CN107879996A - A kind of phenothiazines solar energy dye sensitizing agent and its preparation and application containing Fluorenone - Google Patents
A kind of phenothiazines solar energy dye sensitizing agent and its preparation and application containing Fluorenone Download PDFInfo
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- 230000001235 sensitizing effect Effects 0.000 title claims abstract description 19
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000002990 phenothiazines Chemical class 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000003053 piperidines Chemical class 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003480 eluent Substances 0.000 claims abstract description 5
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- -1 phenothiazine compound Chemical class 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229950000688 phenothiazine Drugs 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 206010070834 Sensitisation Diseases 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 230000008313 sensitization Effects 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- STTKJGDYTHDCLH-UHFFFAOYSA-N 2-cyanoacetate piperidin-1-ium Chemical class N1CCCCC1.C(#N)CC(=O)O STTKJGDYTHDCLH-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 238000003756 stirring Methods 0.000 abstract description 3
- 238000012216 screening Methods 0.000 abstract description 2
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 abstract 4
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WRAFKCSYEDDRQV-UHFFFAOYSA-N O=C1c2cc(-c(cc3)cc4c3N(c3ccccc3)c3ccccc3S4)ccc2-c(cc2)c1cc2-c1ccc[o]1 Chemical compound O=C1c2cc(-c(cc3)cc4c3N(c3ccccc3)c3ccccc3S4)ccc2-c(cc2)c1cc2-c1ccc[o]1 WRAFKCSYEDDRQV-UHFFFAOYSA-N 0.000 description 2
- 229910019213 POCl3 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical class OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 1
- 0 *C(C#N)=C[C@@]1OC(c(cc2)cc3c2-c(ccc(-c(cc2)cc4c2N(c2ccccc2)c(cccc2)c2S4)c2)c2C3=O)=CC1 Chemical compound *C(C#N)=C[C@@]1OC(c(cc2)cc3c2-c(ccc(-c(cc2)cc4c2N(c2ccccc2)c(cccc2)c2S4)c2)c2C3=O)=CC1 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- JCONFMMDTCCBCP-UHFFFAOYSA-N O=C1c2cc(-c(cc3)cc4c3N(c3ccccc3)c3ccccc3S4)ccc2-c(cc2)c1cc2-c1ccc[s]1 Chemical compound O=C1c2cc(-c(cc3)cc4c3N(c3ccccc3)c3ccccc3S4)ccc2-c(cc2)c1cc2-c1ccc[s]1 JCONFMMDTCCBCP-UHFFFAOYSA-N 0.000 description 1
- SDKVXMDKEDDCJG-UHFFFAOYSA-N O=Cc1ccc(-c(cc2)cc(C(c3c4)=O)c2-c3ccc4-c(cc2)cc3c2N(c2ccccc2)c2ccccc2S3)[o]1 Chemical compound O=Cc1ccc(-c(cc2)cc(C(c3c4)=O)c2-c3ccc4-c(cc2)cc3c2N(c2ccccc2)c2ccccc2S3)[o]1 SDKVXMDKEDDCJG-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
- C07D419/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D419/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of phenothiazines solar energy dye sensitizing agent containing Fluorenone and its preparation and application.The phenothiazines solar energy dye sensitizing agent containing Fluorenone is as shown in Formulas I, Formula II or formula III；Synthetic method of the present invention is：Formula IV compound is mixed with cyanoacetic acid with organic solvent; in the presence of piperidines; under nitrogen protection; it is heated to reflux 6~8h of stirring reaction; after reaction completely; solvent is spin-dried for, residue carries out silica gel column chromatography with eluant, eluent solvent, obtains the phenothiazines solar energy dye sensitizing agent containing Fluorenone shown in Formulas I, Formula II or formula III.Phenothiazine compounds of the present invention can be applied to DSSC as dye sensitizing agent, for dye sensitizing agent screening add it is new can applied material.
Description
(1) technical field
The present invention relates to a kind of phenothiazines solar energy dye sensitizing agent containing Fluorenone and its preparation and application.
