CN105859681A - Selenophene vinyl compounds and organic conjugated material thereof, and preparation method of organic conjugated material - Google Patents
Selenophene vinyl compounds and organic conjugated material thereof, and preparation method of organic conjugated material Download PDFInfo
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Abstract
The embodiment of the invention relates to selenophene vinyl compounds and an organic conjugated material thereof, and a preparation method of the organic conjugated material. The structural general formula of the selenophene vinyl compounds is disclosed in the specification, wherein Et is ethyl. The structural general formula of the organic conjugated material of the selenophene vinyl compounds is disclosed in the specification, wherein A is an aromatic conjugated unit with different electron donating and receiving capacities, n is polymerization degree and is any whole number ranging from 2 to 100. The selenophene vinyl compounds are prepared from selenophene, n-butyllithium, hexacarbonyl chromium, triethoxytetrafluoro borate and tetra(triphenylphosphine) palladium by olefin double-decomposition reaction in an organic solvent. The corresponding organic conjugated material is prepared by still coupled reaction. The preparation method provided by the invention has the advantages of simple route, fewer steps and low production cost.
Description
Technical field
The present invention relates to a kind of selenium phenol vinyl compound, particularly relate to a kind of selenium phenol vinyl compound and organic
Conjugated material and its preparation method.
Background technology
Conjugation organic semiconducting materials is with a wide range of applications in fields such as organic photoelectrics, studies its synthesis
Methodology is extremely important to designing and synthesizing high performance conjugation organic semiconducting materials.At organic solar
Battery research aspect, synthesis of narrow band gap, wide absorption, the organic polymer donor material of high hole mobility
It is one of design and the synthesized high-performance conjugation significant challenge that faces of organic semiconducting materials.Selenium in selenium phenol
Atomic radius is big, and electronegativity is little, and polarizability is strong, utilizes selenium phenol structure conjugation organic semiconducting materials to have
It is beneficial to the delocalization of electric charge, obtains the absorption of the organic semiconducting materials of narrow band gap, beneficially sunlight, carry
High photoelectric current.It addition, selenium atom is prone to polarization, there is the strongest Se-Se intermolecular force, favorably
Shift in intramolecular electric charge, carrier mobility can be effectively improved, reduce the compound of carrier.?
Closely, the research containing selenium phenols organic polymer achieves some good achievements.Luping Yu etc. synthesize
One class selenium phenol selenium phenol polymer (PSeBx), its band gap is 1.78ev, bulk heterojunction organic solar electricity
The photoelectric transformation efficiency 6.87% (ACS Macro Lett.2012,1,361-365) in pond.Alex K.-Y.Jen
Etc. having synthesized the conjugated polymer (PlDSe-DFBT) of two selenium phenol benzo two indene derivative, its band gap is
1.8ev, the photoelectric transformation efficiency 6.8% (Chem of bulk heterojunction organic solar batteries
Mater.2013,25,3188-3195) but. the synthesis of above selenium phenols organic polymer have one common
Point, is all to form fused ring compound by covalent bond to improve conjugation organic half by functional group being coupled
The coplanarity (Chem.Rev.1992,92,711-38) of conductor material.The shortcoming of this method is
Synthesis step is complicated, and the production cost of material is high.Therefore, a kind of synthesis step of exploitation is few, production cost
Low synthetic method is extremely important to designing and synthesizing high performance selenium phenols conjugation organic semiconducting materials.
Current olefin metathesis polyreaction is mainly used to synthesize homopolymer, and at organic semiconductor
Field widely used co-polymer then shorter mention；It is therefore believed that development olefin metathesis polymerization
Reacting the application in the conjugation organic semiconducting materials co-polymer containing selenium phenols synthesizes will be to organic semiconductor
Certain facilitation is played in the development in field.
