CN104230849A - Fluorene-based oligomer as well as synthesis method and application thereof - Google Patents

Fluorene-based oligomer as well as synthesis method and application thereof Download PDF

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CN104230849A
CN104230849A CN201410446022.0A CN201410446022A CN104230849A CN 104230849 A CN104230849 A CN 104230849A CN 201410446022 A CN201410446022 A CN 201410446022A CN 104230849 A CN104230849 A CN 104230849A
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fluorenes
oligomer
fluorene
cyclics
fno
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CN104230849B (en
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刘治田
刘菁
李超
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Wuhan Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
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  • Electroluminescent Light Sources (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention discloses a fluorene-based oligomer as well as a synthesis method and application thereof. The synthesis method comprises the following steps: performing heating reflux on 2-bromofluorene, 4-(2-chloroethyl) morpholine hydrochloride and potassium hydroxide in the presence of an inert gas, performing silica gel column chromatography on a coarse reaction product, and recrystallizing in petroleum ether, thereby obtaining an ethyl morpholine substituted bromofluorene monomer; reacting a cycle compound with two bromine-substituted ends with alkyl bromide and 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolan in the presence of a palladium catalyst, thereby obtaining a cycle compound with boric acid ester at two ends; mixing the fluorene monomer with the cycle compound, performing reflux reaction in the presence of an inert gas, cooling, and purifying, thereby obtaining the fluorene-based oligomer. The fluorene-based oligomer is good in electron extraction and transmission property, the potential barrier between an organic active layer and a metal electrode is effectively reduced, and the fluorene-based oligomer can be used in decoration layers of negative electrodes and positive electrodes of organic optical devices such as polymer electroluminescence diodes and organic solar batteries.

