CN103087056A - Spirofluorene derivative and preparation method and application thereof - Google Patents
Spirofluorene derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a spirofluorene derivative. The structure of the spirofluorene derivative is shown as a formula (I); and in the formula (I), R1, R2, R3 and R4 are end group receptor groups and are independently selected from groups shown as a formula (I-a), a formula (I-b) or a formula (I-c).The spirofluorene derivative has a strong absorbing ability to visible light, and can be used as a small molecular donor material and applied in the field of organic solar energy. The invention also discloses a preparation method for the spirofluorene derivative. The spirofluorene derivative is obtained by using 4,7-dibromobenzothiadiazole and 4-hexyl-2-tributyltin thiophene as initial raw materials through Stille coupling reaction, Vilsmeier-Harker reaction, bromination reaction, Suzuki coupling reaction and Knoevenagel condensation reaction sequentially.
Description
Technical field
The invention belongs to the organic solar battery material technical field, be specifically related to a kind of spiral shell fluorene derivatives and its preparation method and application.
Background technology
Sun power is that the mankind are inexhaustible, nexhaustible, the renewable energy source of cleanliness without any pollution.Solar cell is directly light energy conversion to be become the device of electric energy by photovoltaic effect or Photochemical effects, comprises inorganic solar cell and organic solar batteries.
Organic solar batteries is a kind of novel solar battery of studying, compare with inorganic solar cell, have light weight, inexpensive, solution-processible, high mechanical flexibility, can be made into the advantages such as flexible broad area device, its history can be traced back to 1958, Kearns and Calvin are clipped in magnesium phthalocyanine pigment layer and have supported first organic photoelectric between the different electrode of two work functions and transform device, observed the open circuit voltage of 200mV, compare with inorganic solar cell, electricity conversion is extremely low.Between after this 20 years, organic solar batteries is innovated seldom in the field.
1986, doctor Deng Qingyun of Kodak is with a kind of derivative of four carboxylic base perylenes and the duplicature of copper phthalocyanine composition, two membranes is connected with two electrodes has respectively made organic solar batteries, the electricity conversion of this organic solar batteries reaches 1% left and right, although differ far away with inorganic solar cell, it has been a very large breakthrough.Duplicature essence in this organic solar batteries is a heterojunction, be equivalent to imitate inorganic heterogeneous solar cell with two kinds of organic semiconductor material, the structure of this kind duplicature heterojunction is that an a new direction has been opened up in organic solar batteries research, and this structure remains one of emphasis of organic solar batteries research even to this day.
The duplicature of duplicature heterojunction type organic solar batteries is respectively conduct to body and acceptor, wherein, produce hole-electron pair after absorbing photon as the organic semiconductor material of giving body, electronic injection is in the semiconductor material as acceptor, and the hole is separated with electronics.In this system, electron donor(ED) is p-type, and electron acceptor(EA) is N-shaped, thereby hole and electronics are transferred to respectively on two electrodes, forms photoelectric current.
Solvable type organic small molecule material has clear and definite molecular structure, and monodispersity can repeat the advantages such as synthetic and purification step, prepares one of ideal material of organic solar batteries but become the applying soln processing technology.And the solubility organic molecule is applied to need to have film-forming properties preferably in organic solar batteries, mates with the acceptor material energy level and good consistency arranged.Therefore the arrowband is, the solubility of high mobility is organic is the photovoltaic material that a class has development prospect to the body small molecules.
Spiral shell fluorenes class aromatic compound has larger conjugated system and distinctive spiral shell conjugative effect, this distinctive structural performance causes tangling in solid-state molecular, effectively prevented the formation of crystallization, thereby nearly all this material with amorphous state spirane structure all has higher glass transition temperature, simultaneously can effectively reduce molecular aggregates or excite complex formation, thereby more can effectively improve the optical purity of organic electroluminescence device and stability.Therefore, the synthetic spiral shell fluorene derivatives that can absorb preferably sunlight that makes new advances has important application value.
Summary of the invention
The invention provides a kind of spiral shell fluorene derivatives and its preparation method and application, this spiral shell fluorene derivatives has sorption preferably to visible light, can be used for the small molecules donor material.