Present invention polyreaction based on olefin metathesis reaction introduces in conjugated molecule has " conformation lock "
The supermolecular mechanism power of function, such as, the effect of the non-bonding between oxygen-selenium, nitrogen-sulfur and fluoro-sulphur atom
Power, build increase coplanarity " conformation lock " (J.Am.Chem.Soc.2013,135,
10475-10483), a kind of selenium phenol vinyl compound and having containing selenium phenol vinyl compound structure have been synthesized
Machine conjugated material.Have an advantage in that the mult-step synthetic sequence both avoiding complexity, reduce the production of material
Cost, improves again the coplanarity of conjugated structure, obtained a class narrow band gap, wide absorb organic poly-
Compound semi-conducting material.
Summary of the invention
It is an object of the invention to provide a kind of selenium phenol vinyl compound and containing selenium phenol vinyl compound structure
Organic conjugate material and its preparation method.
For achieving the above object, in first aspect, the invention provides a kind of described selenium phenol vinyl compound
General structure such as formula (I) shown in；
Described Et is ethyl.
In second aspect, the invention provides the selenium phenol shown in formula (I) that a kind of above-mentioned first aspect provides
The method of vinyl compound, comprises the following steps；
Utilize olefin metathesis reaction, in organic solvent, first by the preparation of compounds of formula shown in formula (Y)
(Z) intermediate product shown in, then prepared the selenium shown in formula (I) by the intermediate product shown in formula (Z)
Phenol vinyl compound, wherein Et is ethyl.
Preferably, described method also includes using selenium phenol vinyl compound described in silica gel column chromatography separating-purifying.
Preferably, also include during the intermediate product shown in preparation of compounds of formula (Z) shown in formula (Y):
Add n-BuLi, Cr (CO)6, triethoxy tetrafluoroborate prepares metal carbene intermediate.
Preferably, also include during the intermediate product shown in preparation of compounds of formula (Z) shown in formula (Y):
Add tetrakis triphenylphosphine palladium catalytic metal Cabbeen intermediate and prepare selenium phenol vinyl compound.
Preferably, described organic solvent is: the one in oxolane or dichloromethane.
Preferably, the compound shown in described formula (Y) and n-BuLi, Cr (CO)6, triethoxy four
The ratio of the amount of borofluoride material is 1:1.2:1:1.3.
Preferably, the intermediate product shown in formula (Z) the selenium phenol vinyl compound shown in formula (I) is prepared
During add four (triphenyl phosphorus) palladium make catalyst.
Preferably, the mass ratio of the intermediate product shown in described formula (Z) and four (triphenyl phosphorus) palladium is:
1:0.3。
In the third aspect, the invention provides the selenium phenol shown in formula (I) that a kind of above-mentioned first aspect provides
Shown in the general structure such as formula (II) of the organic conjugate material of vinyl compound:
Described A is to have difference to the aromatic conjugated unit by electronic capability, and n is the degree of polymerization, for 2-100
Any integer；
Wherein, the structural formula of described A is formula (I I I-1) to any one in formula (I I I-18):
Described formula (III-1) in formula (III-18), R1It is the alkyl of 1-20 for carbon number, alcoxyl
Base or H atom, R2For alkyl that carbon number is 1-20 or alkoxyl, Y is H atom or F atom.
The present invention utilizes olefin metathesis reaction to synthesize a kind of selenium phenol vinyl compound, and at this selenium phenol
Class phenol ethylene chemical combination on selenium has been synthesized further with still coupled reaction on the basis of vinyl compound
The organic conjugate material of thing structure.Utilize olefin metathesis reaction to prepare selenium phenol vinyl compound and there is synthesis
Route is simple, and synthesis step is few, the advantage that the production cost of material is low.Prepared selenium phenol ethylene chemical combination
The organic conjugate material of thing structure is the organic semiconducting materials of a class narrow band gap, it is anticipated that this type of material
Will have wide practical use in organic photoelectric field.
Accompanying drawing explanation
The ultra-violet absorption spectrum of the polymer P NDI SVSOET film that Fig. 1 provides for the embodiment of the present invention；
The cyclic voltammetry curve of the polymer P NDI SVSOET that Fig. 2 provides for the embodiment of the present invention；
The uv absorption light of the polymer P ffBT2T-30T-SVSOET film that Fig. 3 provides for the embodiment of the present invention
Spectrum；
The cyclic voltammetric of the polymer P ffBT2T-30T-SVSOET that Fig. 4 provides for the embodiment of the present invention is bent
Line；
The ultra-violet absorption spectrum of the polymer P DPP2TSVSOET film that Fig. 5 provides for the embodiment of the present invention；
The cyclic voltammetry curve of the polymer P DPP2TSVSOET that Fig. 6 provides for the embodiment of the present invention.
