CN104672237A - Organic photosensitive dye based on phenanthroline as electron acceptor as well as preparation method and application of organic photosensitive dye - Google Patents
Organic photosensitive dye based on phenanthroline as electron acceptor as well as preparation method and application of organic photosensitive dye Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- 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
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- H—ELECTRICITY
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- 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
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- 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
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- 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
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a compound represented by a formula I. In the formula I, pi is structure-free or is selected from any one of structures represented by a formula II and a formula III; D is selected from any one of structures represented by a formula IV, a formula V and a formula VI, wherein R is alkyl or alkoxy of C1-C6, and alkyl or alkoxy of C1-C6 is a linear chain or a branched chain. Under the action of corresponding catalysts, the compound represented by the formula I can be prepared through a reflux reaction, a friedel-crafts acylation and a condensation reaction, a phenanthroline structural unit is introduced as an electron acceptor, and the organic dye with the structure including the electron donor, the conjugate bridge and the electron acceptor is synthesized. The dye has good absorption performance in the visible and infrared spectral region of a solar spectrum, has higher sunlight utilization rate and has wide application in the aspect of preparation of a dye-sensitized solar cell, especially a dye-sensitized nano-crystalline titanium dioxide solar cell.
Description
Technical field
The invention belongs to organic photosensitive dye field, being specifically related to a kind of is organic photosensitive dye well its preparation method and the application of electron acceptor(EA) based on phenanthroline.
Background technology
Compared to traditional silica-based solar cell, the favor that dye sensitization solar battery is simple with its manufacture craft, low cost and photoelectric transformation efficiency advantages of higher are subject to global scientific research and industry member.From nineteen ninety Switzerland scientist
a kind of etc. reported first with the solar cell of ruthenium pyridine complex (N3) dye-sensitized nano titanium dioxide semiconductor (Brian O ' Regan and Michael.
.Nature, 353,1991,937 – 939) since, countries in the world scientist has carried out a large amount of fruitful research work, has effectively promoted the Theory and applications research work of dye sensitization solar battery.
Typical dye sensitization solar battery is by conductive glass, nano titanium oxide, photosensitizers, ionogen and form electrode 5 part.Wherein organic photosensitive dyestuff is as core, and absorbing sunlight and excite generation photon, is the key component directly determining solar cell properties.Therefore, quite most research work mainly concentrates on design and the synthesis of organic photosensitive dyestuff.
Organic photosensitive dyestuff generally has three parts to form: electron donor(ED) (Donor), conjugation abutment (Bridge) and electron acceptor(EA) (Acceptor) three part form.Electron donor(ED) common are the nitrogenous electron rich structural units such as triaryl amine, carbazole, indoles, excites rear generation photoelectron by sunlight; The structure of conjugation abutment is then of a great variety, generally there is the constitutional features such as large ring or conjugated polycyclic double bond, common are thiophene, thiophthene, porphyrin etc., conjugation abutment mainly plays two aspect effects: one is the absorption spectrum widening light-sensitive coloring agent, improves the utilization ratio of incident sunlight; Two is excited by electron donor(ED) the photoelectron of generation to conduct to electron acceptor(EA).Electron acceptor(EA) is the electron deficiency such as carboxyl, cyanoacetic acid structural unit commonly, and electron acceptor(EA) role is that light-sensitive coloring agent is adsorbed in nano titanium oxide, and the photoelectron conducted by conjugation abutment imports titanium dioxide conduction band thus makes battery functions.But the group such as carboxyl, cyanoacetic acid is through strongly-acid electrolytic solution (I
-/ I
3 -) be easy to cause cell photoelectric efficiency of conversion to decline from nanometer titanium dioxide layer De contamination after immersion, thus have impact on the stability of battery performance.Therefore, the strong adsorptive type electron acceptor(EA) that researchdevelopment is novel has important theory and realistic meaning.
Summary of the invention
The object of this invention is to provide a kind of is the organic photosensitive dye well its preparation method of electron acceptor(EA) based on phenanthroline.
General structure based on the phenanthroline organic photosensitive dyestuff that is electron acceptor(EA) provided by the present invention is such as formula shown in I:
In described formula I, π be selected from that non-structure or π be selected from structure shown in formula II and formula III any one.
