CN106831815B - A kind of A-D-A type small organic molecule receptor of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof - Google Patents
A kind of A-D-A type small organic molecule receptor of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof Download PDFInfo
- Publication number
- CN106831815B CN106831815B CN201710043515.3A CN201710043515A CN106831815B CN 106831815 B CN106831815 B CN 106831815B CN 201710043515 A CN201710043515 A CN 201710043515A CN 106831815 B CN106831815 B CN 106831815B
- Authority
- CN
- China
- Prior art keywords
- formula
- receptor
- small organic
- yuan
- organic molecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- 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
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a kind of A-D-A type small organic molecule receptors and the preparation method and application thereof of seven yuan of condensed ring (DTCC) of carbazoles containing thieno.The structure of the small molecule receptor is shown in formula I.The synthetic route of intermediate and its interesting small organic molecules receptor provided by the invention has many advantages, such as to be simple and efficient, raw material are cheap and easy to get, universality is high, reproducible, can promote the use of the synthesis that all kinds of DTCC base A-D-A type small organic molecules are received.The organic micromolecule receptor have the advantages that stable structure, raw material be commonly easy to get, lower production costs.This organic micromolecule receptor is used to prepare non-fullerene polymer solar battery, it can get 4.8-6% or so energy conversion efficiency, the excellent potentiality that such small molecule receptor is applied in organic solar batteries are sufficiently illustrated, there is certain practical application value.
Description
Technical field
The invention belongs to organic semiconductor material field, it is related to the small organic molecule receptor material for organic solar batteries
Material and preparation method thereof.
Background technique
Solar energy has the characteristics that inexhaustible, nexhaustible and without limitations, is a kind of most potential
Renewable energy.In recent years, due to organic solar batteries (Organic Solar Cells, OSCs) have lightweight, flexibility,
It is at low cost and can the advantages such as solwution method large area processing, thus paid close attention to by people.Wherein, the organic sun of bulk heteroj junction type
Energy battery achieves fast development.Currently, the energy conversion of the unijunction OSCs device based on fullerene derivate receptor structure is imitated
Rate (PCE) is more than 10%.However, fullerene derivate receptor haves the defects that some essence, and such as: it is caught in the light of visible region
Capacitation power is weak, synthesis and purification difficult and intermolecular aggregation tendency are strong etc., dramatically limit fowler alkenyl OSCs into
The development of one step.Therefore, be solve fullerene acceptor disadvantages mentioned above, develop novel non-fullerene acceptor (such as: organic small point
Sub- receptor) there is important research significance, it has been found as the substitute of most promising fullerene derivate receptor.
Seven yuan of condensed ring (Dithienocyclopentacarbazole, DTCC) of thieno carbazoles are a kind of classical ladders
Shape conjugation and ring element, there is strong electron donation, good coplanarity and molecular structure to be easy to cut out for it
Advantage, thus it is widely used in the p-type polymer semiconducting material of design, synthesized high-performance.Wherein, it is based on DTCC- base
The hole mobility of the organic field effect tube of polymer film construction is up to 0.001~0.14cm2V–1s–1
(Macromolecules,2013,46,7687-7695).Fowler alkenyl OSCs's based on DTCC- based polymer film construction
PCE up to 3.7~4.6% (Chem.Commun., 2010,46,3259-3261；Adv.Funct.Mater.,2012,22,1711–
1722).Although p-type DTCC derivative unit is widely used in the p-type polymer semiconducting material of synthesized high-performance,
It is that DTCC- base n-type small organic molecule acceptor material is not reported still.The present invention passes through in the thiophene end of DTCC derivative position
Two strong electrophilic end groups of upper introducing, design have synthesized a kind of A-D-A type small organic molecule receptor of unit of derivative containing DTCC,
Obtain the electronic transmission performance of excellent combination property.As acceptor material, have in non-fullerene solar battery good
Application potential.By molecular structure and organic solar batteries device optimization, it is expected to obtain high photoelectric conversion efficiency.
Summary of the invention
In view of problem above, the present invention provides a kind of A-D-A type small organic molecule of seven yuan of condensed ring of carbazoles containing thieno
Receptor and preparation method thereof.