Detailed description of the invention
Below by drawings and Examples, technical scheme is described in further detail.Need
Being noted that following embodiment is not limiting the scope of the invention, any invention is in the present invention
On the basis of the improvement made and change all within protection scope of the present invention.
Embodiment one
Present embodiments provide a kind of selenium phenol vinyl compound, shown in general structure such as formula (I)；
Described Et is ethyl.
Present embodiments provide that to prepare the method for selenium phenol vinyl compound shown in above-mentioned formula (I) as follows:
Utilize olefin metathesis reaction, in organic solvent, first by the preparation of compounds of formula shown in formula (Y)
(Z) intermediate product shown in, following referred to as intermediate product Z, then prepared formula (X) by intermediate product Z
Shown selenium phenol vinyl compound, wherein Et is ethyl.
The first step: prepared intermediate product Z by the compound shown in formula (Y).
First, under-78 DEG C and nitrogen are protected, n-BuLi (1.8mmol；0.72ml) it is slowly dropped into
Selenium phenol (194mg；In anhydrous THF (20mL) solution 1.5mmol), then heat to 0 DEG C, stir
Mix reaction 30 minutes；And then, under-78 DEG C and nitrogen are protected, Cr (CO) is added6(332
mg；1.5mmol), mixture is warming up to room temperature, reacts 30 minutes；Then, triethyl group oxygen four is taken
Borofluoride (390mg；1.95mmol) it is dissolved in anhydrous CH2Cl2(20ml), in, protect at-78 DEG C and nitrogen
Protect lower by the prepared triethyl group oxygen Tetrafluoroboric acid saline solution above-mentioned reaction bulb of addition, stir reaction 8
Hour.Rotation is evaporated off solvent and obtains crude product, and through silica gel column chromatography, eluant is petroleum ether (PE),
Obtain product red solid 280mg, productivity 50%.
Second step: obtained the selenium phenol vinyl compound shown in formula (X) by intermediate product Z reaction.Middle
Product Z (100mg, 0.26mmol) and Pd (PPh3)4(30mg) anhydrous THF (20mL) it is dissolved in,
Being heated to 80 DEG C to react 17 hours, red solution gradually becomes buff.It is cooled to room temperature, adds
Enter water (50mL) cancellation reaction, CH2Cl2Extraction (3 × 50mL), washes (3 × 50mL), has
Machine phase MgSO4Being dried, be concentrated to give crude product, through silica gel column chromatography, eluant is PE:CH2Cl2=8:
1, obtain colorless crystalline solid 45mg, productivity 90%.
Embodiment two
The present embodiment provides monomer M, and its structural formula is as follows:
The preparation method of monomer M is as follows:
Under-78 DEG C and nitrogen are protected, n-butyllithium solution (0.38mL, 0.94mmol) is slowly dropped into
In anhydrous THF (50mL) solution of compound I (160mg, 0.43mmol), mixture is at-78 DEG C
React 30 minutes, be warming up to room temperature reaction 1 hour；It is cooled to-78 DEG C again, Me3SnCl(0.94mL,0.94
Mmol) it is slowly added dropwise into reaction system, is slowly increased to room temperature, stirring reaction 8 hours.Add KF water-soluble
Liquid cancellation is reacted, CH2Cl2Extraction (3 × 50mL), washes (3 × 50mL), organic facies MgSO4Dry
Dry, it is concentrated to give crude product, recrystallizing methanol obtains red colored crystalline shape solid 211mg, productivity 70%.