A kind of spiral shell fluorene derivatives, its structure is suc as formula shown in (I);
In formula (I), R
1, R
2, R
3And R
4Be the end group acceptor groups, be independently selected from suc as formula the group shown in (I-a), formula (I-b) or formula (I-c):
In formula (I-a), formula (I-b) and formula (I-c), " * " represents link position.
The spiral shell at described spiral shell fluorene derivatives center is fluorene structured is large conjugated structure, this conjugated structure is conducive to occur ionization and provides electronics, this spiral shell fluorene derivatives contains the end group acceptor groups simultaneously, its sucting electronic effect can be strengthened described spiral shell fluorene derivatives effectively, thereby can be applied to the small molecules donor material.
As preferably, described spiral shell fluorene derivatives is Compound I-1, Compound I-2 or Compound I-3;
The structural formula of Compound I-1 is as follows:
The structural formula of Compound I-2 is as follows:
The structural formula of Compound I-3 is as follows:
The symmetrical configuration of these organic compound is easy to preparation and synthetic.
The present invention also provides the preparation method of above-mentioned spiral shell fluorene derivatives, comprises the steps:
(1) under protection of inert gas, under the condition that palladium catalyst exists, the Stille linked reaction occurs in 4,7-dibromo diazosulfide and 4-hexyl-2-tributyl tin thiophene, obtains Compound I I through aftertreatment, and the structure of Compound I I is as follows:
(2) under protection of inert gas, Compound I I and DMF and phosphorus oxychloride are carried out Wei Er David Smail-Haake reaction, obtain compound III through aftertreatment, and the structure of compound III is as follows:
(3) under the lucifuge condition, compound III and N-bromo-succinimide generation bromo-reaction obtain compound IV through aftertreatment, and the structure of compound IV is as follows:
(4) under protection of inert gas, under the condition of palladium catalyst and alkali existence, the Suzuki linked reaction occurs in compound IV and two spiral shell fluorenes tetraboric acid esters in water and organic solvent two-phase system, obtain compound V through aftertreatment, and the structure of compound V is as follows:
The structure of two spiral shell fluorenes tetraboric acid esters is as follows:
(5) under protection of inert gas, under solvent and catalyzer existence condition, compound V and contain acceptor end group monomer the Fei Nageer condensation reaction occurs obtains described spiral shell fluorene derivatives;
The described acceptor end group monomer that contains is at least a in the rich tannin of propane dinitrile, cyanoacetic acid monooctyl ester and 3-ethyl.
This preparation method's operating process is easy to control, and purifies convenient, and the spiral shell fluorene derivatives extinction ability that finally obtains is strong, can effectively satisfy the application requiring of organic solar batteries.
As preferably, the described acceptor end group monomer that contains is the rich tannin of propane dinitrile, cyanoacetic acid monooctyl ester or 3-ethyl, and the reaction conditions in step this moment (5) is easy to control, and product is easy to purify.
In above-mentioned steps, described rare gas element is nitrogen or argon gas.
In step (1), (2), (4) and (5), the purification process that described aftertreatment is adopted is the silica gel chromatography column chromatography.
In step (1), the condition of described Stille linked reaction is known by those skilled in the art.Reaction is carried out in solvent, and solvent is generally toluene, dimethylbenzene or Isosorbide-5-Nitrae-dioxane, is preferably toluene for substrate of the present invention, can make productive rate higher, and consumption fully dissolves raw material and gets final product.Reaction is carried out at the temperature of solvent refluxing.
In step (1), the palladium catalyst of the catalysis Stille linked reaction that described palladium catalyst is well known to those skilled in the art, be preferably tetrakis triphenylphosphine palladium, palladium, Palladous chloride or bi triphenyl phosphorus palladium chloride, be preferably tetrakis triphenylphosphine palladium, with 4,7-dibromo diazosulfide meter, the consumption of described palladium catalyst is 1～20mol%.
In step (1), the consumption of 4-hexyl-2-tributyl tin thiophene is excessive, and is described 4, the mol ratio of 7-dibromo diazosulfide and 4-hexyl-2-tributyl tin thiophene is preferably 1: 2.0～and 2.4.