(2) background technology
DSSC will have the big pi-conjugated structure organic dyestuff key of intramolecular charge transport system (ICT)
Close on semiconductor surface, semiconductor spectral response is widened into visible region even by means of strong absorption of the dyestuff to visible ray
Infrared region, produces photoelectric current, and luminous energy is converted into electric energy by natural imitation circle green plants photosynthesis.With first generation crystalline silicon too
Positive energy battery is compared with second generation multicomponent compound film solar cell, and the dye sensitization as third generation solar cell is too
It is positive can battery (DSSCs), have the advantages that cost is low, technique is simple, can dim light generating and photoelectric transformation efficiency it is high.
In DSSC (DSSCs), nonmetallic organic dye sensitized dose can be repaiied due to its flexible structure
Decorations, molar absorption coefficient are high, cost is low, the advantage such as environment-friendly causes increasing concern.Phenthazine be it is a kind of containing nitrogen,
The Electron rich aromatic heterocyclic compound of sulphur atom, its nitrogen-atoms and sulphur atom add the electron of compound, have good
Cavity transmission ability and unique photoelectric property.Meanwhile the non-co-planar molecular structure of buttferfly-type of phenthazine can effectively suppress
Molecule is assembled.In addition, phenthazine have C (3), C (7) and N- etc. it is multiple can decorating site, make it in medicine, dyestuff, optics material
Extensive concern is obtained in the numerous areas such as material.In addition, Fluorenone and its derivative have, heat endurance is high, electron-transporting is good, easy
In prepare the advantages that, be widely used in the preparation and research of photoelectric material.Fluorenone is incorporated into bridged bond by the present invention, respectively
Using Fluorenone-benzene, Fluorenone-furans and Fluorenone-thiophene as π bridges, using N- phenyl phenthazine as electron donor, using cyanoacetic acid as electronics by
Body, three D- π-A type phenothiazines dye sensitizing agents I~III are designed and synthesized.
(3) content of the invention
It is an object of the invention to provide a kind of phenothiazine compound containing Fluorenone and preparation method thereof.
A kind of phenothiazine compound containing Fluorenone, there is the structure shown in formula I, Formula II or formula III：
Present invention also offers the preparation method of the above-mentioned phenothiazine compound containing Fluorenone, described method is by following step
It is rapid to carry out：
Compound shown in Formulas I va, Ivb or Ivc is organic molten with the cyanoacetic acid shown in Formula V, piperidines, polarity respectively
After agent mixing, 6-8h is heated to reflux, after reaction completely, gained reaction mixture is post-treated to respectively obtain Formulas I, Formula II or formula
Compound shown in III；Described Formulas I va, Ivb or compound shown in Ivc and the cyanoacetic acid shown in described Formula V and
The ratio between amount of material of piperidines is 1：2-3.6：9-22；
Further, the polar organic solvent is one or more kinds of mixing in acetonitrile, chloroform and tetrahydrofuran
Thing.
Further, chemical combination of the volumetric usage of described polar organic solvent shown in described Formulas I va, Ivb or IVc
The amount of the material of thing is calculated as 57-67mL/mmol.
Further, the post-processing approach of reaction mixture of the present invention is：Compound shown in Iva, Ivb or Ivc
After terminating respectively with the cyanoacetic acid shown in Formula V, piperidines, polar organic solvent reaction, after solvent is evaporated off in gained reaction mixture,
Residue carries out silica gel column chromatography with eluant, eluent solvent, using the mixed solution that dichloromethane and methanol and acetic acid form as elution
Agent, the eluent containing target compound is collected, be concentrated and dried to obtain compound shown in Formulas I, Formula II or formula III.
Further, it is preferred that described eluting solvent is that volume ratio is 300:2:1 dichloromethane, methanol and acetic acid
Mixed solvent.
The present invention does not have particular/special requirement to the source of compound shown in the formula IV, using commercially available or those skilled in the art
It is prepared by known preparation method.