Embodiment three
The structure present embodiments providing a kind of conjugated polymer material PNDISVSOET is as follows:
Described conjugated polymer material PNDISVSOET preparation method is as follows:
At N2Under gas shielded, schlenk pipe adds monomer a (128.1mg, 0.13mmol),
Monomer M (91mg, 0.13mmol), Pd2(dba)3(8mg), P (O-Tol)3(11mg), add
Dry toluene (7mL), is heated to 130 DEG C and reacts 48 hours.Add 2-(tributyl tin) thiophene,
130 DEG C are reacted 6 hours；Add 2-iodothiophen, react 6 hours at 130 DEG C, be cooled to room temperature.
Reactant solution is poured into coagulation in methanol (500ml), filters to obtain crude product.Crude product soxhlet extraction
Device is successively with acetone, normal hexane, THF and chloroform. and chloroform extract is concentrated, is deposited in methanol
In obtain dark green solid 106.1mg, productivity 67.9%.
Gained copolymer p NDISVSOET has wider absorption (such as Fig. 1), its band gap at 350-1000nm
For 1.36ev, polymer electrochemical cyclic voltammetry curve is as shown in Figure 2.
Embodiment four
Present embodiments providing a kind of conjugated polymer material PffBT2T-30T-SVSOET, structural formula is as follows:
The synthetic method of described conjugated polymer material PffBT2T-30T-SVSOET is as follows:
At N2Under gas shielded, schlenk pipe adds monomer b (0.051g, 0.047mmol),
Monomer M (0.0329g, 0.047mmol), Pd2(dba)3(6mg), P (O-Tol)3(12mg),
Add anhydrous chlorobenzene (7mL), be heated to 145 DEG C and react 48 hours.Add 2-(tributyl tin) thiophene,
React 6 hours at 130 DEG C；Add 2-bromothiophene, react 6 hours at 130 DEG C, be cooled to room temperature.
Reactant solution is poured into coagulation in methanol (500ml), filters to obtain crude product.Crude product soxhlet extraction
Device is successively with acetone, normal hexane, THF, chloroform and chlorobenzene extracting. and chlorobenzene extract is concentrated, is deposited in
Methanol obtains atrous solid 0.0116g, productivity 19%.
Gained copolymer p ffBT2T-30T-SVSOET has wider absorption (such as Fig. 3) at 400-800nm,
Its band gap is 1.60ev, and polymer electrochemical cyclic voltammetry curve is as shown in Figure 4.
Embodiment five
The present embodiment provides a kind of conjugated polymer material PDPP2TSVSOET, and structural formula is as follows:
Described conjugated polymer material PDPP2TSVSOET preparation method is as follows:
At N2Under gas shielded, schlenk pipe adds monomer c (0.1284g, 0.126mmol),
Monomer M (0.0882g, 0.126mmol), Pd2(dba)3(10mg), P (O-Tol)3(12mg), add
Enter dry toluene (10mL), be heated to 130 DEG C and react 48 hours.Add 2-(tributyl tin) thiophene,
React 6 hours at 130 DEG C；Add 2-iodothiophen, react 6 hours at 130 DEG C, be cooled to room temperature.
Reactant solution is poured into coagulation in methanol (500ml), filters to obtain crude product.Crude product soxhlet extraction
Device is successively with acetone, normal hexane, THF, chloroform. and chloroform extract is concentrated, is deposited in methanol
Obtain blue solid 0.0419g, productivity 26.9%.
Gained copolymer p DPP2TSVSOET has wider absorption (such as Fig. 5) at visible ray 400-900nm,
Its band gap is 1.55ev, and polymer electrochemical cyclic voltammetry curve is as shown in Figure 6.
Embodiment six
The present embodiment provides the organic conjugate material of the selenium phenol vinyl compound described in embodiment 1, and structure is led to
Shown in formula such as formula (II):
Described A is to have difference to the aromatic conjugated unit by electronic capability, and n is the degree of polymerization, for 2-100
Any integer；
Wherein, the structural formula of described A is formula (III-1) to any one in formula (III-18):
Described formula (III-1) in formula (III-18), R1 be carbon number be the alkyl of 1-20, alkoxyl
Or H atom, R2 be carbon number be alkyl or the alkoxyl of 1-20, Y is H atom or F atom.
The organic conjugate material of the present embodiment can use still coupled reaction to prepare.