In described formula I, D be selected from structure shown in structure and formula VI shown in structure shown in formula IV, formula V any one, wherein, R is alkyl or the alkoxyl group of C1-C6, and the alkyl of described C1-C6 or alkoxyl group are straight or branched.
Preferred, organic photosensitive dyestuff of the present invention be selected from following any one:
D1: π is structure shown in formula II; D is structure shown in formula IV;
D2: π is structure shown in formula III; D is structure shown in formula VI, and R is methyl;
D3: π is non-structure; D is structure shown in formula V, and R is hexyloxy.
Provided by the present invention is that the preparation method of the organic photosensitive dyestuff of electron acceptor(EA) is as follows based on phenanthroline:
Preparation π be selected from structure shown in formula II and formula III any one, and D is selected from structure shown in structure and formula V shown in formula IV, and the method for compound described in any one formula I comprises the steps:
1) under Pd catalyst action, reactant 1, reactant 2 and alkaline matter are carried out linked reaction in organic solvent, obtain intermediate P1, wherein, described reactant 1 is selected from the (N of compound shown in formula VII, the boronic acid compounds of N-Diethyl Aniline) or formula VIII shown in the compound boronic acid compounds of triphenylamine (replace), described reactant 2 is selected from compound shown in compound shown in formula IX (2-halogenated thiophene) or formula X (2-halo 1,4-Dithiapentalene);
2) under aluminum trichloride catalyst effect, compound (oxalyl chloride) shown in described intermediate P1 and formula XI is carried out friedel-crafts acylation reaction in organic solvent, obtains intermediate P2;
3) compound shown in described intermediate P2 and formula XII (5,6-diaminostilbene, 10-phenanthroline) is carried out condensation reaction in organic solvent, obtain compound shown in formula I.
In described formula VIII, the definition of R in the definition cotype I of R; A in formula IX and formula X is halogen atom, described halogen atom specifically optional from following any one: Cl, Br or I.
In aforesaid method, step 1) in, described Pd catalyzer is selected from following at least one: Pd (Ph
3)
2cl
2, Pd (OAc)
2with Pd (PPh
3)
4, specifically can be Pd (PPh
3)
4.
Described alkaline matter is selected from following at least one: K
2cO
3, Na
2cO
3, KOH and NaOH etc., specifically can be K
2cO
3.
The mol ratio of described Pd catalyzer, reactant 1, reactant 2 and alkaline matter is 1:(20-100): (20-120): (40-200), specifically can be 1:66.7:66.7:100.
Described organic solvent is selected from as follows: the mixed system of at least one in toluene, dimethylbenzene, dioxane and tetrahydrofuran (THF) or itself and water, wherein, in described mixed system, the volume ratio of organic solvent and water is 3:(1-3), specifically can be the mixed system of tetrahydrofuran (THF) and water.
Described reaction is the back flow reaction of carrying out under rare gas element (as: nitrogen) atmosphere.
The temperature of reaction of described reaction is 100-140 DEG C, and the reaction times is 12-36h, is specially 24h.
In aforesaid method, step 2) in, shown in described aluminum chloride, intermediate P1 and formula XI, the mol ratio of compound is (1-1.5): (1-1.2): 0.5, is specially 1.2:1:0.5.
The temperature of reaction of described friedel-crafts acylation reaction is 5-30 DEG C, is specially 25 DEG C, and the reaction times is 5-20h, is specially 6h.
Described friedel-crafts acylation reaction organic solvent used is at least one in methylene dichloride and ethylene dichloride, is specially methylene dichloride.
In aforesaid method, step 3) in, shown in described intermediate P2 and formula XII, the mol ratio of compound is (1-2.0): 1, is specially 1:1.
The temperature of reaction of described condensation reaction is 100-140 DEG C, and the reaction times is 12-36h.
Described condensation reaction organic solvent used is at least one in Glacial acetic acid and propionic acid, is specially Glacial acetic acid.