In step (2), the condition of described Wei Er David Smail-Haake reaction is known by those skilled in the art, when described Compound I I carries out this reaction in backflow in 1,2-ethylene dichloride, has higher productive rate.The consumption of solvent is generally 10～20 times of Compound I I quality.
The mole dosage of described DMF and phosphorus oxychloride about equally, is generally 1.05 times of Compound I I mole dosage.
In step (3), solvent used is chloroparaffin, be preferably trichloromethane or tetrachloromethane, consumption is roughly 20 times of effects of described compound III quality, without strict especially requirement, compare with compound III, the mole dosage of described NBS is excessive slightly, is generally 1～1.2 times of compound III.
Temperature of reaction in step (3) is difficult for too high, generally at room temperature carries out.
As preferably, in step (3), described aftertreatment comprises uses the mixed solvent of trichloromethane and ethanol to carry out recrystallization, when adopting this mixed solvent to carry out recrystallization, the step that can greatly simplify the operation, and the product purity that obtains is high, and be suitable for extensive preparation.
As further preferred, in step (3), in described mixed solvent, the volume ratio of trichloromethane and ethanol is 1: 0.8～1.2.
In step (4), experimental result shows, described Suzuki linked reaction can make productive rate be greatly improved when carrying out in two-phase solvent, and described organic solvent is water-immiscible solvent, is preferably toluene.
In step (4), described Suzuki linked reaction is when carrying out for 100～120 ℃, and productive rate is higher.
In step (4), described palladium catalyst is preferably Pd (PPh
3)
4, described alkali is preferably K
2CO
3, this moment, reaction yield was higher and cost is lower.
In step (4), in molar weight, described compound IV: two spiral shell fluorenes tetraboric acid esters: alkali: palladium catalyst=1: 0.12～0.13: 4 :～6: 0.01～0.1.
In step (5), described catalyzer is basic cpd, is preferably organic bases, and more preferably alkylamine, comprise triethylamine and piperidines, most preferably is triethylamine, and when using triethylamine, reaction has higher yield.
In step (5), described solvent is preferably trichloromethane.
The described mol ratio that contains acceptor end group monomer and described compound V is 4～4.4: 1.
The present invention also provides a kind of small molecule material that is applied to the organic solar batteries field, comprise above-mentioned spiral shell fluorene derivatives, because this spiral shell fluorene derivatives is better to visible Optical Absorption, therefore, can improve described small molecule material to the utilising efficiency of sun power.
Compare with prior art, beneficial effect of the present invention is embodied in:
(1) contain the end group acceptor groups in described spiral shell fluorene derivatives, have sucting electronic effect, can strengthen this spiral shell fluorene derivatives to the receptivity of visible light;
(2) preparation method of described spiral shell fluorene derivatives is easy to control, and the purity of the product that obtains is high, can satisfy the service requirements of organic solar batteries.
Description of drawings
Fig. 1 is the absorption curve of the Compound I that obtains-3 of embodiment 7, and wherein X-coordinate is wavelength, and ordinate zou is absorbancy;
Fig. 2 be the cyclic voltammetry curve of compound (I-3) in dichloromethane solution that obtain of implementation column 7 wherein X-coordinate be voltage, ordinate zou is electric current.
Fig. 3 is the syntheti c route figure of compound V.
Embodiment
Compound I I's is synthetic
Add 4,7-dibromo diazosulfide (8.82g, 30mmol) in 200ml single port bottle, 4-hexyl-2-tributyl tin thiophene (34.29g, 75mmol), N
2Under protection, add Pd (PPh
3)
4(347mg, 0.3mmol) is injected into toluene 110mL, 115 ℃ of backflow 24h.Stopped reaction is cooled to room temperature, adds 150mL water, and chloroform extraction three times merges organic phase, uses anhydrous Na
2SO
4Drying is filtered, be spin-dried for to get thick product, through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=do at 1: 3 eluent) Compound I I (11.67g, 83%).