The technical solution of the present invention is as follows:
A kind of A-D-A type small organic molecule receptor containing seven yuan of condensed ring of thieno carbazoles has following general formula (I):
Wherein, R1For C1-C16Linear or branched alkyl group；
In formula (I), R2For in structure shown in formula (II), formula (III), formula (IV), formula (VI), formula (VII), formula (VIII)
It is a kind of；
Wherein, R can be C1-C16Linear or branched alkyl group；
The preparation method of the above-mentioned A-D-A type small organic molecule receptor containing seven yuan of condensed ring of thieno carbazoles, including such as
Lower synthesis step:
(1) carbazole borate is reacted with thiophene ester halogenated compound, obtains intermediate a:
The structural formula of the carbazole borate are as follows:
Wherein, R1It is C1-C16Linear or branched alkyl group；
The thiophene ester halogenated compound structural formula are as follows:
The structural formula of the intermediate a are as follows:
Wherein, R1It is C1-C16Linear or branched alkyl group；
(2) at high temperature, intermediate a elder generation and R2Grignard reagent reaction, using acetic acid cyclization, obtain intermediate b:
The R2Grignard reagent structural formula be R2MgBr；
The R2For in structure shown in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII), formula (VIII)
It is a kind of；Wherein, R can be C1-C16Linear or branched alkyl group；
The structural formula of the intermediate b are as follows:
Wherein, R1It can be C1-C16Linear or branched alkyl group；
The R2For in structure shown in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII) or formula (VIII)
One kind；Wherein, R can be C1-C16Linear or branched alkyl group；
(3) at high temperature, intermediate b and phosphorus oxychloride and N, N '-dimethyl formamide obtain intermediate c:
The structural formula of the intermediate c are as follows:
Wherein, R1It can be C1-C16Linear or branched alkyl group；
The R2For in structure shown in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII), formula (VIII)
It is a kind of；Wherein, R can be C1-C16Linear or branched alkyl group；
(4) at high temperature, intermediate c is reacted with intermediate d, obtains final product shown in following structures:
The structural formula of the intermediate d are as follows:
The structural formula of the final product are as follows:
Wherein, R1It can be C1-C16Linear or branched alkyl group；
The R2For in structure shown in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII) or formula (VIII)
One kind；Wherein, R can be C1-C16Linear or branched alkyl group；
Preferably, the preparation method of the above-mentioned A-D-A type small organic molecule receptor containing seven yuan of condensed ring of thieno carbazoles,
Wherein step (1) is done as follows: by 10mmol carbazole borate, 20-100mmol thiophene ester halogenated compounds are (through business
Approach purchase, is commercially available if other chemical reagent are not explained clearly), 10-100mmol anhydrous Ks2CO3, in right amount
Water, 1-10mmol tetrabutylammonium bromide, 0.1-0.5g palladium catalyst, 200mL toluene is added in reaction flask.Nitrogen protection,
It is protected from light, is reacted 5-15 hours at 100 DEG C.It is cooled to room temperature, is extracted with methylene chloride and water, anhydrous MgSO4It is dry, it was spin-dried for
Column obtains yellow solid, as intermediate a.
Preferably, the preparation method of the above-mentioned A-D-A type small organic molecule receptor containing seven yuan of condensed ring of thieno carbazoles,
Wherein step (2) is done as follows: by 10mmol magnesium chips, appropriate iodine is as catalyst, 10-30mmol bromo chemical combination
Object, the THF of 50-150mL, is added in reaction flask.Nitrogen protection is caused at 100 DEG C.It reacts 8-20 hours at this temperature
Afterwards, the THF solution of 1-3mmol intermediate a is added in reaction system at normal temperature, and subsequent temperature rises to 110 DEG C of stirrings 10-15
Hour.It is cooled to room temperature, is extracted with methylene chloride and water, through anhydrous MgSO4It is dry, after being spin-dried for column, 50-150mL second are added
Acid stirs 3-8 hours at nitrogen protection, 100 DEG C.Reaction stop after, directly filtered, obtain yellow solid, as in
Mesosome b.
Preferably, the preparation method of the above-mentioned A-D-A type small organic molecule receptor containing seven yuan of condensed ring of thieno carbazoles,
Wherein step (3) is done as follows: by 0.5mmol intermediate product c, 10-30mmol phosphorus oxychloride, the N of 30-100mL, N '-
Dimethylformamide reaction, is added in reaction flask.Nitrogen protection stirs 15-30 hours at 110 DEG C.It is cooled to room temperature, with two
Chloromethanes and water extraction, anhydrous MgSO4It is dry, it was spin-dried for column, obtains yellow solid, as intermediate c.