Description

A kind of oligomer based on fluorenes and synthetic method thereof and application
Technical field
The invention belongs to organic solar batteries field, be specifically related to a kind of novel oligomer based on fluorenes and synthetic method thereof and application.
Background technology
Organic solar batteries is subject to various circles of society's extensive concern due to the advantage of its uniqueness.Polymer electroluminescence material applies in solar cell, have inexpensive, device making technics is simple, it is specific that driving voltage is low, brightness, efficiency are high etc., and have good mechanical property, processing characteristics and thermostability, overcome the shortcoming of inorganic materials, make polymer electroluminescence material become the new study hotspot in one, electroluminescent field.
Mainly include active coating film and the two end electrodes of machine semi-conductor in the basic sandwich structure of organic solar batteries, for obtaining efficient battery efficiency, the interfacial property between regulation and control organic layer and metal electrode becomes most important.
Low work function metal (as Ba and Ca) is commonly used to do battery cathode material, but Ba and Ca is responsive to water oxygen, reduces stability and the life-span of battery.Metallic cathode (as Al, Ag and Au) stable in the air can improve stability test, but its work content is very high.Reduce to make the potential barrier between organic active layer and high work function cathode, just must introduce interface-modifying layer betwixt, the modifying interface material with good electronics/hole transport performance inserts between organic active layer and metal electrode and improves electrons extract content, reduce interface potential barrier, thus solar battery efficiency is improved.
Water-soluble or alcohol molten conjugacy organic compound is embellishing cathode interface material newer at present, the conjugated polymers that this material has pertinent literature to report comparatively before, needs to be studied further.
Summary of the invention
Based on an oligomer for fluorenes, its structure is:
In formula, R represents cyclics, and described cyclics is phenyl, fluorenyl, carbazyl or pyrryl.
By such scheme, the described oligomer based on fluorenes has following structure:
By such scheme, the described oligomer based on fluorenes has following structure:
Wherein, R ' is C 1~ C 18alkyl.
By such scheme, the described oligomer based on fluorenes has following structure:
The preparation method of the above-mentioned oligomer based on fluorenes, comprises the following steps:
1) 2-bromine fluorenes, 4-(2-chloroethyl) morpholine hydrochloride and potassium hydroxide reflux under protection of inert gas, reacting coarse product after silica gel column chromatography in sherwood oil recrystallization, obtain ethyl morpholine replace bromine fluorenes monomer;
2) cyclics of two ends bromo reacts with alkyl bromide, 2-sec.-propyl-4,4,5,5-tetramethyl--1,3,2-dioxaborinate under palladium catalyst condition, obtains the cyclics of two end band boric acid esters;
3) cyclics of the bromine fluorenes monomer replaced by above-mentioned ethyl morpholine and two end band boric acid esters is with the mixed in molar ratio of 2:1, and back flow reaction under protection of inert gas, cooling, obtains the oligomer based on fluorenes after purification.
The above-mentioned oligomer based on fluorenes is in the application of organic solar batteries cathode plane decorative material.
Beneficial effect of the present invention is:
The oligo structures based on fluorenes of the present invention's synthesis is single, and molecular weight is determined; There is good solvability and film-forming properties; Methyl alcohol can be dissolved in, THF, DMSO and water polar solvent.
The oligomer based on fluorenes of the present invention's synthesis all has good electronics extracting and transmission performance, effectively reduce the potential barrier between organic active layer and metal electrode, can be applicable to the negative electrode of organic electro-optic device or the decorative layers of anode such as polymer electroluminescence diode, organic solar batteries.
Accompanying drawing explanation
Fig. 1: embodiment 1,2 product ultra-violet absorption spectrum in the solution;
Fig. 2: the ultra-violet absorption spectrum of embodiment 1,2 product solid film.
Embodiment
Following embodiment explains technical scheme of the present invention further, but not as limiting the scope of the invention.
The present invention's synthesis is as follows based on the process of the oligomer of fluorenes:
1) 2-bromine fluorenes, 4-(2-chloroethyl) morpholine hydrochloride and potassium hydroxide reflux under protection of inert gas, reacting coarse product after silica gel column chromatography in sherwood oil recrystallization, obtain ethyl morpholine replace bromine fluorenes monomer;
2) cyclics of two ends bromo reacts with alkyl bromide, 2-sec.-propyl-4,4,5,5-tetramethyl--1,3,2-dioxaborinate under palladium catalyst condition, obtains the cyclics of two end band boric acid esters;
3) cyclics of the bromine fluorenes monomer replaced by above-mentioned ethyl morpholine and two end band boric acid esters is with the mixed in molar ratio of 2:1, and back flow reaction under protection of inert gas, cooling, obtains the oligomer based on fluorenes after purification.
The oligomer based on fluorenes of synthesis has following structure:
Cyclics R represents phenyl, fluorenyl, carbazyl or pyrryl.The present invention is based on the oligomer of fluorenes, have comparatively regular two dimensional structure, Heat stability is good, synthetic method is simple.
The obtained application of oligomer in organic solar batteries cathode plane decorative material based on fluorenes.Result shows, it has good electronics extracting and transmission performance, effectively reduces the potential barrier between organic active layer and metal electrode, can be applicable to the negative electrode of organic electro-optic device or the decorative layers of anode such as polymer electroluminescence diode, organic solar batteries.
Example 1
1) synthesis of bromo-9,9-bis-(2-ethyl morpholine) fluorenes (M1) of 2-:
By 2-bromine fluorenes (4.9g, 20mmol), 4-(2-chloroethyl) morpholine hydrochloride (9.3g, 50mmol) and potassium hydroxide (11.2g, 200mmol) be dissolved in 200mL tetrahydrofuran (THF), 80 DEG C of reaction 48h under the Ar environment of anhydrous and oxygen-free.By solvents tetrahydrofurane underpressure distillation after having reacted, first product purifies (silica gel, ethyl acetate: methyl alcohol=10:1 is eluent) with column chromatography, obtains Off-white solid recrystallization in sherwood oil, finally obtain white crystal 6.5g, productive rate is 69%.
