CN103087056B - A kind of spiral shell fluorene derivatives and its preparation method and application - Google Patents
A kind of spiral shell fluorene derivatives and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of spiral shell fluorene derivatives, its structure is such as formula shown in (I); In formula (I), R
1, R
2, R
3and R
4for end group acceptor groups, independently selected from such as formula the group shown in (I-a), formula (I-b) or formula (I-c).This spiral shell fluorene derivatives is strong to the receptivity of visible ray, can be applied to organic solar field as a kind of small molecules donor material.The invention also discloses the preparation method of spiral shell fluorene derivatives, with 4,7-dibromo diazosulfide and 4-hexyl-2-tributyl tin thiophene are starting raw material, obtain spiral shell fluorene derivatives successively through Stille linked reaction, Wei Er David Smail-Haake reaction, bromo-reaction, Suzuki linked reaction and Fei Nageer condensation reaction.
Description
Technical field
The invention belongs to 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 the device directly light energy conversion being become 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 carrying out studying, compared with inorganic solar cell, there is light weight, inexpensive, solution-processible, high mechanical flexibility, can be made into the advantages such as flexible broad area device, its history can trace back to 1958, magnesium phthalocyanine pigment layer is clipped between the different electrode of two work functions and supports first organic photoelectric conversion devices by Kearns and Calvin, observed the open circuit voltage of 200mV, compare with inorganic solar cell, electricity conversion is extremely low.Between Two decades years after this, in organic solar batteries field, innovation is few.
1986, doctor Deng Qingyun of Kodak is by the duplicature of a kind of derivative of four carboxylic base perylenes and copper phthalocyanine composition, two membranes is carried out being connected having made organic solar batteries with two electrodes respectively, the electricity conversion of this organic solar batteries reaches about 1%, although differ comparatively 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 of duplicature heterojunction is that 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 as to body and acceptor, wherein, after giving the organic semiconductor material absorb photons of body, produce hole-electron pair, be electronically injected in the semiconductor material as acceptor, hole is separated with electronics.In this system, electron donor(ED) is p-type, and electron acceptor(EA) is then N-shaped, thus hole and electronics are transferred on two electrodes respectively, forms photoelectric current.
Soluble type organic small molecule material has clear and definite molecular structure, monodispersity, can repeat synthesis and the advantage such as purification step, and having become can one of the applying soln processing technology ideal material preparing organic solar batteries.And solubility organic molecule is applied in organic solar batteries and needs to have good film-forming properties, there is good consistency with acceptor material level-density parameter.Therefore arrowband system, the solubility organic donor small molecules of high mobility is the photovoltaic material that a class has development prospect.
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 prevent the formation of crystallization, thus nearly all this material with amorphous state spirane structure all has higher glass transition temperature, simultaneously can effectively reduce molecular aggregates or excite the formation of mixture, thus more can effectively improve, the optical purity of organic electroluminescence device and stability.Therefore, synthesize the spiral shell fluorene derivatives that can absorb sunlight preferably made new advances and there is 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 good sorption to visible ray, may be used for small molecules donor material.
A kind of spiral shell fluorene derivatives, its structure is such as formula shown in (I);
In formula (I), R
1, R
2, R
3and R
4for end group acceptor groups, independently selected from such 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 that ionization occurs and provides electronics, this spiral shell fluorene derivatives contains end group acceptor groups simultaneously, its sucting electronic effect can strengthen described spiral shell fluorene derivatives effectively, thus can be applied to 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 synthesis.