In embodiments of the present invention, compound shown in the formula IV a is preferably prepared with the following method, including following
Step：
In N2Under conditions of protection, by with shown in the compound of structure shown in Formula IV a, tetra-triphenylphosphine palladium and formula VII
Formyl phenylboronic acid compound is dissolved in tetrahydrofuran, obtains tetrahydrofuran solution, by the tetrahydrofuran solution and carbonic acid
The aqueous solution mixing of potassium is heated to reflux, and obtains the compound of structure shown in formula IV a；The change of structure shown in described Formula IV a
The ratio between amount of material of compound, tetra-triphenylphosphine palladium and formyl phenylboronic acid compound is 1：0.11：1.2；Described tetrahydrochysene
The addition of furans is calculated as 40mL/mmol with the amount of the material of the compound of structure shown in Formula IV a；The material of described potassium carbonate
Amount concentration be 0.3mmol/mL, it is described in terms of the addition of described wet chemical is come by the amount of the material of potassium carbonate
The addition of potassium carbonate is calculated as 4mmol/mmol with the amount of the material of the compound of structure shown in Formula IV a；
In embodiments of the present invention, compound shown in the formula IV b or IVc is preferably prepared with the following method, bag
Include following steps：
It will be mixed under DMF and POCl3 ice bath, Vilsmeier reagents be made；By Formula IV b
Or the compound shown in VIc is dissolved in dichloroethanes, it is added in Vilsmeier reagents, 10h is reacted at 65 DEG C, after post processing
Column chromatography obtains the compound shown in formula IV b or IVc；Compound, N shown in described Formula IV b or VIc, N- dimethyl formyls
The ratio between amount of material of amine and POCl3 is 1:2:2；Change of the addition of described dichloroethanes shown in Formula IV b or VIc
The amount of the material of compound is calculated as 5mL/mmol；
Present invention also offers the above-mentioned phenothiazine compound containing Fluorenone dye sensitization is being prepared as dye sensitizing agent
Application in solar cell, specific application are as follows：
The phenothiazines solar energy dye sensitizing agent containing Fluorenone is dissolved in chloroform-methanol (V:V=10:1) mixed
In bonding solvent, immersion titanium dioxide nano particle film optoelectronic pole 24 hours, described phenothiazine-type solar energy dye has been loaded
Expect the titanium dioxide electrodes of sensitizer, then dripped by its battery with platinum to electrode assembling into sandwich structure, and in battery edge
Enter electrolyte, electrolyte is introduced into inside battery using capillary percolation principle, with 100mV/cm2Under light intensity irradiation, photoelectricity is determined
Piezo-electric properties of flow curve.Its result shows, the photoelectricity for the DSSC that such solar energy dye sensitizing agent makes
Transformation efficiency is between 5.24-5.75%.
Compared with prior art, the beneficial effects of the present invention are：
The invention provides a kind of new phenothiazine compound containing Fluorenone, preparation technology is simple, the compound conduct
The DSSC that dye sensitizing agent is assembled into has preferable photoelectric transformation efficiency, is the screening of dye sensitizing agent
Add it is new can applied material.
(4) illustrate
Fig. 1 is as dye sensitizing agent based on the phenothiazine compound containing Fluorenone shown in Formulas I, Formula II or formula III