2) synthesis of Isosorbide-5-Nitrae-two [9,9-bis-(2-ethyl morpholine) fluorenes] benzene (FNO-B-FNO):
By M1 (471mg in the there-necked flask of 50mL, 1mmol), 1.4-bis-boric acid (83mg, 0.5mmol), tetraphenyl phosphatization palladium (15mg, 0.01mmol), salt of wormwood (1.38g, 10mmol) join in the mixed solution of 10mL toluene 5mL water.Reaction system refluxes 48h under argon shield, is cooled to room temperature.First product purifies (silica gel, ethyl acetate: methyl alcohol: triethylamine=10:1:0.1 is eluent) with column chromatography, obtains faint yellow toner end 220mg, productive rate 51%.
Example 2
1) synthesis of 2,7-bis-bromo-9,9-dioctyl fluorene (M2)
By 2,7-dibromo fluorenes (5g, 15.5mmol), Tetrabutyl amonium bromide (0.1g, 0.31mmol), 200mL dimethyl sulfoxide (DMSO) is put in there-necked flask and forms suspension under violent stirring, instillation 50wt% aqueous sodium hydroxide solution 5mL, after reaction 1h, then drip 1-bromooctane (6.2g, 31mmol).Reaction mixture at room temperature stirs stopped reaction after 6h, and with ether (150mL × 3) extraction, organic phase saturated common salt is washed, and uses anhydrous magnesium sulfate drying.Solvent under reduced pressure distills, and product recrystallization in the mixed solvent of methanol/acetone obtains white, needle-shaped crystals 8g, productive rate 80%.
2) synthesis of 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxaborinate-two base)-9,9-dioctyl fluorene (M3)
By M2 (5.4g, 10mmol) be dissolved in 60mL tetrahydrofuran (THF), at-78 DEG C, dropwise add the n-Butyl Lithium 15mL of 1.6mol/L, react 2h in a nitrogen atmosphere, and then add 2-sec.-propyl-4 fast, 4,5,5-tetramethyl--1,3,2-dioxaborinate 13mL, low-temp reaction 2h, slowly rise to room temperature reaction 24h.Reaction mixture is poured into water, and uses extracted with diethyl ether.Organic layer brine It also uses anhydrous magnesium sulfate drying.Faint yellow solid is obtained except after desolventizing, obtain white powdery solids with methyl alcohol/tetrahydrofuran (THF) recrystallization, and then purify (silica gel, ethyl acetate: normal hexane=1:15 is eluent) with column chromatography, obtain white, needle-shaped crystals 4.8g, productive rate 75%.
3) synthesis of FNO-F8-FNO
By M1 (471mg in the there-necked flask of 50mL, 1mmol), M3 (321mg, 0.5mmol) tetraphenyl phosphatization palladium (15mg, 0.01mmol), salt of wormwood (1.38g, 10mmol) join in the mixed solution of 10mL toluene 5mL water.Reaction system refluxes 48h under argon shield, is cooled to room temperature.First product purifies (silica gel, ethyl acetate: methyl alcohol: triethylamine=10:1:0.1 is eluent) with column chromatography, obtains creamy white crystal 340mg, productive rate 58%.
The ultra-violet absorption spectrum of above-described embodiment 1,2 products therefrom is shown in accompanying drawing 1,2.
As shown in Figure 1, the absorption peak of embodiment 1,2 product FNO-B-FNO and FNO-F8-FNO in trichloromethane is respectively 330nm and 351nm, can see that oligomer FNO-F8-FNO has obvious red shift relative to FNO-B-FNO, illustrate to have stronger interaction between FNO-F8-FNO molecular chain, the conjugated structure that FNO-B-FNO is relatively weak simultaneously causes its relative FNO-F8-FNO blue shift.
As shown in Figure 2, embodiment 1,2 product FNO-B-FNO and FNO-F8-FNO is prepared by spin coating chloroform soln on silica glass at solid film.The absorption peak of oligomer FNO-B-FNO and FNO-F8-FNO lays respectively at 338nm and 357nm.The absorption of oligomer under solid film state can be found out relative to having red shift under solution state.This may be interact cause because the conjugated backbone of molecule under solid film state is more tending towards complanation and strong π-π.
The application of embodiment 1,2 product in organic solar batteries, prepare with PTB7 (poly [4,8-bis (2-ethylhexyloxyl) benzo [1,2-b:4,5-b'] dithiophen-e-2,6-diyl-alt-ethylh-exyl-3-fluorothithieno [3,4-b] thiophene-2-carboxylate-4,6-diyl] and PC 70bM ((6,6)-phenyl-C 70-butyric acid methylester) be the solar cell device of organic active layer.The structure of solar cell device is: ITO (tin indium oxide)/PEDOT:PSS/PTB7:PC 70bM/interlayer/Ca/Al.Modifying interface material FNO-B-FNO and FNO-F8-FNO is dissolved in methyl alcohol under mild acid conditions, is mixed with solution respectively and is spin-coated on PTB7:PC 70on BM active coating, the Al electrode of Ca and 100nm that finally evaporation 20nm is thick on polymer interface decorative layer.There is no the solar cell device ITO/PEDOT:PSS/PTB7:PC of interfacial layer 70bM/Ca/Al is as control group reference device, and all devices are all prepared under same environmental conditions.(wherein, interlayer represents FNO-B-FNO and FNO-F8-FNO)
Embodiment 1,2 is applied to solar cell at simulated solar irradiation AM1.5G (100mW/cm 2) irradiation under short-circuit current (J sc), open circuit voltage (V oc), packing factor (FF) and effciency of energy transfer (PCEs) parameter as shown in table 1.
Table 1
Do not add oligomer interface-modifying layer as can be seen from the table, only make the solar cell device efficiency of cathode material for 6.86% with Ca/Al, corresponding V ocfor 0.71V, J scfor 16.53mA/cm 2, FF is 59.After adding oligomer embellishing cathode interface layer FNO-B-FNO and FNO-F8-FNO, open circuit voltage and packing factor all increase, and make device final energy efficiency of conversion reach 8.72% and 8.90% respectively.The open circuit voltage V of solar cell ocbe the important indicator affecting overall device performance, experimental result can find out the V of device ocget a promotion after insertion interface-modifying layer comparatively large, be increased to 0.76V from 0.71V.In the solar cell system of other structures a lot, observe insertion interface-modifying layer equally and make V octhe phenomenon increased, researchist utilizes its mechanism of action of technical study such as ac impedance spectroscopy and scanning Kelvin probe microscope, and key effect is played in the lifting being formed in voltage of discovery interface dipole.By introducing interface-modifying layer FNO-B-FNO and FNO-F8-FNO, between interfacial layer and negative electrode, defining interface dipole thus reduce the work function of negative electrode.