Preparation π be selected from structure shown in formula II and formula III any one, and D be selected from structure shown in formula VI formula I described in the method for compound comprise the steps:
A) under Cu catalyzer existence condition, compound shown in formula XIII, described reactant 2, part and alkaline matter are reacted in organic solvent, obtain intermediate P3, wherein, described reactant 2 is selected from compound shown in compound shown in formula IX (2-halogenated thiophene) or formula X (2-halo 1,4-Dithiapentalene), and described part is selected from following at least one: 4,7-dimethyl-phenanthroline, 3, the bromo-phenanthroline of 8-bis-and 1,10-phenanthroline;
B) under aluminum chloride effect, compound (oxalyl chloride) shown in described intermediate P3 and formula XI is carried out friedel-crafts acylation reaction in organic solvent, obtains intermediate P4;
C) compound shown in described intermediate P4 and formula XII (5,6-diaminostilbenes, 10-phenanthroline) is carried out condensation reaction in organic solvent, obtain compound shown in formula I.
In described formula XIII, the definition of R in the definition cotype I of R.
In aforesaid method, step a) in, described Cu catalyzer is selected from following at least one: CuCl, CuBr and CuI, specifically can be CuI.
Described alkaline matter is selected from following at least one: K
2cO
3, Na
2cO
3, KOH and NaOH etc., specifically can be KOH.
Described part specifically can be 1,10-phenanthroline.
The mol ratio of described Cu catalyzer, part, reactant 2, compounds X III and alkaline matter is 1:(2-4): (30-100): (20-100): (20-100), specifically can be 1:2:80:66.7:100.
Described organic solvent is selected from as follows: the mixed system of at least one in toluene, dimethylbenzene and trimethylbenzene or itself and water, specifically can be the mixed system of dimethylbenzene and water.
Described reaction is the back flow reaction of carrying out under rare gas element (as: nitrogen) atmosphere.
The temperature of reaction of described reaction is 100-150 DEG C, and the reaction times is 12-36h, is specially 24h.
In aforesaid method, step b) in, shown in described aluminum chloride, intermediate P3 and formula XI, the mol ratio of compound is (1-1.5): (1-1.2): 0.5.
The temperature of reaction of described friedel-crafts acylation reaction is 5-30 DEG C, and the reaction times is 5-20h.
Described friedel-crafts acylation reaction organic solvent used is at least one in methylene dichloride and ethylene dichloride, is specially methylene dichloride.
In aforesaid method, step c) in, shown in described intermediate P4 and formula XII, the mol ratio of compound is (1-2.0): 1.
The temperature of reaction of described condensation reaction is 100-140 DEG C, and the reaction times is 12-36h.
Described condensation reaction organic solvent used is at least one in Glacial acetic acid and propionic acid, is specially Glacial acetic acid.
Preparation π is selected from non-structure, and D is selected from structure shown in structure and formula VI shown in structure shown in formula IV, formula V, and the method for compound described in any one formula I comprises the steps:
I) under aluminum chloride effect, compound shown in reactant 3 and formula XI (oxalyl chloride) is carried out friedel-crafts acylation reaction in organic solvent, obtain intermediate P5, described reactant 3 be selected from compound shown in compound and formula XIII shown in compound shown in formula VII, formula VIII any one;
II) compound shown in described intermediate P5 and formula XII (5,6-diaminostilbene, 10-phenanthroline) is carried out condensation reaction in organic solvent, obtain compound shown in formula I.
In aforesaid method, step I) in, shown in described aluminum chloride, reactant 3 and formula XI, the mol ratio of compound is (1-1.5): (1-1.2): 0.5.
The temperature of reaction of described friedel-crafts acylation reaction is 5-30 DEG C, and the reaction times is 5-20h.
Described friedel-crafts acylation reaction organic solvent used is at least one in methylene dichloride and ethylene dichloride, is specially methylene dichloride.
In aforesaid method, Step II) in, shown in described intermediate P5 and formula XII, the mol ratio of compound is (1-2.0): 1.
The temperature of reaction of described condensation reaction is 100-140 DEG C, and the reaction times is 12-36h.
Described condensation reaction organic solvent used is at least one in Glacial acetic acid and propionic acid, is specially Glacial acetic acid.
The present invention preparation-obtained a kind of be that the organic photosensitive dyestuff of electron acceptor(EA) also belongs to protection scope of the present invention preparing the application in solar cell based on phenanthroline.
Described solar cell is nanometer titanium dioxide titanium solar battery.