Its structure is shown below:
Embodiment 2
Synthesizing of compound III
In two mouthfuls of round-bottomed bottles of 250ml, add Compound I I (5.63g, 12mmol), N
2Protection is made a bet and is injected 100mL1, the 2-ethylene dichloride, and N ', N '-dimethyl formamide (0.94mL, 12.6mmol) is made a bet for 0 ℃ and is injected phosphorus oxychloride (1.10mL, 12.6mmol), back flow reaction 12h.Stopped reaction is cooled to room temperature, and reaction solution is poured in the 100mL2M sodium acetate aqueous solution, stirs 2h, chloroform extraction, and anhydrous Na is used in washing twice
2SO
4Drying is filtered, be spin-dried for to get thick product, through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=do at 1: 1 eluent) compound III (5.00g, 84%).
Its structural formula is as follows:
Synthesizing of compound IV
In 150mL single port bottle, compound III (4.52g, 9.1mmol) is dissolved in the 100mL trichloromethane, and NBS (1.72g, 9.56mmol) divides and adds reaction solution five times, room temperature lucifuge reaction 12h.Reaction solution is poured in 200mL water, and chloroform extraction merges organic phase, uses anhydrous Na
2SO
4Drying is filtered, and is spin-dried for to get thick product, and trichloromethane and ethanol (1: 1) recrystallization gets compound IV (5g, 95%).
1H?NMR(400MHz，CDCl
3)：δ10.11(s，1H)，8.07(s，1H)，7.97(d，1H)，7.83(s，1H)，7.80(d，1H)，3.03(t，2H)，2.64(t，2H)，1.81(m，2H)，1.67(m，2H)，1.34-1.44(m，12H)，0.92(m，6H)。
Its structural formula is as follows:
Compound V's is synthetic
Add compound IV (2.76g, 4.8mmol) in 200mL single port bottle, two spiral shell fluorenes tetraboric acid esters (0.49g, 0.6mmol), N
2Under protection, add K
2CO
3(3.31g, 24mmol), Pd (PPh
3)
4(55.5mg, 0.048mmol) is injected into toluene 60mL, water 18mL, 115 ℃ of backflow 24h.Stopped reaction is cooled to room temperature, adds 100mL water, and chloroform extraction three times merges organic phase, uses anhydrous Na
2SO
4Drying is filtered, be spin-dried for to get thick product, through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=do at 3: 1 eluent) compound V (0.142g, 62%).
1H?NMR(400MHz，CDCl
3)：δ10.08(s，4H)，8.04(s，4H)，7.99(s，4H)，7.95(d，4H)，7.91(d，4H)，7.81(d，4H)，7.61(m，4H)，7.02(m，4H)，3.00(t，8H)，2.53(t，8H)，1.73(m，8H)，1.17-1.42(m，56H)，0.91(t，12H)，0.80(t，12H)。
Its structural formula is as follows:
Embodiment 5
Synthesizing of Compound I-1
Add compound V (0.13g, 0.058mmoL) in 25ml single port bottle, propane dinitrile (0.016g, 0.24mmol), N
2Under protection, be injected into trichloromethane 10mL, three triethylamines, room temperature reaction 12h.Stopped reaction adds 20mL water, and chloroform extraction three times merges organic phase, uses anhydrous Na
2SO
4Drying is filtered, be spin-dried for to get thick product, through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=do at 3: 1 eluent) Compound I-1 (0.096g, 67%).
1H?NMR(400MHz，CDCl
3)：δ8.14(s，4H)，8.01(s，4H)，7.96(d，4H)，7.93(d，4H)，7.87(s，4H)，7.81(d，4H)，7.61(d，4H)，7.03(s，4H)，2.82(t，8H)，2.53(t，8H)，1.68(m，8H)，1.18-1.34(m，56H)，0.92(t，12H)，0.80(t，12H)。
Its structural formula is as follows:
Fig. 3 is the route map of above-described embodiment 1～5 synthetic compound V.
Embodiment 6
Synthesizing of Compound I-2
Add compound V (0.30g, 0.13mmol) in 50ml single port bottle, cyanoacetic acid n-octyl (1.05g, 5.3mmol), N
2Under protection, be injected into trichloromethane 20mL, three triethylamines, room temperature reaction 12h.Stopped reaction adds 20mL water, and chloroform extraction three times merges organic phase, uses anhydrous Na
2SO
4Drying is filtered, be spin-dried for to get thick product, through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=do at 3: 1 eluent) Compound I-2 (0.27g, 69%).