Present invention also offers the preparation method of above-mentioned spiral shell fluorene derivatives, comprise the steps:
(1), under protection of inert gas, under palladium catalyst existent condition, there is Stille linked reaction in 4,7-dibromo diazosulfide and 4-hexyl-2-tributyl tin thiophene, obtain Compound II per through aftertreatment, the structure of Compound II per is as follows:
(2) under protection of inert gas, Compound II per and DMF and phosphorus oxychloride are carried out Wei Er David Smail-Haake and are reacted, and obtain compound III through aftertreatment, the structure of compound III is as follows:
(3) under lucifuge condition, compound III and N-bromo-succinimide generation bromo-reaction, obtain compound IV through aftertreatment, the structure of compound IV is as follows:
(4) under protection of inert gas; under palladium catalyst and alkali existent condition, in water and organic solvent two-phase system, there is Suzuki linked reaction in compound IV and two spiral shell fluorenes tetraboric acid ester; obtain compound V through aftertreatment, the structure of compound V is as follows:
The structure of two spiral shell fluorenes tetraboric acid ester is as follows:
(5), under protection of inert gas, under solvent and catalyzer existence condition, compound V and Fei Nageer condensation reaction occurs containing acceptor end monomers, obtains described spiral shell fluorene derivatives;
Described containing acceptor end monomers be propane dinitrile, cyanoacetic acid monooctyl ester and the 3-ethyl at least one of having mercy in tannin.
This preparation method's operating process is easy to control, and purify convenient, the spiral shell fluorene derivatives absorbing ability finally obtained is strong, effectively can meet the application requiring of organic solar batteries.
As preferably, described containing acceptor end monomers be propane dinitrile, cyanoacetic acid monooctyl ester or 3-ethyl have mercy on tannin, the reaction conditions now in step (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 adopts is 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 a solvent, and solvent is generally toluene, dimethylbenzene or Isosorbide-5-Nitrae-dioxane, is preferably toluene for substrate of the present invention, and productive rate can be made higher, and raw material fully dissolves by consumption.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 the mol ratio of 4,7-described dibromo diazosulfides and 4-hexyl-2-tributyl tin thiophene is preferably 1: 2.0 ~ 2.4.
In step (2), the condition of described Wei Er David Smail-Haake reaction when described Compound II per refluxes and carries out this reaction in 1,2-ethylene dichloride, has higher productive rate known by those skilled in the art.The consumption of solvent is generally 10 ~ 20 times of Compound II per quality.
Described DMF and the mole dosage of phosphorus oxychloride roughly equal, be generally 1.05 times of Compound II per 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 requirement strict especially, 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 not easily too high, generally at room temperature carries out.
As preferably, in step (3), described aftertreatment comprises and uses the mixed solvent of trichloromethane and ethanol to carry out recrystallization, when adopting this mixed solvent to carry out recrystallization, can be simplified the operation step greatly, and the product purity obtained 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, productive rate can be made to be greatly improved when described Suzuki linked reaction is carried 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 DEG C, and productive rate is higher.
In step (4), described palladium catalyst is preferably Pd (PPh
3)
4, described alkali is preferably K
2cO
3, now reaction yield is higher and cost is lower.
In step (4), with molar amount, described compound IV: two spiral shell fluorenes tetraboric acid ester: 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, more preferably alkylamine, comprises triethylamine and piperidines, most preferably be triethylamine, and when using triethylamine, reaction has higher yield.
In step (5), described solvent is preferably trichloromethane.
The described mol ratio containing acceptor end monomers and described compound V is 4 ~ 4.4: 1.
Present invention also offers a kind of small molecule material being applied to organic solar batteries field, comprise above-mentioned spiral shell fluorene derivatives, because this spiral shell fluorene derivatives is better to the absorption of visible ray, therefore, the utilising efficiency of described small molecule material to sun power can be improved.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) containing end group acceptor groups in the spiral shell fluorene derivatives described in, there is sucting electronic effect, this spiral shell fluorene derivatives can be strengthened to the receptivity of visible ray;
(2) preparation method of the spiral shell fluorene derivatives described in is easy to control, and the purity of the product obtained is high, can meet the service requirements of organic solar batteries.
Accompanying drawing explanation
Fig. 1 is the absorption curve of the Compound I-3 obtained of embodiment 7, and wherein X-coordinate is wavelength, and ordinate zou is absorbancy;
Fig. 2 be the cyclic voltammetry curve of the compound (I-3) that obtains of implementation column 7 in dichloromethane solution wherein X-coordinate be voltage, ordinate zou is electric current.
Fig. 3 is the syntheti c route figure of compound V.