Preferably, the preparation method of the above-mentioned A-D-A type small organic molecule receptor containing seven yuan of condensed ring of thieno carbazoles,
Wherein step (4) is done as follows: by 0.5mmol intermediate c, 1-10mmol intermediate d, 1-4mL of pyridine, 20-40mL chlorine
It is imitative, it is added in reaction flask.Nitrogen protection is reacted 8-15 hours at 100 DEG C.After stopping reaction, column is crossed, it is solid to obtain navy blue
Body, as final goal product.
Donor using commercially available PCE10 as solar battery, with the A-of seven yuan of condensed ring of carbazoles containing thieno
D-A type small organic molecule receptor is the receptor of solar battery, using classical sandwich device architecture (ITO/PEDOT:PSS/
PCE10:DTCC-IC/Ca/Al solar device) is constructed.
The present invention has the advantages that
(1) synthesis of small organic molecule receptor shown in the present invention is simple, and raw material can be easy to get, and synthetic method has generalization
The advantages that high and reproducible；
(2) small organic molecule receptor shown in the present invention is used to prepare non-fullerene polymer solar battery, can get 6%
The energy conversion efficiency of left and right has certain practical application value.
Detailed description of the invention
Fig. 1 is the ultraviolet-visible-near-infrared for the small organic molecule receptor that chemical structural formula shown in the present invention is DTCC-IC
Abosrption spectrogram.
Fig. 2 is the ultraviolet-visible-near-infrared for the small organic molecule receptor that chemical structural formula shown in the present invention is DTCC8-IC
Abosrption spectrogram.
Fig. 3 be chemical structural formula shown in the present invention be DTCC-IC and DTCC8-IC small organic molecule receptor prepare it is non-lipid
Strangle the J-V curve of alkene solar battery.
Specific embodiment
The present invention will be further described combined with specific embodiments below, but the present invention and is only not limited to following embodiment
The structure.
Embodiment 1
The small organic molecule receptor that a kind of chemical structural formula is DTCC-IC, synthetic route are as follows:
(1) chemical structural formula is the synthesis of the intermediate of a: by (2.7g, 5.1mmol) carbazole borate, (3.7g,
15.3mmol) thiophene ester halogenated compound, (13.8g, 100.0mmol) anhydrous K2CO3, suitable water, 2 drop tetrabutylammonium bromide,
0.5g palladium catalyst, 100mL toluene, is added in reaction flask.Nitrogen protection is protected from light, and is reacted 24 hours at 100 DEG C.It is cooled to
Room temperature is extracted, anhydrous MgSO with methylene chloride and water4It is dry, it was spin-dried for column, obtains yellow solid, as intermediate a, yield
It is 75%.1H NMR(400MHz,CDCl3),δ(ppm):8.08–8.10(d,2H),7.54–7.56(m,4H),7.36–7.38
(dd,2H),7.27–7.28(d,2H),4.30(t,2H),4.17–4.22(m,4H),1.85–1.91(m,2H),1.23–1.42
(m,10H),1.12–1.16(t,3H),0.82–0.86(t,3H)；13C NMR(100MHz,CDCl3),δ(ppm):163.59,
151.79,140.60,131.04,130.08,128.41,124.02,122.76,121.29,119.87,110.26,60.49,
43.29,31.81,29.38,29.19,29.06,27.31,22.62,14.11,14.07.
(2) chemical structural formula is the synthesis of the intermediate of b: by (0.48g, 20mmol) magnesium chips, appropriate iodine is used as and urges
Agent, (5.0g, 17.0mmol) are added in reaction flask bromooctane oxygroup benzene, 120mL THF.Nitrogen protection, at 100 DEG C
Caused.After reacting 12 hours at this temperature, the THF solution of (1.0g, 1.7mmol) intermediate a is added to instead at normal temperature
It answers in system, subsequent temperature rises to 110 DEG C and stirs 12 hours.It is cooled to room temperature, is extracted with methylene chloride and water, through anhydrous
MgSO4It is dry, after being spin-dried for column, 100mL acetic acid is added, is stirred 6 hours at nitrogen protection, 100 DEG C.After reaction stops, directly
Capable suction filtration is tapped into, yellow solid, as intermediate b, yield 73% are obtained.1H NMR(400MHz,CDCl3),δ(ppm):
7.80(s,2H),7.37(s,2H),7.27–7.29(d,2H),7.16–7.19(d,8H),6.99–7.01(d,2H),6.73–
6.75(d,8H),4.30–4.34(t,2H),3.86–3.89(t,8H),1.90–1.94(m,2H),1.69–1.75(m,12H),
1.26–1.47(m,46H),0.85–0.88(m,15H)；13C NMR(100MHz,CDCl3),δ(ppm):157.87,156.93,
145.84,141.45,140.67,137.66,135.04,129.04,127.53,123.17,121.28,117.66,114.16,
99.43,67.93,61.53,43.43,31.91,31.85,29.47,29.39,29.36,29.26,27.38,26.11,
22.68,14.13.