Photoelectric current-voltage curve of solar cell.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：
Under nitrogen protection, by compound VIa (0.40g, 0.75mmol), 4- formyl phenylboronic acids (0.13g,
0.90mmol),Pd(PPh3)4(0.09g, 0.08mmol), K2CO3(0.41g, 3.00mmol) is dissolved in H2O-THF mixed solvents
(40mL, VH2O:VTHF=1:3), it is heated to reflux 10h.Solvent is evaporated off in reaction solution, dissolves residue with DCM, molten through saturated sodium-chloride
Liquid washs, anhydrous Na2SO4Dry, after concentration, column chromatography (VPE:VDCM=1:2) isolated red powder IVa (0.28g,
67.0%).282~283 DEG C of fusing point；1H NMR(500MHz,CDCl3) δ 10.08 (s, 1H), 7.99 (d, J=8.2Hz, 2H),
7.96 (d, J=1.4Hz, 1H), 7.84-7.78 (m, 4H), 7.67 (d, J=8.0Hz, 2H), 7.65-7.62 (m, 2H), 7.58
(d, J=8.0Hz, 1H), 7.54 (t, J=7.5Hz, 1H), 7.44 (d, J=7.2Hz, 2H), 7.29 (d, J=2.1Hz, 1H),
7.10 (dd, J=8.6,2.2Hz, 1H), 7.04 (dd, J=7.2,1.9Hz, 1H), 6.89-6.82 (m, 2H), 6.24 (d, J=
8.6Hz, 1H), 6.19 (dd, J=7.9,1.4Hz, 1H)
Under nitrogen protection, by compound IVa (0.25g, 0.45mmol), cyanoacetic acid (0.14g, 1.60mmol) and piperidines
(1mL, 10mmol) is dissolved in CHCl3In (30mL), 8h is heated to reflux.Column chromatography (V after reaction solution concentrationDCM:VMeOH:VAcOH=
300:2:1) isolated black powder I (0.23g, 81.9%).276~278 DEG C of fusing point；1H NMR(500MHz,DMSO)δ
8.40 (s, 1H), 8.16 (d, J=8.6Hz, 2H), 8.07 (dd, J=7.9,1.7Hz, 1H), 8.02 (d, J=8.5Hz, 2H),
8.00 (d, J=1.4Hz, 1H), 7.96 (d, J=7.8Hz, 1H), 7.91 (d, J=7.8Hz, 1H), 7.88 (dd, J=7.9,
1.6Hz, 1H), 7.83 (s, 1H), 7.73 (t, J=7.8Hz, 2H), 7.60 (t, J=7.5Hz, 1H), 7.52 (d, J=2.2Hz,
1H), 7.50-7.47 (m, 2H), 7.36 (dd, J=8.7,2.2Hz, 1H), 7.11 (dd, J=7.5,1.5Hz, 1H), 6.96-
6.92 (m, 1H), 6.88 (td, J=7.5,1.2Hz, 1H), 6.18 (d, J=8.6Hz, 1H), 6.13 (dd, J=8.2,1.0Hz,
1H).HRMS(ESI)m/z623.1440[M-H]+,Calcd for C41H23N2O3S:623.1429.
Embodiment 2：
Under nitrogen protection, dry DMF (0.15g, 2.00mmol), POCl are added into there-necked flask3(0.31g,
2.00mmol), 0.5h is stirred under ice bath and Vilsmeier reagents is made.Compound VIb (0.52g, 1.00mmol) is used into DCE
It is added to after (5mL) dissolving in above-mentioned system, reacts 10h at 65 DEG C.It is cooled to after room temperature plus 50mL water stirs 0.5h, uses DCM
Extraction, organic layer washs through saturated nacl aqueous solution, anhydrous Na2SO4Dry, after concentration, column chromatography (VPE:VDCM=1:4) separate
Obtain red powder IVb (0.42g, 76.7%).330~332 DEG C of fusing point；1H NMR(500MHz,CDCl3)δ9.69(s,1H),
8.07 (s, 1H), 8.03 (d, J=7.2Hz, 1H), 7.84 (s, 1H), 7.67-7.64 (m, 2H), 7.54 (d, J=6.7Hz,
2H), 7.44 (d, J=7.2Hz, 2H), 7.38-7.35 (m, 2H), 7.14 (d, J=9.0Hz, 1H), 7.11-7.08 (m, 2H),
7.04 (d, J=6.4Hz, 1H), 6.93 (d, J=3.6Hz, 1H), 6.85 (t, J=7.5Hz, 2H), 6.24 (d, J=8.0Hz,
1H), 6.19 (d, J=7.2Hz, 1H)；
Under nitrogen protection, by compound IVb (0.27g, 0.50mmol), cyanoacetic acid (0.09g, 1.06mmol) and piperidines
(0.5mL, 5mmol) is dissolved in CH3In CN (30mL), 7h is heated to reflux.Column chromatography (V after reaction solution concentrationDCM:VMeOH:VAcOH=
300:2:1) isolated black powder II (0.26g, 85.2%).303~305 DEG C of fusing point；1H NMR(500MHz,DMSO)δ
12.07 (bs, 1H), 8.13-8.07 (m, 2H), 8.06 (s, 1H), 7.96 (d, J=7.9Hz, 1H), 7.86 (s, 2H), 7.79
(s, 1H), 7.72 (t, J=7.7Hz, 2H), 7.59 (t, J=7.4Hz, 1H), 7.55 (d, J=3.2Hz, 2H), 7.49 (s,
1H), 7.47 (d, J=1.5Hz, 2H), 7.33 (d, J=9.3Hz, 1H), 7.10 (d, J=7.4Hz, 1H), 6.93 (t, J=
7.1Hz, 1H), 6.87 (t, J=7.3Hz, 1H), 6.15 (d, J=8.6Hz, 1H), 6.11 (d, J=8.0Hz, 1H) .HRMS
(ESI)m/z 613.1224[M-H]-,Calcd for C39H21N2O4S:613.1222.