Because phenanthroline class formation is widely used in transition metal-catalyzed and organic photoelectrical material field as a bitooth ligand.Two nitrogen-atoms in phenanthroline structure can form stronger coordination chemistry key (therefore the preparation-obtained organic photosensitive dyestuff being electron acceptor(EA) based on phenanthroline has stronger adsorptivity) with various metals, and phenanthroline molecular skeleton is three ring conjugated structure systems, there is good electronic conduction ability, it is an excellent electron acceptor(EA) candidate structure unit, the present invention introduces phenanthroline structural unit first as electron acceptor(EA), synthesize the organic dye with electricity Gei Ti – electronics Zhong Ji – electron acceptor(EA) structure, this kind of dyestuff has good absorption at the visible of solar spectrum and IR regions, organic dye molecule of the present invention has large delocalized pi-bond, and photo-excited electron by the transition of π-π antibonding, thus has higher uptake factor, partly leads in film in same thickness, higher to the absorption rate of light, compared with the dye molecule being electron acceptor(EA) with carboxyl, structure is simple, novel, has higher photoelectric transformation efficiency, with other non-carboxy group acceptor dyestuffs, as: pyridine, hydroxyquinoline or nitro etc. are compared, and photoelectric transformation efficiency is quite or better.
Accompanying drawing explanation
The preparation flow figure of Fig. 1 to be of the present invention based on phenanthroline be organic photosensitive dyestuff of electron acceptor(EA).
Embodiment
Be described method of the present invention below by specific embodiment, but the present invention is not limited thereto, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Based on phenanthroline be the preparation flow figure of the organic photosensitive dyestuff of electron acceptor(EA) as shown in Figure 1.
Embodiment 1, be the preparation (wherein, in formula I, π is structure shown in formula II, and D is structure shown in formula IV) of the organic photosensitive dyestuff D1 of electron acceptor(EA) based on phenanthroline:
1) 4-(N, N-diethylin)-phenylo boric acid (1.93g, 10mmol), Pd (PPh
3)
4(187mg, 0.15mmol), K
2cO
3the bromo-thiophene of (2.07g, 15mmol), 2-(1.63g, 10mmol), water (7mL) and tetrahydrofuran (THF) (20mL) under nitrogen atmosphere, back flow reaction 24 hours at 80 DEG C.In reaction solution impouring methylene dichloride (50mL), washing, collect organic phase, anhydrous sodium sulfate drying, removes solvent under reduced pressure, and resistates crosses silicagel column, and moving phase is methylene dichloride and the sherwood oil mixed solvent of volume ratio 1:3, obtains intermediate P1;
2) step 1) made intermediate P1 (2.31g, 10mmol) is dissolved in dry methylene chloride (50mL), at 0 DEG C, add aluminum trichloride (anhydrous) (1.6g, 12mmol) in batches.Stir after 20 minutes, slowly drip methylene dichloride (10mL) solution of oxalyl chloride (5mmol).Drip and finish, rise to room temperature and continue stirring 6 hours.Reaction is finished, and drips 10% aqueous hydrochloric acid (10mL) to reaction solution.Collect organic phase, respectively with saturated sodium bicarbonate solution and washing, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, resistates crosses silicagel column, and moving phase is methylene dichloride and the sherwood oil mixed solvent of volume ratio 1:1, obtains intermediate P2;
3) 5,6-diaminostilbenes, 10-phenanthroline A (2.10g, 10mmol), intermediate P2 (10mmol) and Glacial acetic acid (40mL), back flow reaction 24 hours at 120 DEG C.Be down to room temperature, remove solvent under reduced pressure.Resistates, with chloroform extraction, is washed with 10% sodium hydrogen carbonate solution and saturated common salt, anhydrous sodium sulfate drying respectively.Remove solvent under reduced pressure, resistates crosses silicagel column, and moving phase is methylene dichloride and the ethyl acetate mixed solvent of volume ratio 1:1, obtains organic photosensitive dyestuff D1, yield 62%,
1hNMR (CDCl
3): 1.15 (t, 12H), 3.41 (q, 8H), 6.82 (d, 4H), 6.95 (d, 4H), 7.58 (m, 2H), 7.73 (d, 4H), 9.23 (d, 2H), 9.57 (d, 2H).