(3) chemical structural formula is the synthesis of the intermediate of c: by (0.9g, 0.7mmol) intermediate b, (1.7g,
10.5mmol) phosphorus oxychloride, 50mL DMF, is added in reaction flask.Nitrogen protection stirs 24 hours at 110 DEG C.It is cooled to room
Temperature is extracted, anhydrous MgSO with methylene chloride and water4It is dry, it was spin-dried for column, obtains yellow solid, as intermediate c, yield is
78%.1H NMR(400MHz,CDCl3),δ(ppm):9.87(s,2H),7.90(s,2H),7.68(s,2H),7.55(s,2H),
7.18–7.20(d,8H),6.78–6.81(d,8H),4.39(t,2H),3.90–3.93(t,8H),1.96(m,2H),1.72–
1.77(m,8H),1.29–1.44(m,50H),0.88–0.89(m,15H)；13C NMR(100MHz,CDCl3),δ(ppm):
182.84,158.24,157.34,151.38,146.84,145.91,141.18,136.44,133.99,132.20,128.88,
123.14,118.10,114.40,101.32,68.01,61.74,43.51,31.83,29.44,29.37,29.31,29.24,
27.32,26.09,22.66,14.11.
(4) chemical structural formula is the synthesis of the small organic molecule receptor of DTCC-IC: by (0.4g, 0.3mmol) intermediate c,
(0.4g, 2.1mmol) intermediate d, pyridine 1.5mL, 30mL chloroform, is added in reaction flask.Nitrogen protection is reacted at 100 DEG C
12 hours.It after stopping reaction, pours the mixture into and stirs a period of time in methanol, then filtered, cross column, obtain navy blue
Solid, as final goal product DTCC-IC, yield 73%.1H NMR(400MHz,CDCl3),δ(ppm):8.70–8.73
(t,4H),7.97(s,2H),7.93(d,2H),7.79–7.81(m,4H),7.69(s,2H),7.29–7.33(t,8H),7.18
(s,2H),6.87–6.89(d,8H),3.94–3.97(t,8H),3.72(t,2H),1.74–1.81(m,8H),1.67(m,2H),
1.29–1.45(m,50H),0.86–0.91(m,15H)；13C NMR(100MHz,CDCl3),δ(ppm):187.88,160.82,
159.70,158.46,158.24,148.06,141.41,141.15,139.75,136.79,136.36,135.28,134.63,
134.50,129.15,124.06,123.78,121.36,114.52,101.98,68.40,68.10,61.50,31.94,
31.82,29.57,29.39,29.34,29.24,29.17,28.85,27.25,26.10,22.65,14.09.
Embodiment 2
Chemical structural formula is that the synthetic route of the small organic molecule receptor of DTCC8-IC is as follows:
(1) chemical structural formula is the synthesis of the intermediate of a with embodiment 1
(2) chemical structural formula is the synthesis of the intermediate of e: by (0.6g, 25mmol) magnesium chips, appropriate iodine is as catalysis
Agent, (5.0g, 18.6mmol) are added in reaction flask bromooctane base benzene, 120mL THF.Nitrogen protection, by it at 100 DEG C
Cause.After reacting 12 hours at this temperature, the THF solution of (1.5g, 2.6mmol) intermediate a is added to reactant at normal temperature
In system, subsequent temperature rises to 110 DEG C and stirs 12 hours.It is cooled to room temperature, is extracted with methylene chloride and water, through anhydrous MgSO4It is dry
It is dry, after being spin-dried for column, 100mL acetic acid is added, is stirred 6 hours at nitrogen protection, 100 DEG C.After reaction stops, directly being taken out
Filter, obtains peak green solid, as intermediate e, yield 73%.1H NMR(400MHz,CDCl3),δ(ppm):7.83(s,
2H),7.38(s,2H),7.27–7.29(d,4H),7.16–7.18(d,4H),7.01–7.03(d,10H),4.30–4.33(t,
2H),2.50–2.54(t,8H),1.87–1.93(m,2H),1.53–1.57(m,8H),1.24–1.28(m,50H),0.84–
0.87(m,15H)；13C NMR(100MHz,CDCl3),δ(ppm):156.60,145.40,142.98,141.65,141.13,
140.68,135.12,128.25,127.90,127.44,123.35,121.27,117.92,99.41,62.28,43.42,
35.62,31.94,31.44,29.56,29.51,29.29,29.09,27.39,22.72,14.17.