Embodiment
Embodiment 1
The synthesis of Compound II per
4,7-dibromo diazosulfide (8.82g, 30mmol) is added, 4-hexyl-2-tributyl tin thiophene (34.29g, 75mmol), N in 200ml single port bottle
2under protection, add Pd (PPh
3)
4(347mg, 0.3mmol), is injected into toluene 110mL, 115 DEG C of backflow 24h.Stopped reaction, is cooled to room temperature, adds 150mL water, chloroform extraction three times, merges organic phase, uses anhydrous Na
2sO
4drying, filters, and is spin-dried for and obtains thick product, obtain Compound II per (11.67g, 83%) through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=1: 3 do eluent).
Its structure is shown below:
Embodiment 2
The synthesis of compound III
In 250ml two mouthfuls of round-bottomed bottles, add Compound II per (5.63g, 12mmol), N
2protection bet injects 100mL1,2-ethylene dichloride, and N ', N '-dimethyl formamide (0.94mL, 12.6mmol), 0 DEG C of bet injects phosphorus oxychloride (1.10mL, 12.6mmol), back flow reaction 12h.Stopped reaction, is cooled to room temperature, and reaction solution is poured in 100mL2M sodium acetate aqueous solution, stirs 2h, chloroform extraction, and washing twice, uses anhydrous Na
2sO
4drying, filters, and is spin-dried for and obtains thick product, obtain compound III (5.00g, 84%) through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=1: 1 does eluent).
Its structural formula is as follows:
Embodiment 3
The synthesis of compound IV
In 150mL single port bottle, compound III (4.52g, 9.1mmol) is dissolved in 100mL trichloromethane, and NBS (1.72g, 9.56mmol) point adds reaction solution five times, room temperature lucifuge reaction 12h.Reaction solution is poured in 200mL water, chloroform extraction, merge organic phase, use anhydrous Na
2sO
4drying, filters, and be spin-dried for obtain thick product, trichloromethane and ethanol (1: 1) recrystallization obtain compound IV (5g, 95%).
1HNMR(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:
Embodiment 4
The synthesis of compound V
Compound IV (2.76g, 4.8mmol) is added, two spiral shell fluorenes tetraboric acid ester (0.49g, 0.6mmol), N in 200mL single port bottle
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 DEG C of backflow 24h.Stopped reaction, is cooled to room temperature, adds 100mL water, chloroform extraction three times, merges organic phase, uses anhydrous Na
2sO
4drying, filters, and is spin-dried for and obtains thick product, obtain compound V (0.142g, 62%) through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=3: 1 does eluent).
1HNMR(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
The synthesis of Compound I-1
Compound V (0.13g, 0.058mmoL) is added, propane dinitrile (0.016g, 0.24mmol), N in 25ml single port bottle
2under protection, be injected into trichloromethane 10mL, three triethylamines, room temperature reaction 12h.Stopped reaction, adds 20mL water, chloroform extraction three times, merges organic phase, uses anhydrous Na
2sO
4drying, filters, and is spin-dried for and obtains thick product, obtain Compound I-1 (0.096g, 67%) through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=3: 1 does eluent).
1HNMR(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
The synthesis of Compound I-2
Compound V (0.30g, 0.13mmol) is added, cyanoacetic acid n-octyl (1.05g, 5.3mmol), N in 50ml single port bottle
2under protection, be injected into trichloromethane 20mL, three triethylamines, room temperature reaction 12h.Stopped reaction, adds 20mL water, chloroform extraction three times, merges organic phase, uses anhydrous Na
2sO
4drying, filters, and is spin-dried for and obtains thick product, obtain Compound I-2 (0.27g, 69%) through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=3: 1 does eluent).
1HNMR(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
The synthesis of Compound I-3
In 50mL single port bottle, add compound V (0.20g, 0.087mmol), 3-ethyl is had mercy on tannin (0.29g, 1.74mmol), N
2under protection, be injected into trichloromethane 20mL, three piperidines, back flow reaction 12h.Stopped reaction, adds 20mL water, chloroform extraction three times, merges organic phase, uses anhydrous Na
2sO
4drying, filters, and is spin-dried for and obtains thick product, obtain Compound I-3 (0.20g, 80%) through silica gel chromatography column chromatography for separation (trichloromethane/sherwood oil=2.5: 1 does eluent).