Embodiment 2, be the preparation (wherein, in formula I, π is structure shown in formula III, and D is structure shown in formula VI, and R=methyl wherein) of the organic photosensitive dyestuff D2 of electron acceptor(EA) based on phenanthroline:
1) under nitrogen atmosphere, 4,4 '-dimethyl pentanoic (1.97g, 10mmol), CuI (28.5mg, 0.15mmol), 1,10-phenanthroline (54mg, 0.3mmol), potassium hydroxide (1.12g, 15mmol), the iodo-1,4-Dithiapentalene (3.16g, 12mmol) of 2-, water (7mL) and dimethylbenzene (20mL) reacts 24 hours at 130 DEG C, is down to room temperature, in reaction solution impouring methylene dichloride (100mL), washing, collects organic phase, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, resistates crosses silicagel column, and moving phase is methylene dichloride and the sherwood oil mixed solvent of volume ratio 1:3, obtains intermediate P3;
2) step 1) made intermediate P3 (3.35g, 10mmol) be dissolved in dry methylene chloride (50mL), add aluminum trichloride (anhydrous) (1.6g at 0 DEG C in batches, 12mmol), stir after 20 minutes, methylene dichloride (10mL) solution of slow dropping oxalyl chloride (5mmol), drip and finish, rise to room temperature and continue stirring 6 hours, reaction is finished, 10% aqueous hydrochloric acid (10mL) is dripped to reaction solution, collect organic phase, respectively with saturated sodium bicarbonate solution and washing, anhydrous sodium sulfate drying, remove solvent under reduced pressure, resistates crosses silicagel column, moving phase is methylene dichloride and the sherwood oil mixed solvent of volume ratio 1:1, obtain intermediate P4,
3) 5,6-diaminostilbene, 10-phenanthroline A (2.10g, 10mmol), intermediate P4 (10mmol) and Glacial acetic acid (40mL) back flow reaction 24 hours at 120 DEG C, be down to room temperature, remove solvent under reduced pressure, resistates is with chloroform extraction, respectively with 10% sodium hydrogen carbonate solution and saturated common salt washing, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, resistates crosses silicagel column, and moving phase is methylene dichloride and the ethyl acetate mixed solvent of volume ratio 1:1, obtains organic photosensitive dyestuff D2, yield 56%,
1hNMR (CDCl
3): 2.34 (s, 12H), 6.01 (s, 2H), 6.51 (d, 8H), 6.98 (d, 8H), 7.36 (s, 2H), 7.75 (m, 2H), 9.36 (d, 2H), 9.61 (d, 2H).
Embodiment 3, be the preparation (wherein, in formula I, π is nothing, and D is structure shown in formula V, and R=hexyloxy wherein) of the organic photosensitive dyestuff D3 of electron acceptor(EA) based on phenanthroline:
1) N, N-(4-Hexyloxy-phenyl)-aniline (2.23g, 5mmol) be dissolved in dry methylene chloride (50mL), add aluminum trichloride (anhydrous) (0.80g at 0 DEG C in batches, 6mmol), stir after 20 minutes, methylene dichloride (10mL) solution of slow dropping oxalyl chloride (2.5mmol), drip and finish, rise to room temperature and continue stirring 6 hours, reaction is finished, 10% aqueous hydrochloric acid (10mL) is dripped to reaction solution, collect organic phase, respectively with saturated sodium bicarbonate solution and washing, anhydrous sodium sulfate drying, remove solvent under reduced pressure, resistates crosses silicagel column, moving phase is methylene dichloride and the sherwood oil mixed solvent of volume ratio 1:1, obtain intermediate P5,
2) 5,6-diaminostilbene, 10-phenanthroline A (1.05g, 5.0mmol), intermediate P5 (5.0mmol) and Glacial acetic acid (20mL) back flow reaction 24 hours at 120 DEG C, be down to room temperature, remove solvent under reduced pressure, resistates is with chloroform extraction, respectively with 10% sodium hydrogen carbonate solution and saturated common salt washing, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, resistates crosses silicagel column, and moving phase is methylene dichloride and the ethyl acetate mixed solvent of volume ratio 1:1, obtains organic photosensitive dyestuff D3, yield 67%,
1hNMR (CDCl
3): 0.89 (t, 12H), 1.26-1.37 (m, 16H), 1.44-1.49 (m, 8H), 1.76-1.83 (m, 8H), 3.96 (t, 8H), 6.89 (t, 12H), 7.13 (d, 8H), 7.59 (d, 4H), 7.97 (m, 2H), 9.50 (d, 2H), 9.69 (d, 2H).