1H?NMR(400MHz，CDCl
3)：δ8.44(s，4H)，8.17(s，4H)，8.00(s，4H)，7.94(dd，4H)，7.91(dd，4H)，7.81(d，4H)，7.61(d，4H)，7.06(s，4H)，4.31(t，8H)，2.86(t，8H)，2.57(t，8H)，1.79(m，8H)，1.68(m，8H)，1.58(m，8H)，1.20-1.44(m，84H)，0.91(m，24H)，0.84(m，12H)。
Its structural formula is as follows:
Embodiment 7
Synthesizing of Compound I-3
Add compound V (0.20g, 0.087mmol) in 50mL single port bottle, the 3-ethyl tannin (0.29g, 1.74mmol) of having mercy on, N
2Under protection, be injected into trichloromethane 20mL, three piperidines, back flow reaction 12h.Stopped reaction adds 20mL water, and chloroform extraction three times merges organic phase, uses anhydrous Na
2SO
4Drying is filtered, be spin-dried for to get thick product, through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=do at 2.5: 1 eluent) Compound I-3 (0.20g, 80%).
1HNMR(400MHz，CDCl
3)：δ7.93(s，4H)，7.91(s，4H)，7.80(d，4H)，7.77(d，4H)，7.68(d，4H)，7.64(d，4H)，7.47(dd，4H)，7.11(s，4H)，4.14(m，8H)，2.72(t，8H)，2.57(t，8H)，1.62(m，16H)，1.22-1.34(m，12H)，0.85(t，12H)，0.87(t，12H)。
Its structural formula is as follows:
Fig. 1 is the absorption curve of the Compound I-3 that obtains of embodiment 7, and wherein X-coordinate is wavelength, and ordinate zou is absorbancy, calculates its optical energy band E
op g=1.91eV; Compound I-3 pair visible light has receptivity preferably as can be known, and under room temperature, compound (I-3) is at 0.1mol L
-1Bu
4NPF
6Dichloromethane solution in cyclic voltammogram as shown in Figure 2, HOMO and the LUMO value that calculates compound by redox peak in figure be respectively-5.59eV and-3.69eV, this value and acceptor material be such as the energy level of PC60BM is complementary, so Compound I-3 can be used as a kind of donor material and are applied to the organic solar batteries field.
Claims (10)
1. a spiral shell fluorene derivatives, is characterized in that, its structure is suc as formula shown in (I);
In formula (I), R
1, R
2, R
3And R
4Be the end group acceptor groups, be independently selected from suc as formula the group shown in (I-a), formula (I-b) or formula (I-c):
In formula (I-a), formula (I-b) and formula (I-c), " * " represents link position.
2. the spiral shell fluorene derivatives shown according to claim 1, is characterized in that, described spiral shell fluorene derivatives is Compound I-1, Compound I-2 or Compound I-3;
The structural formula of Compound I-1 is as follows:
The structural formula of Compound I-2 is as follows:
The structural formula of Compound I-3 is as follows:
3. the preparation method of spiral shell fluorene derivatives according to claim 1 and 2, is characterized in that, comprises the steps:
(1) under protection of inert gas, under the condition that palladium catalyst exists, the Stille linked reaction occurs in 4,7-dibromo diazosulfide and 4-hexyl-2-tributyl tin thiophene, obtains Compound I I through aftertreatment, and the structure of Compound I I is as follows:
(2) under protection of inert gas, Compound I I and DMF and phosphorus oxychloride are carried out Wei Er David Smail-Haake reaction, obtain compound III through aftertreatment, and the structure of compound III is as follows:
(3) under the lucifuge condition, compound III and N-bromo-succinimide generation bromo-reaction obtain compound IV through aftertreatment, and the structure of compound IV is as follows:
(4) under protection of inert gas, under the condition of palladium catalyst and alkali existence, the Suzuki linked reaction occurs in compound IV and two spiral shell fluorenes tetraboric acid esters in water and organic solvent two-phase system, obtain compound V through aftertreatment, and the structure of compound V is as follows:
The structure of two spiral shell fluorenes tetraboric acid esters is as follows:
(5) under protection of inert gas, under solvent and catalyzer existence condition, compound V and contain acceptor end group monomer the Fei Nageer condensation reaction occurs obtains described spiral shell fluorene derivatives;
The described acceptor end group monomer that contains is at least a in the rich tannin of propane dinitrile, cyanoacetic acid monooctyl ester and 3-ethyl.