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 embodiment 7 obtains, and wherein X-coordinate is wavelength, and ordinate zou is absorbancy, calculates its optical energy band E
op g=1.91eV; ; Known Compound I-3 pairs of visible rays have good receptivity, and under room temperature, compound (I-3) is at 0.1molL
-1bu
4nPF
6dichloromethane solution in cyclic voltammogram as shown in Figure 2, HOMO and the LUMO value being calculated compound by redox peak in figure is-5.59eV and-3.69eV respectively, the energy level of this value and acceptor material such as PC60BM matches, and therefore Compound I-3 can be applied to organic solar batteries field as a kind of donor material.
Claims (4)
1. a preparation method for spiral shell fluorene derivatives, is characterized in that, comprises the steps:
(1), under protection of inert gas, under palladium catalyst existent condition, there is Stille linked reaction in 4,7-dibromo diazosulfide and 4-hexyl-2-tributyl tin thiophene, obtain Compound II per through aftertreatment, the structure of Compound II per is as follows:
(2) under protection of inert gas, Compound II per and DMF and phosphorus oxychloride are carried out Wei Er David Smail-Haake and are reacted, and obtain compound III through aftertreatment, the structure of compound III is as follows:
(3) under lucifuge condition, compound III and N-bromo-succinimide generation bromo-reaction, obtain compound IV through aftertreatment, the structure of compound IV is as follows:
(4) under protection of inert gas; under palladium catalyst and alkali existent condition, in water and organic solvent two-phase system, there is Suzuki linked reaction in compound IV and two spiral shell fluorenes tetraboric acid ester; obtain compound V through aftertreatment, the structure of compound V is as follows:
The structure of two spiral shell fluorenes tetraboric acid ester is as follows:
(5), under protection of inert gas, under solvent and catalyzer existence condition, compound V and Fei Nageer condensation reaction occurs containing acceptor end monomers, obtains described spiral shell fluorene derivatives;
Described is that 3-ethyl is had mercy on tannin containing acceptor end monomers;
The structure of described spiral shell fluorene derivatives is as follows:
In step (3), the mixed solvent that described aftertreatment comprises use trichloromethane and ethanol carries out recrystallization;
In step (5), solvent is trichloromethane, and described catalyzer is alkylamine.
2. the preparation method of spiral shell fluorene derivatives according to claim 1, is characterized in that, in step (3), in described mixed solvent, the volume ratio of trichloromethane and ethanol is 1:0.8 ~ 1.2.
3. the preparation method of spiral shell fluorene derivatives according to claim 1, is characterized in that, in step (4), described organic solvent is toluene.
4. the preparation method of spiral shell fluorene derivatives according to claim 1, is characterized in that, described alkylamine is piperidines.
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| CN1634927A (en) * | 2004-11-11 | 2005-07-06 | 复旦大学 | Spirofluorene materials containing non-benzene aromatic ring and synthesis and use thereof |
| CN1651369A (en) * | 2004-01-27 | 2005-08-10 | 三星Sdi株式会社 | Spirofluorene-based polymer and organic electroluminescent device using the same |
| WO2007043354A1 (en) * | 2005-09-30 | 2007-04-19 | Semiconductor Energy Laboratory Co., Ltd. | Spirofluorene derivative, material for light-emitting element, light-emitting element, light-emitting device, and electronic device |
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| CN1651369A (en) * | 2004-01-27 | 2005-08-10 | 三星Sdi株式会社 | Spirofluorene-based polymer and organic electroluminescent device using the same |
| CN1634927A (en) * | 2004-11-11 | 2005-07-06 | 复旦大学 | Spirofluorene materials containing non-benzene aromatic ring and synthesis and use thereof |
| WO2007043354A1 (en) * | 2005-09-30 | 2007-04-19 | Semiconductor Energy Laboratory Co., Ltd. | Spirofluorene derivative, material for light-emitting element, light-emitting element, light-emitting device, and electronic device |
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