The preparation and property of embodiment 4, solar cell device measures:
1) preparation process: FTO glass is used water and washing with alcohol respectively, O
3/ UV process 18 minutes, then applies one deck nano-TiO
2colloid (nano-TiO
2colloid is purchased from Wuhan Guang Jing Science and Technology Ltd.), heat 30 minutes at 500 DEG C, immerse after being cooled to room temperature in the ethanol solution of organic photosensitive dyestuff D1, D2 or D3 of 0.5mmol/L and keep 12 hours, wherein, the dielectric substrate content in electrolytic solution is the N-methyl-N-butylimidazolium salt of 0.6M, the I of 0.05M
2, 0.1M the tert .-butylpyridine of LiI and 0.5M, second cyanogen and the penta cyanogen mixed solvent of to be volume ratio the be 1:1 of the solvent in electrolytic solution, then with platinum solar cell device D1, D2 and D3 to electrode composition sandwich structure.
Above-mentioned " organic photosensitive dyestuff D1, D2 or D3 " is changed into current efficiency best " ruthenium dye N3 " outward, and all the other then prepare solar cell device by above-mentioned preparation process completely, as a comparison solar cell device.
N3 dyestuff is the maker post type molecule of generally acknowledging in field of dye-sensitized solar cells, but it also has himself shortcoming, as: as: expensive, use rare metal is difficult to extensive preparation, synthesizing and purifying process complexity etc.
2) performance measurement: be carry out photoelectric properties test under the xenon lamp of 300W at light source by preparation-obtained solar cell device D1, solar cell device D2, solar cell device D3 and contrast solar cell device, test result is as shown in table 1:
The experimental data table of table 1 three kinds of organic dye and N3 dyestuff
| Dyestuff | J sc(mA/cm 2) | V oc(mV) | FF | η(％) |
| D1 | 8.7 | 638 | 0.65 | 3.61 |
| D2 | 10.5 | 645 | 0.60 | 4.06 |
| D3 | 9.5 | 652 | 0.63 | 3.90 |
| Ruthenium dye N3 | 13.4 | 660 | 0.67 | 5.03 |
J
sc: short-circuit current V
oc: open circuit voltage FF: injection efficiency η: transformation efficiency, η=J
sc× V
oc× FF.
Can learn from table 1: the solar cell device D1 obtained with dyestuff D1, D2, D3 and ruthenium dye N3, solar cell device D2, solar cell device D3 and contrast solar cell device electricity conversion be respectively 3.61%, 4.06% and 5.03%, two kinds of dyestuff D1 and D2 have good absorption in visible and near infrared spectrum district, compared with traditional metal complex dyes (as: ruthenium dye N3), (molar absorptivity of absorption peak is respectively D1:4.2 × 10 to have higher uptake factor
4lmol
-1cm
-1; D2:6.1 × 10
4lmol
-1cm
-1; D3:6.5 × 10
4lmol
-1cm
-1; The uptake factor of ruthenium dye N3 is N3:1.8 × 10
4lmol
-1cm
-1).These two kinds of dyestuffs successfully can be adsorbed on TiO
2on semi-conducting electrode, not easily De contamination, can produce higher electricity conversion (D1:3.61%, D2:4.06%, D3:3.90%), have the application prospect as sensitizing dye in dye-sensitized nanocrystalline titanium dioxide solar cell.
Claims (11)
1. compound shown in formula I:
In described formula I, π be selected from that non-structure or π be selected from structure shown in formula II and formula III any one;
In described formula I, D be selected from structure shown in structure and formula VI shown in structure shown in formula IV, formula V any one, wherein, R is alkyl or the alkoxyl group of C1-C6, and the alkyl of described C1-C6 or alkoxyl group are straight or branched;
2. compound shown in formula I according to claim 1, is characterized in that: compound shown in formula I be selected from following any one:
D1: π is structure shown in formula II; D is structure shown in formula IV;
D2: π is structure shown in formula III; D is structure shown in formula VI, and R is methyl;
D3: π is non-structure; D is structure shown in formula V, and R is hexyloxy.
