, union II furans, three furans, tetrad furans, thiophene, 1,4-Dithiapentalene, union II thiophene, terthienyl, tetrad thiophene
Pheno, 3,4- ethene dioxythiophene, selenophen and two selenophens, union II selenophen, three selenophens, tetrad selenophen, aromatic radical, itrile group, nitro
Derivative, fluorine-containing thiophene, fluorine-containing furans, fluorine-containing selenophen, phenyl, 1- naphthalene or 2- naphthalene；X is halogen.
5. the preparation method of the pyrrolopyrrole class organic semiconducting materials according to claim 2 containing free radical, special
Sign is, the detailed process of pyrrolopyrrole class organic semiconducting materials is prepared in step (1) are as follows: it is organic that pyrrolopyrrole is added
Tin compound, monomer I ', palladium catalyst and Phosphine ligands, in inert gas atmosphere protection under 80 DEG C~120 DEG C reaction temperatures
Reaction 6h~10h is condensed back in dry and the toluene of deoxygenation or the solvent of tetrahydrofuran；
Wherein, the molar ratio between pyrrolopyrrole organo-tin compound, monomer I ', palladium catalyst and Phosphine ligands be 1:(2~
3): (0.05~0.1): (0.15~0.4).
6. the preparation method of the pyrrolopyrrole class organic semiconducting materials according to claim 2 containing free radical, special
Sign is that pyrrolopyrrole organo-tin compound structure is as shown in formula IV:
Wherein, R4For H atom, the straight chained alkyl or branched alkyl of C1-C60；R5For oxygen atom, sulphur atom or imido grpup；R6For furan
It mutters, and two furans, union II furans, three furans, tetrad furans, thiophene, 1,4-Dithiapentalene, union II thiophene, terthienyl, tetrad thiophene
Pheno, 3,4- ethene dioxythiophene, selenophen and two selenophens, union II selenophen, three selenophens, tetrad selenophen, aromatic radical, itrile group, nitro
Derivative, fluorine-containing thiophene, fluorine-containing furans, fluorine-containing selenophen, phenyl, 1- naphthalene or 2- naphthalene；R8For 3 methyl or 3 butyl.
7. according to the preparation side of the described in any item pyrrolopyrrole class organic semiconducting materials containing free radical of claim 2-6
Method, which is characterized in that the detailed process of step (2) are as follows: under room temperature, pyrrolopyrrole class organic semiconducting materials are dissolved
After be added oxidant, react 10min~20min；Wherein, the molar ratio of pyrrolopyrrole class organic semiconducting materials and oxidant
For 1:(50~70).
8. the pyrrolopyrrole class organic semiconducting materials described in claim 1 containing free radical are preparing narrowband photodetector
In application.
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