(3) chemical structural formula is the synthesis of the intermediate of f: by (1.3g, 1.1mmol) intermediate e, (4.2g,
27.3mmol) phosphorus oxychloride, 50mL DMF, is added in reaction flask.Nitrogen protection stirs 24 hours at 110 DEG C.It is cooled to room
Temperature is extracted, anhydrous MgSO with methylene chloride and water4It is dry, it was spin-dried for column, obtains orange/yellow solid, as intermediate f, yield
It is 76%.1H NMR(400MHz,CDCl3),δ(ppm):9.84(s,2H),7.90(s,2H),7.68(s,2H),7.54(s,
2H),7.15–7.17(d,8H),7.04–7.06(d,8H),4.35–4.39(t,2H),2.52–2.56(t,8H),1.92–1.95
(m,2H),1.52–1.58(m,8H),1.25–1.28(m,50H),0.84–0.88(m,15H)；13C NMR(100MHz,
CDCl3),δ(ppm):182.92,157.01,151.60,146.39,145.79,141.83,141.79,141.21,134.07,
132.46,128.51,127.72,123.16,118.39,101.33,62.46,43.54,35.58,31.91,31.87,
31.41,29.51,29.48,29.27,29.24,29.06,27.35,22.70,22.66,14.15.
(4) chemical structural formula is the synthesis of the small organic molecule receptor of DTCC8-IC: by (0.4g, 0.3mmol) intermediate
F, the intermediate d of (0.4g, 2.1mmol), pyridine 1.5mL, 30mL chloroform, are added in reaction flask.Nitrogen protection, at 100 DEG C
Reaction 12 hours.It after stopping reaction, pours the mixture into and stirs a period of time in methanol, then filtered, cross column, obtain depth
Blue solid, as final goal product DTCC8-IC, yield 73%.1H NMR(400MHz,CDCl3),δ(ppm):8.68
(s,2H),8.66(d,2H),7.96(s,2H),7.85–7.87(d,2H),7.73–7.79(t,4H),7.67(s,2H),7.33
(s,2H),7.24–7.26(d,8H),7.12–7.14(d,8H),3.84(t,2H),2.55–2.59(t,8H),1.70(m,2H),
1.59–1.51(m,8H),1.25–1.29(m,50H),0.84–0.87(m,15H)；13C NMR(100MHz,CDCl3),δ
(ppm):187.96,160.97,159.81,157.93,147.55,142.06,141.74,141.54,140.99,140.19,
139.79,138.17,136.77,135.22,134.60,128.65,127.96,125.18,124.19,123.78,121.32,
118.38,114.56,114.46,102.13,68.38,62.30,42.78,35.65,31.92,31.46,29.55,29.51,
29.29,28.88,27.35,22.70,14.14.
The absorption spectra property of the preparation gained of above-described embodiment 1 and 2 small organic molecule receptor DTCC-IC and DTCC8-IC and
Non- fullerene solar cell properties measurement:
(1) absorption spectra property of small organic molecule receptor DTCC-IC and DTCC8-IC
Fig. 1 is ultraviolet-visible-near-infrared of small organic molecule receptor DTCC-IC film on chloroformic solution and quartz plate
Absorption spectrum.As shown in Figure 1, DTCC-IC solution and film show wide absorption region, film absorption absorption maximum side
Band value is all 778nm or so, and corresponding optical band gap is that (optical band gap is according to formula E by 1.59eVg=1240/ λ is calculated, wherein Eg
For optical band gap, λ is film absorption absorption maximum sideband value).