Claims (6)

1., based on an oligomer for fluorenes, it is characterized in that structure is:
In formula, R represents cyclics, and described cyclics is phenyl, fluorenyl, carbazyl or pyrryl.
2., as claimed in claim 1 based on the oligomer of fluorenes, it is characterized in that there is following structure:
3., as claimed in claim 1 based on the oligomer of fluorenes, it is characterized in that there is following structure:
Wherein, R ' is C 1~ C 18alkyl.
4., as claimed in claim 1 based on the oligomer of fluorenes, it is characterized in that there is following structure:
5. described in any one of claim 1-4 based on the preparation method of the oligomer of fluorenes, it is characterized in that comprising the following steps:
1) 2-bromine fluorenes, 4-(2-chloroethyl) morpholine hydrochloride and potassium hydroxide reflux under protection of inert gas, reacting coarse product after silica gel column chromatography in sherwood oil recrystallization, obtain ethyl morpholine replace bromine fluorenes monomer;
2) cyclics of two ends bromo reacts with alkyl bromide, 2-sec.-propyl-4,4,5,5-tetramethyl--1,3,2-dioxaborinate under palladium catalyst condition, obtains the cyclics of two end band boric acid esters;
3) cyclics of the bromine fluorenes monomer replaced by above-mentioned ethyl morpholine and two end band boric acid esters is with the mixed in molar ratio of 2:1, and back flow reaction under protection of inert gas, cooling, obtains the oligomer based on fluorenes after purification.
6. described in any one of claim 1-4 based on the application of the oligomer of fluorenes at organic solar batteries cathode plane decorative material.
CN201410446022.0A 2014-09-03 2014-09-03 A kind of oligomer based on fluorenes and synthetic method thereof and application Expired - Fee Related CN104230849B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090230362A1 (en) * 2008-01-25 2009-09-17 Bazan Guillermo C Conjugated oligoelectrolyte electron transporting layers
CN103172836A (en) * 2013-01-28 2013-06-26 武汉工程大学 Polymer containing indole [3,2-b] carbazole unit and preparation method thereof
CN103319378A (en) * 2013-06-27 2013-09-25 中国科学院宁波材料技术与工程研究所 Zwitterionic organic small molecular solar cell cathode interface material, as well as preparation method and use thereof
CN103396321A (en) * 2013-06-27 2013-11-20 中国科学院宁波材料技术与工程研究所 Alcohol-soluble conjugate organic micromolecular material for cathode interface of solar cell, and preparation method and purpose thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090230362A1 (en) * 2008-01-25 2009-09-17 Bazan Guillermo C Conjugated oligoelectrolyte electron transporting layers
CN103172836A (en) * 2013-01-28 2013-06-26 武汉工程大学 Polymer containing indole [3,2-b] carbazole unit and preparation method thereof
CN103319378A (en) * 2013-06-27 2013-09-25 中国科学院宁波材料技术与工程研究所 Zwitterionic organic small molecular solar cell cathode interface material, as well as preparation method and use thereof
CN103396321A (en) * 2013-06-27 2013-11-20 中国科学院宁波材料技术与工程研究所 Alcohol-soluble conjugate organic micromolecular material for cathode interface of solar cell, and preparation method and purpose thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARTIN STORK等: "Energy Transfer in Mixtures of Water-Soluble Oligomers: Effect of Charge, Aggregation, and Surfactant Complexation", 《ADVANCED MATERIALS》 *

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