3. prepare that π is selected from structure shown in formula II and formula III any one, and the method for D is selected from structure shown in structure and formula V shown in formula IV compound shown in any one formula I according to claim 1, comprises the steps:
1) under Pd catalyst action, reactant 1, reactant 2 and alkaline matter are carried out linked reaction in organic solvent, obtain intermediate P1, wherein, described reactant 1 is selected from compound shown in compound shown in formula VII or formula VIII, and described reactant 2 is selected from compound shown in compound shown in formula IX or formula X;
2) under aluminum chloride effect, compound shown in described intermediate P1 and formula XI is carried out friedel-crafts acylation reaction in organic solvent, obtains intermediate P2;
3) compound shown in described intermediate P2 and formula XII is carried out condensation reaction in organic solvent, obtains compound shown in formula I,
In described formula VIII, the definition of R in the definition cotype I of R; A in formula IX and formula X is halogen atom, described halogen atom be selected from following any one: Cl, Br or I.
4. method according to claim 3, is characterized in that: step 1) in, described pd catalyzer is selected from following at least one: Pd (Ph
3)
2cl
2, Pd (OAc)
2with Pd (PPh
3)
4;
Described alkaline matter is selected from following at least one: K
2cO
3, Na
2cO
3, KOH and NaOH;
The mol ratio of described pd catalyzer, reactant 1, reactant 2 and alkaline matter is 1:(20-100): (20-120): (40-200);
Described organic solvent is selected from as follows: the mixed system of at least one in toluene, dimethylbenzene, dioxane and tetrahydrofuran (THF) or itself and water, and wherein, in described mixed system, the volume ratio of organic solvent and water is 3:(1-3);
Described reaction is the back flow reaction of carrying out under inert gas atmosphere;
The temperature of reaction of described reaction is 100-140 DEG C, and the reaction times is 12-36h.
5. the method according to claim 3 or 4, is characterized in that: step 2) in, shown in described aluminum chloride, intermediate P1 and formula XI, the mol ratio of compound is (1-1.5): (1-1.2): 0.5;
The temperature of reaction of described friedel-crafts acylation reaction is 5-30 DEG C, and the reaction times is 5-20h;
Step 2) in, described friedel-crafts acylation reaction organic solvent used is at least one in methylene dichloride and ethylene dichloride;
Step 3) in, shown in described intermediate P2 and formula XII, the mol ratio of compound is (1-2.0): 1;
The temperature of reaction of described condensation reaction is 100-140 DEG C, and the reaction times is 12-36h;
Step 3) in, described condensation reaction organic solvent used is at least one in Glacial acetic acid and propionic acid.
6. prepare that π is selected from structure shown in formula II and formula III any one, and D be selected from structure shown in formula VI formula I according to claim 1 shown in the method for compound, comprise the steps:
A) under Cu catalyzer existence condition, compound shown in formula XIII, described reactant 2, part and alkaline matter are reacted in organic solvent, obtain intermediate P3, described reactant 2 is selected from compound shown in compound shown in formula IX or formula X, described part is selected from following at least one: 4,7-dimethyl-phenanthroline, 3,8-bis-bromo-phenanthroline and 1,10-phenanthroline;
B) under aluminum chloride effect, compound shown in described intermediate P3 and formula XI is carried out friedel-crafts acylation reaction in organic solvent, obtains intermediate P4;
C) compound shown in described intermediate P4 and formula XII is carried out condensation reaction in organic solvent, obtain compound shown in formula I;
In described formula XIII, the definition of R in the definition cotype I of R.
7. method according to claim 6, is characterized in that: step a) in, described Cu catalyzer is selected from following at least one: CuCl, CuBr and CuI;
Described alkaline matter is selected from following at least one: K
2cO
3, Na
2cO
3, KOH and NaOH;
Described part is selected from 1,10-phenanthroline;
The mol ratio of described Cu catalyzer, part, reactant 2, compounds X III and alkaline matter is 1:(2-4): (30-100): (20-100): (20-100);
Described reaction is the back flow reaction of carrying out under inert gas atmosphere;
The temperature of reaction of described reaction is 100-150 DEG C, and the reaction times is 12-36h;
Described organic solvent is selected from as follows: the mixed system of at least one in toluene, dimethylbenzene and trimethylbenzene or itself and water.