Fig. 2 is ultraviolet-visible-near-infrared of small organic molecule receptor DTCC8-IC film on chloroformic solution and quartz plate
Absorption spectrum.As shown in Figure 2, DTCC8-IC solution and film show wide absorption region, film absorption absorption maximum
Sideband value is all 765nm or so, and corresponding optical band gap is that (optical band gap is according to formula E by 1.62eVg=1240/ λ is calculated,
Middle EgFor optical band gap, λ is film absorption absorption maximum sideband value).
(2) the non-fullerene solar cell properties measurement of small organic molecule receptor DTCC-IC:
Donor using commercially available PCE10 as solar battery, 1 gained DTCC-IC of embodiment are solar-electricity
The receptor in pond constructs solar energy using classical sandwich device architecture (ITO/PEDOT:PSS/PCE10:DTCC-IC/Ca/Al)
Device.Wherein, indium oxide (ITO) glass (- 15 Ω of sheet resistance=10–1), it is first placed in acetone and isopropanol and carries out
Ultrasonic prerinse, then handled 20 minutes in UV ozone case.PEDOT:PSS aqueous solution is spin-coated on using solution spin-coating method
On ITO electro-conductive glass, dry 15 minute formation one layer PEDOT:PSS film (40nm) is subsequently placed in air under the conditions of 150 DEG C.
In nitrogen glove box, the dichlorobenzene solution spin-on deposition of PCE10:DTCC-IC (w/w=1:1) is existed using solution spin-coating method
On PEDOT:PSS film, the photosensitive activity layer film that a layer thickness is about 100-150nm is formed.Under the conditions of condition of high vacuum degree, first
The Al of the Ca and 100nm of 20nm is deposited afterwards as anode electrode.Effective work area of prepared solar battery is about
4mm2.In simulated solar radiant (light intensity 100mW/cm2) under irradiation, the J-V curve of solar battery is measured, such as Fig. 3 institute
Show.
Test results are shown in figure 3: short circuit current JscFor 11.23mA/cm2, open-circuit voltage VocFor 0.95V, fill factor
FF is 0.56, and the energy conversion efficiency for thus calculating battery is 6%.
(3) the non-fullerene solar cell properties measurement of small organic molecule receptor DTCC-IC:
With 1 the method for embodiment and condition preparation and test is receptor based on DTCC-IC and PCE10 is the non-lipid of donor
Strangle alkene solar battery.Test results are shown in figure 3: short circuit current JscFor 10.74mA/cm2, open-circuit voltage VocFor 0.95V, fill out
Filling factor FF is 0.47, and the energy conversion efficiency for thus calculating battery is 4.8%.
Claims (4)
1. a kind of A-D-A type small organic molecule receptor of seven yuan of condensed ring of carbazoles containing thieno, it is characterised in that have formula (I) institute
The structure shown:
Wherein, R1For C1-C16Linear or branched alkyl group；R2For formula (II), formula (III), formula (IV), formula (VI), formula (VII), formula
(VIII) one of structure shown in, wherein R C1-C16Linear or branched alkyl group
2. the preparation side of the A-D-A type small organic molecule receptor described in claim 1 containing seven yuan of condensed ring of thieno carbazoles
Method, it is characterised in that including following synthesis step:
(1) carbazole borate is reacted with thiophene ester halogenated compound, obtains intermediate a, the structural formula of the carbazole borate are as follows:
Wherein, R1It is C1-C16Linear or branched alkyl group；The thiophene ester halogenated compound structural formula are as follows:
The structural formula of the intermediate a are as follows:
Wherein, R1It is C1-C16Linear or branched alkyl group；
(2) at 100 DEG C, intermediate a elder generation and R2Grignard reagent reaction, using acetic acid cyclization, obtain intermediate b: in described
The structural formula of mesosome b are as follows:
Wherein, R2Grignard reagent structural formula be R2- MgBr, R2For above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula
(VII), one of structure shown in formula (VIII)；R1It can be C1-C16Linear or branched alkyl group；
(3) at 110 DEG C, intermediate b and phosphorus oxychloride and N, N '-dimethyl formamide obtain intermediate c, it is described in
The structural formula of mesosome c are as follows:
Wherein, R1For C1-C16Linear or branched alkyl group；
The R2For one of structure shown in above-mentioned formula (II), formula (III), formula (IV), formula (VI), formula (VII), formula (VIII)；
(4) at 100 DEG C, intermediate c is reacted with intermediate d, obtains having containing the A-D-A type of seven yuan of condensed ring of thieno carbazoles