Embodiment 3：
Under nitrogen protection, dry DMF (0.29g, 3.97mmol), POCl are added into there-necked flask3(0.61g,
3.98mmol), 0.5h is stirred under ice bath and Vilsmeier reagents is made.Compound VIc (1.07g, 2.00mmol) is used into DCE
It is added to after (10mL) dissolving in above-mentioned system, reacts 10h at 65 DEG C.It is cooled to after room temperature plus 50mL water stirs 0.5h, uses DCM
Extraction, organic layer washs through saturated nacl aqueous solution, anhydrous Na2SO4Dry, after concentration, column chromatography (VPE:VDCM=1:4) separate
Obtain red powder IVc (0.75g, 66.6%).298~300 DEG C of fusing point；1H NMR(500MHz,DMSO)δ9.94(s,1H),
8.10-8.06 (m, 2H), 8.02 (d, J=1.5Hz, 1H), 7.97-7.93 (m, 2H), 7.93-7.88 (m, 2H), 7.86 (s,
1H), 7.73 (t, J=7.8Hz, 2H), 7.61 (d, J=6.0Hz, 1H), 7.54 (d, J=2.1Hz, 1H), 7.49 (d, J=
7.4Hz, 2H), 7.37 (dd, J=8.9,2.3Hz, 1H), 7.11 (d, J=7.3Hz, 1H), 6.94 (d, J=8.5Hz, 1H),
6.89 (d, J=7.8Hz, 1H), 6.18 (d, J=8.8Hz, 1H), 6.13 (d, J=6.9Hz, 1H)
Under nitrogen protection, by compound IVc (0.30g, 0.53mmol), cyanoacetic acid (0.09g, 1.06mmol) and piperidines
(0.5mL, 5mmol) is dissolved in tetrahydrofuran (30mL), is heated to reflux 6h.Column chromatography (V after reaction solution concentrationDCM:VMeOH:VAcOH
=300:2:1) isolated black powder III (0.28g, 83.0%).Fusing point>350℃；1H NMR(500MHz,DMSO)δ
8.47(s,1H),8.03-7.99(m,2H),7.96(s,1H),7.94-7.91(m,2H),7.90-7.86(m,2H),7.83(s,
1H), 7.72 (t, J=7.7Hz, 2H), 7.60 (t, J=7.5Hz, 1H), 7.51 (d, J=2.1Hz, 1H), 7.48 (d, J=
7.3Hz, 2H), 7.35 (dd, J=8.6,2.2Hz, 1H), 7.10 (dd, J=7.5,1.5Hz, 1H), 6.96-6.92 (m, 1H),
6.89-6.86 (m, 1H), 6.17 (d, J=8.6Hz, 1H), 6.12 (d, J=8.1Hz, 1H) .HRMS (ESI) m/z 629.1025
[M-H]-,Calcd for C39H21N2O3S2:629.0994.
Embodiment 4：
Application of the phenothiazine compound as dye sensitizing agent
The double-deck TiO prepared using silk-screen printing2Film of nanoparticles is as optoelectronic pole：Printed first on electro-conductive glass FTO
The 20nm of one layer of 12 μ m-thick TiO2Particle, 30min is calcined in Muffle furnace at 450 DEG C.By burned film before material is contaminated
Immerse 0.04molL-1TiCl470 DEG C of pretreatment 30min of the aqueous solution, then use water and alcohol flushing, hair dryer blows respectively
It is dry.After calcining 30min again at 450 DEG C of Muffle furnace, 3 × 10 are immersed after being cooled to 80 DEG C-4mol·L-1Chloroform-first of dyestuff
Alcohol (V:V=10:1) solution room temperature 24h is sensitized.Preparation to electrode：Using method for printing screen, by certain density H2PtCl6
Solution is printed on FTO electro-conductive glass, then 400 DEG C of Muffle furnace sintering 20min.Adsorb the TiO of dyestuff2Electrode and platinum are to electrode
Sandwich structure is assembled into, and electrolyte is instilled at edge, inside battery is introduced using capillary percolation principle.In 100mW/
cm2Under light intensity irradiation, photovoltage-current characteristic curve is determined.Its result is as shown in table 1：
The phenothiazine compound of table 1 assembles obtained DSSC performance parameters
a:Jsc is short-circuit current density；b:Voc is open-circuit voltage；c:Ff is fill factor, curve factor；d:η is photoelectric transformation efficiency.