8. the method according to claim 6 or 7, is characterized in that: step b) in, shown in described aluminum chloride, intermediate P3 and formula XI, the mol ratio of compound is (1-1.5): (1-1.2): 0.5;
The temperature of reaction of described friedel-crafts acylation reaction is 5-30 DEG C, and the reaction times is 5-20h;
Step b) in, described friedel-crafts acylation reaction organic solvent used is at least one in methylene dichloride and ethylene dichloride;
Step c) in, shown in described intermediate P4 and formula XII, the mol ratio of compound is (1-2.0): 1;
The temperature of reaction of described condensation reaction is 100-140 DEG C, and the reaction times is 12-36h;
Step c) in, described condensation reaction organic solvent used is at least one in Glacial acetic acid and propionic acid.
9. prepare π and be selected from non-structure, and the method for D is selected from structure shown in structure and formula VI shown in structure shown in formula IV, formula V compound described in any one formula I according to claim 1, comprise the steps:
I) under aluminum chloride effect, compound shown in reactant 3 and formula XI is carried out friedel-crafts acylation reaction in organic solvent, obtain intermediate P5, described reactant 3 be selected from compound shown in compound and formula XIII shown in compound shown in formula VII, formula VIII any one;
II) compound shown in described intermediate P5 and formula XII is carried out condensation reaction in organic solvent, obtain compound shown in formula I.
10. method according to claim 9, is characterized in that: step I) in, shown in described aluminum chloride, reactant 3 and formula XI, the mol ratio of compound is (1-1.5): (1-1.2): 0.5;
The temperature of reaction of described friedel-crafts acylation reaction is 5-30 DEG C, and the reaction times is 5-20h.
Described friedel-crafts acylation reaction organic solvent used is at least one in methylene dichloride and ethylene dichloride;
Step II) in, shown in described intermediate P5 and formula XII, the mol ratio of compound is (1-2.0): 1;
The temperature of reaction of described condensation reaction is 100-140 DEG C, and the reaction times is 12-36h;
Described condensation reaction organic solvent used is at least one in Glacial acetic acid and propionic acid.
Compound shown in formula I described in 11. claims 1 or 2 is preparing the application in solar cell, it is characterized in that: described solar cell is nanometer titanium dioxide titanium solar battery.
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| CN111647140A (en) * | 2020-05-25 | 2020-09-11 | 湘潭大学 | Novel polymeric carbazole derivative cadmium complex and preparation method and application thereof |
| CN113651817A (en) * | 2021-07-16 | 2021-11-16 | 深圳市国华光电科技有限公司 | Organic dye and preparation method and application thereof |
| CN115260490A (en) * | 2022-08-18 | 2022-11-01 | 井冈山大学 | Electron donor-acceptor two-dimensional conjugated organic framework material and preparation method and application thereof |
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| US20070000539A1 (en) * | 2005-06-30 | 2007-01-04 | General Electric Company | Compositions and use thereof in dye sensitized solar cells |
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| US20060138453A1 (en) * | 2004-11-24 | 2006-06-29 | Entire Interest | Organic photosensitive optoelectronic device having a phenanthroline exciton blocking layer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647140A (en) * | 2020-05-25 | 2020-09-11 | 湘潭大学 | Novel polymeric carbazole derivative cadmium complex and preparation method and application thereof |
| CN111647140B (en) * | 2020-05-25 | 2022-05-03 | 湘潭大学 | Polymeric carbazole derivative cadmium complex and preparation method and application thereof |
| CN113651817A (en) * | 2021-07-16 | 2021-11-16 | 深圳市国华光电科技有限公司 | Organic dye and preparation method and application thereof |
| CN115260490A (en) * | 2022-08-18 | 2022-11-01 | 井冈山大学 | Electron donor-acceptor two-dimensional conjugated organic framework material and preparation method and application thereof |
| CN115260490B (en) * | 2022-08-18 | 2023-07-25 | 井冈山大学 | Electron donor-acceptor two-dimensional conjugated organic framework material and preparation method and application thereof |
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