Above-described detailed description of the invention, is carried out the purpose of the present invention, technical scheme and beneficial effect
Further describe, be it should be understood that the foregoing is only the present invention detailed description of the invention and
, the protection domain being not intended to limit the present invention, all within the spirit and principles in the present invention, done
Any modification, equivalent substitution and improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a selenium phenol vinyl compound, it is characterised in that the general structure of described selenium phenol vinyl compound
As shown in formula I；
Described Et is ethyl.
2. preparing the selenium phenol vinyl compound method shown in formula described in claim 1 (I), it is special
Levy and be, said method comprising the steps of:
Utilize olefin metathesis reaction, in organic solvent, first by the preparation of compounds of formula shown in formula (Y)
(Z) intermediate product shown in, then prepared the selenium shown in formula (I) by the intermediate product shown in formula (Z)
Phenol vinyl compound, wherein Et is ethyl.
Preparation method the most according to claim 2, it is characterised in that described method also includes using
Selenium phenol vinyl compound described in silica gel column chromatography separating-purifying.
Preparation method the most according to claim 2, it is characterised in that the chemical combination shown in formula (Y)
Also include during intermediate product shown in thing formula (Z): add n-BuLi, Cr (CO)6, three second
Epoxide tetrafluoroborate prepares metal carbene intermediate.
Preparation method the most according to claim 2, it is characterised in that the chemical combination shown in formula (Y)
Also include during intermediate product shown in thing formula (Z): add tetrakis triphenylphosphine palladium catalytic metal
Cabbeen intermediate prepares selenium phenol vinyl compound.
Preparation method the most according to claim 2, it is characterised in that described organic solvent is: four
One in hydrogen furan or dichloromethane.
Preparation method the most according to claim 2, it is characterised in that shown in described formula (Y)
Compound and n-BuLi, Cr (CO)6, the mol ratio of triethoxy tetrafluoroborate is 1:1.2:1:1.3.
Preparation method the most according to claim 2, it is characterised in that in shown in formula (Z)
Between product prepare and add four (triphenyl phosphorus) palladium during the selenium phenol vinyl compound shown in formula (I) and urge
Agent.
9. preparation method as claimed in claim 8, it is characterised in that in shown in described formula (Z)
Between the mass ratio of product and four (triphenyl phosphorus) palladium be: 1:0.3.
10. an organic conjugate material based on the selenium phenol vinyl compound described in the claims 1, its
It is characterised by, shown in the general structure such as formula (II) of the organic conjugate material of described selenium phenol vinyl compound:
Described A is to have difference to the aromatic conjugated unit by electronic capability, and n is the degree of polymerization, for 2-100
Any integer；Wherein, what the structural formula of described A was formula (III-1) in formula (III-18) is any
A kind of:
Described formula (III-1) in formula (III-18), R1It is the alkyl of 1-20 for carbon number, alcoxyl
Base or H atom, R2For alkyl that carbon number is 1-20 or alkoxyl, Y is H atom or F atom.
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| KR101821971B1 (en) | 2016-08-26 | 2018-01-26 | 한국과학기술원 | Electron accepting polymer of formed random terpolymer, producing method of the same and inverted type polymer solar cells comprising the same |
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| CN102906892A (en) * | 2010-03-25 | 2013-01-30 | 破立纪元有限公司 | Conjugated polymers and devices incorporating same |
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| CN102906892A (en) * | 2010-03-25 | 2013-01-30 | 破立纪元有限公司 | Conjugated polymers and devices incorporating same |
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| HUI HUANG,ET AL.: "Alkoxy-Functionalized Thienyl-Vinylene Polymers for Field-Effect Transistors and All-Polymer Solar Cells", 《ADV. FUNCT. MATER.》 * |
| HUI HUANG,ET AL.: "Combining Electron-Neutral Building Blocks with Intramolecular "Conformational Locks" Affords Stable, High-Mobility P-and N-Channel Polymer Semiconductors", 《J. AM. CHEM. SOC.》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101821971B1 (en) | 2016-08-26 | 2018-01-26 | 한국과학기술원 | Electron accepting polymer of formed random terpolymer, producing method of the same and inverted type polymer solar cells comprising the same |
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