Machine small molecule receptor, the structural formula of the intermediate d are as follows:
The concrete operations of the step (1) are as follows: by 10mmol carbazole borate, 20-100mmol thiophene ester halogenated compounds, 10-
100mmol anhydrous K2CO3, suitable water, 1-10mmol tetrabutylammonium bromide, 0.1-0.5g palladium catalyst, 200mL toluene, addition
Into reaction flask.Nitrogen protection is protected from light, and is reacted 10-15 hours, is cooled to room temperature at 100 DEG C, is extracted with methylene chloride and water,
Anhydrous MgSO4It is dry, it was spin-dried for column, obtains yellow solid, as intermediate a；
The concrete operations of the step (2) are as follows: by 10mmol magnesium chips, for appropriate iodine as catalyst, 10-30mmol are bromo
Object is closed, 50-150mL THF are added in reaction flask, nitrogen protection, are caused at 100 DEG C, and it is small to react 8-20 at this temperature
The THF solution of Shi Hou, 1-3mmol intermediate a are added in reaction system at normal temperature, and subsequent temperature rises to 110 DEG C of stirrings 10-
It 15 hours, is cooled to room temperature, is extracted with methylene chloride and water, through anhydrous MgSO4It is dry, after being spin-dried for column, 50-150mL are added
Acetic acid stirs 3-8 hours at nitrogen protection, 100 DEG C, after reaction stops, directly being filtered, obtains yellow solid, as
Intermediate b；
The concrete operations of the step (3) are as follows: by 0.5mmol intermediate product c, 10-30mmol phosphorus oxychloride, 30-100mL
DMF is added in reaction flask, nitrogen protection, is stirred 15-30 hours, is cooled to room temperature at 110 DEG C, is extracted with methylene chloride and water
It takes, anhydrous MgSO4It is dry, it was spin-dried for column, obtains yellow solid, as intermediate c；
The concrete operations of the step (4) are as follows: by 0.5mmol intermediate c, 1-10mmol intermediate d, pyridine 1-4mL, 20-
40mL chloroform, is added in reaction flask, nitrogen protection, reacts 8-15 hours at 100 DEG C, after stopping reaction, crosses column, obtains dark blue
Color solid, the as A-D-A type small organic molecule receptor containing seven yuan of condensed ring of thieno carbazoles.
3. A-D-A type small organic molecule the receptor described in claim 1 containing seven yuan of condensed ring of thieno carbazoles is in solar energy
Application in battery, to contain the A-D-A type small organic molecule receptor of seven yuan of condensed ring of thieno carbazoles as solar battery
Receptor.
4. A-D-A type small organic molecule receptor the preparation described in claim 1 containing seven yuan of condensed ring of thieno carbazoles is too
Positive energy battery device, the donor using commercially available PCE10 as solar battery, with seven yuan of condensed ring of carbazoles containing thieno
A-D-A type small organic molecule receptor be solar battery receptor, using classical sandwich device architecture construct solar energy device
Part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710043515.3A CN106831815B (en) | 2017-01-19 | 2017-01-19 | A kind of A-D-A type small organic molecule receptor of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710043515.3A CN106831815B (en) | 2017-01-19 | 2017-01-19 | A kind of A-D-A type small organic molecule receptor of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106831815A CN106831815A (en) | 2017-06-13 |
| CN106831815B true CN106831815B (en) | 2019-06-28 |
Family
ID=59120155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710043515.3A Expired - Fee Related CN106831815B (en) | 2017-01-19 | 2017-01-19 | A kind of A-D-A type small organic molecule receptor of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106831815B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573722B (en) * | 2017-08-03 | 2019-06-28 | 湘潭大学 | A kind of D-A-π-A type organic photosensitizing dyestuff of penta carbazole of ring containing Dithiophene and the preparation method and application thereof |
| WO2019052935A1 (en) * | 2017-09-13 | 2019-03-21 | Merck Patent Gmbh | Organic semiconducting compounds |
| WO2019137354A1 (en) * | 2018-01-10 | 2019-07-18 | The Hong Kong University Of Science And Technology | Thiophene-based fused aromatic systems |
| CN108299449B (en) * | 2018-01-15 | 2020-08-25 | 华南协同创新研究院 | Electroluminescent material based on carbazole five-membered heterocyclic unit and preparation method and application thereof |