Dye sensitizing agent provided by the present invention is respectively provided with photoelectric conversion ability, Ke Yizuo it can be seen from Fig. 1 and table 1
For the dye sensitizing agent of DSSC, and its electricity conversion has excellent up to being 5.24~5.75%
Photoelectric conversion performance.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of phenothiazine compound containing Fluorenone of structure as shown in Formulas I, Formula II or formula III,
2. a kind of preparation method of the phenothiazine compound containing Fluorenone as claimed in claim 1, it is characterised in that described
Method is carried out as follows：
Compound shown in Formulas I va, Ivb or Ivc is mixed with the cyanoacetic acid shown in Formula V, piperidines and polar organic solvent respectively
After conjunction, 6-8h is heated to reflux, after reaction completely, gained reaction mixture is post-treated to respectively obtain Formulas I, Formula II or formula III institute
The compound shown；Described Formulas I va, Ivb or compound shown in Ivc and the cyanoacetic acid shown in described Formula V and piperidines
The ratio between amount of material is 1：2-3.6：9-22；
3. preparation method as claimed in claim 2, it is characterised in that described polar organic solvent is chloroform, acetonitrile or four
One or more kinds of mixtures in hydrogen furans.
4. preparation method as claimed in claim 2, it is characterised in that the volumetric usage of described polar organic solvent is with described
Formulas I va, Ivb or IVc shown in the amount of material of compound be calculated as 57-67mL/mmol.
5. preparation method as claimed in claim 2, it is characterised in that the post-processing approach of described reaction mixture is：Institute
The compound shown in Formulas I va, Ivb or Ivc stated is organic molten with the cyanoacetic acid piperidines shown in described Formula V and polarity respectively
After agent reaction terminates, after gained reaction mixture is evaporated off into solvent, residue carries out silica gel column chromatography, with dichloromethane and methanol
And the mixed solution of acetic acid is eluant, eluent, the eluent containing target compound is collected, is concentrated and dried and obtains Formulas I, Formula II or formula respectively
Phenothiazine compound shown in III.
6. a kind of phenothiazine compound containing Fluorenone as claimed in claim 1 is preparing dye sensitization as dye sensitizing agent
Application in solar cell.
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| CN108822100A (en) * | 2018-07-31 | 2018-11-16 | 江苏理工学院 | D-A- π-A type three-dimensional phenothiazines dye sensitizing agent and its preparation method and application |
| CN108997335A (en) * | 2018-07-19 | 2018-12-14 | 浙江工业大学 | A kind of Pyridine-quinazolinocompound compound and its preparation method and application |
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| WO2013008951A1 (en) * | 2011-07-13 | 2013-01-17 | National Institute For Materials Science | Organic dye, dye-sensitized metal oxide semiconductor electrode and dye-sensitized solar cell |
| CN105777613A (en) * | 2016-04-08 | 2016-07-20 | 浙江工业大学 | N-butylcarbazole compounds containing fluorenone and preparation method and application of N-butylcarbazole compounds |
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| WO2013008951A1 (en) * | 2011-07-13 | 2013-01-17 | National Institute For Materials Science | Organic dye, dye-sensitized metal oxide semiconductor electrode and dye-sensitized solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108997335A (en) * | 2018-07-19 | 2018-12-14 | 浙江工业大学 | A kind of Pyridine-quinazolinocompound compound and its preparation method and application |
| CN108822100A (en) * | 2018-07-31 | 2018-11-16 | 江苏理工学院 | D-A- π-A type three-dimensional phenothiazines dye sensitizing agent and its preparation method and application |
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