4. the preparation method of spiral shell fluorene derivatives according to claim 3, is characterized in that, the described acceptor end group monomer that contains is the rich tannin of propane dinitrile, cyanoacetic acid monooctyl ester or 3-ethyl.
5. the preparation method of according to claim 3 or 4 described spiral shell fluorene derivativess, is characterized in that, in step (3), described aftertreatment comprises uses the mixed solvent of trichloromethane and ethanol to carry out recrystallization.
6. the preparation method of spiral shell fluorene derivatives according to claim 5, is characterized in that, in step (3), in described mixed solvent, the volume ratio of trichloromethane and ethanol is 1: 0.8～1.2.
7. the preparation method of according to claim 3 or 4 described spiral shell fluorene derivativess, is characterized in that, in step (4), described organic solvent is toluene.
8. the preparation method of according to claim 3 or 4 described spiral shell fluorene derivativess, is characterized in that, in step (5), described catalyzer is alkylamine.
9. the preparation method of spiral shell fluorene derivatives according to claim 8, is characterized in that, described alkylamine is triethylamine.
10. a small molecule material that is applied to the organic solar batteries field, is characterized in that, comprises the described spiral shell fluorene derivatives of claim 1 or 2.
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| TWI585090B (en) * | 2014-04-21 | 2017-06-01 | Ｌｇ化學股份有限公司 | Heterocyclic compound and organic solar cell comprising the same |
| CN112375079A (en) * | 2020-11-20 | 2021-02-19 | 常州大学 | Micromolecular receptor material based on naphthalene diimide unit derivative, preparation method and application |
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| KERSTIN SCHULZE，等: ""Efficient Vacuum-Deposited Organic Solar Cells Based on a New Low-Bandgap Oligothiophene and Fullerene C60"", 《ADV. MATER.》 * |
| KRISTINA DRISCOLL，等: ""Enhanced Photoresponse in Solid-State Excitonic Solar Cells via Resonant Energy Transfer and Cascaded Charge Transfer from a Secondary Absorber"", 《NANO LETT.》 * |
| PRASHANT SONAR，等: ""Thiophene–benzothiadiazole–thiophene (D–A–D) based polymers: effect of donor/acceptor moieties adjacent to D–A–D segment on photophysical and photovoltaic properties"", 《J. MATER. CHEM.》 * |
| YONGSHENG LIU，等: ""Spin-Coated Small Molecules for High Performance Solar Cells"", 《ADV. ENERGY MATER.》 * |
| ZHI LI，等: ""Solution Processable Rhodanine-Based Small Molecule Organic Photovoltaic Cells with a Power Conversion Efficiency of 6.1%"", 《ADV. ENERGY MATER.》 * |
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| US10355221B2 (en) | 2014-04-21 | 2019-07-16 | Lg Chem, Ltd. | Heterocyclic compound and organic solar cell comprising the same |
| CN105017090A (en) * | 2015-06-16 | 2015-11-04 | 天长市天佳化工科技有限公司 | 4-(N-methyl-N-sulfoethyl)aminobenzaldehyde sodium salt synthesis method |
| CN105017090B (en) * | 2015-06-16 | 2017-07-25 | 天长市天佳化工科技有限公司 | A kind of synthetic method of 4 (N methyl Ns sulfoethvl) aminobenzaldehyde sodium salts |
| CN112375079A (en) * | 2020-11-20 | 2021-02-19 | 常州大学 | Micromolecular receptor material based on naphthalene diimide unit derivative, preparation method and application |
| CN112375079B (en) * | 2020-11-20 | 2022-03-25 | 常州大学 | Micromolecular receptor material based on naphthalene diimide unit derivative, preparation method and application |
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| CN103087056B (en) | 2016-02-03 |
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