| CN108299408A (en) * | 2018-01-23 | 2018-07-20 | 西安近代化学研究所 | Condensed ring A-D-A type conjugated molecules based on carbazole and preparation method thereof |
| CN109081825A (en) * | 2018-08-02 | 2018-12-25 | 常州大学 | A based on hexichol thio phenyl sulfone2(π-A1)2Non- fullerene acceptor material of type broad-band gap and its preparation method and application |
| CN110256460B (en) * | 2019-07-09 | 2021-06-15 | 湘潭大学 | Organic small molecule receptor material and preparation method and application thereof |
| CN110606857A (en) * | 2019-09-25 | 2019-12-24 | 湘潭大学 | A-D-A type organic small molecule based on nine-ring fused aromatic hydrocarbon and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101860084B1 (en) * | 2012-07-06 | 2018-05-23 | 삼성전자주식회사 | Organic photoelectric material and organic photoelectronic device and image sensor |
| CN105315298B (en) * | 2014-08-04 | 2017-10-10 | 中国科学院化学研究所 | A D A conjugated molecules and its preparation method and application based on seven and condensed ring unit |
-
2017
- 2017-01-19 CN CN201710043515.3A patent/CN106831815B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106831815A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106831815B (en) | A kind of A-D-A type small organic molecule receptor of seven yuan of condensed ring of carbazoles containing thieno and preparation method thereof | |
| CN106543201B (en) | A-D-A type conjugated molecule based on substituted indenothiophene fused ring unit and preparation method thereof | |
| CN108912140A (en) | A kind of asymmetry A-D-A type conjugation small molecule and its intermediate and application | |
| CN101665563B (en) | Donor-acceptor conjugated polymer and application thereof in solar cells | |
| CN101885732B (en) | Heterocyclic-sulfur fused naphthalenetetracarboxylic acid diimide derivatives, preparation method and application thereof | |
| CN106188506A (en) | One class closes polymer-metal complex dye sensitizing agent of Cu (II) and preparation method thereof containing 8 8-hydroxyquinoline derivatives | |
| CN105153189A (en) | Narrow-band-gap oligomer containing quinone type Methyl-Dioxocyano-Pyridine unit, and preparation method and application thereof | |
| CN105968329A (en) | Polymer containing 1,2,5-benzoselenadiazole-N-R1-5,6-imide dicarboxylate, and preparation method and application thereof | |
| Jiang et al. | Charge transfer in cross conjugated 4, 8-dithienylbenzo [1, 2-b: 4, 5-b′] dithiophene based organic sensitizers | |
| CN114805763A (en) | Three copolymerization complexes taking benzodithiophene derivatives as ligands, and preparation method and application thereof | |
| CN110357874B (en) | Phenothiazinyl benzothiadiazole dye, preparation method thereof and dye-sensitized solar cell using same | |
| CN113321791B (en) | Cadmium and nickel complex of two polymerized bithiophene derivatives and preparation method and application thereof | |
| CN110156616A (en) | The synthetic method for exempting to adulterate hole mobile material based on fluorene ethylene bridging aromatic rings core and its application in perovskite battery | |
| CN107365318B (en) | A kind of small organic molecule donor photovoltaic material containing fluorine with benzotriazole and preparation method thereof and its application | |
| CN110600612B (en) | P-i-n type perovskite battery hole transport layer based on self-assembly engineering | |
| CN110256460B (en) | Organic small molecule receptor material and preparation method and application thereof | |
| CN111333665B (en) | Conjugated small molecule electron acceptor material and preparation method thereof | |
| CN102295748B (en) | Fluorine polymer containing anthracene and pyrrole-pyrrole-dione units and preparation method and use thereof | |
| CN101864187B (en) | Dye with low energy level difference, intermediate and preparation method and application thereof | |
| CN103588677B (en) | 1, 2-2(benzophenone-hydrazone-yl)-acenaphthequinone-dihydrazone and preparation method thereof | |
| CN114479019B (en) | Triazine polymer material, preparation method thereof and application thereof in photoelectric device | |
| CN113321790B (en) | Cadmium and nickel complex of two polymeric imine derivatives and preparation method and application thereof | |
| CN105153182B (en) | A kind of Dihydrobenzofuranes C of 5 alkyl 2,360Fullerene double adduct and its production and use | |
| CN103044244A (en) | Pyrene D-pi-A type asymmetric disc dye compound | |
| CN106518905A (en) | Three-dimensional organic/inorganic hybrid cathode interface modification material, synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190628 Termination date: 20220119 |