CN104672237B - Based on phenanthroline for electron acceptor organic photosensitive dyestuff and preparation method and application - Google Patents
Based on phenanthroline for electron acceptor organic photosensitive dyestuff and preparation method and application Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- 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
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- 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
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- Y02E10/549—Organic PV cells
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Abstract
The invention discloses compound shown in Formulas I, wherein, in described Formulas I, π is selected from no any one in Formula II and structure shown in formula III of structure or π；D is selected from any one in structure and structure shown in Formula IV shown in structure, Formula V shown in formula IV, and wherein, R is alkyl or the alkoxyl of C1 C6, and the alkyl of described C1 C6 or alkoxyl are straight or branched.In the presence of corresponding catalyst; compound shown in Formulas I can be prepared by back flow reaction, friedel-crafts acylation and condensation reaction; introducing phenanthroline construction unit is electron acceptor, has synthesized and has had the organic dyestuff that electron donor is conjugated abutment electron acceptor structure.This kind of dyestuff has good absorption in the visible of solar spectrum and IR regions, higher to the utilization rate of sunlight, has a wide range of applications in terms of preparing DSSC, particularly dye-sensitized nanocrystalline titanium dioxide solaode.
Description
Technical field
The invention belongs to organic photosensitive dye field and in particular to a kind of based on phenanthroline for electron acceptor organic photosensitive
Dyestuff and preparation method and application.
Background technology
Compared to traditional silica-based solar cell, DSSC is simple, inexpensive with its processing technology
Favored by global scientific research and industrial quarters the advantages of high with photoelectric transformation efficiency.From nineteen ninety Switzerland scientistDeng
Reported first one kind is with solaode (the Brian O ' of ruthenium pyridine complex (N3) dye-sensitized nano titanium dioxide semiconductor
Regan and Michael..Nature, since 353,1991,937 939), countries in the world scientist carried out greatly
Measure fruitful research work, effectively promote theory and the applied research work of DSSC.
Typical DSSC is by electro-conductive glass, nano titanium oxide, photosensitizer, electrolyte and to electrode
5 part compositions.Wherein organic photosensitive dyestuff, as core, absorbs sunlight and excites generation photon, is directly to determine the sun
The key component of energy battery performance.Therefore, considerable fraction of research work focus primarily upon organic photosensitive dyestuff design and
Synthesis.
Organic photosensitive dyestuff typically has three parts to constitute：Electron donor (Donor), conjugation abutment (Bridge) and electronics are subject to
Body (Acceptor) three part forms.Electron donor common are the nitrogenous electron rich construction unit such as triaryl amine, carbazole, indole,
Photoelectron is produced after being excited by sunlight；Then species is various for the structure of conjugation abutment, typically has big ring or conjugated polycyclic double bond
Etc. architectural feature, common are thiophene, bithiophene, porphyrin etc., conjugation abutment acts primarily as two aspect effects：One is to widen photosensitive dye
The absorption spectrum of material, improves the utilization rate of incident sunlight；Two is that the photoelectron that electron donor is excited generation conducts to electronics
Receptor.The electron acceptor commonly electron deficiency construction unit such as carboxyl, cyanoacetic acid, electron acceptor role is by photosensitive dye
Material is adsorbed in nano titanium oxide, and the photoelectron of conjugation abutment conduction is imported titanium dioxide conduction band so that battery starts work
Make.But, the group such as carboxyl, cyanoacetic acid is through highly acid electrolyte (I-/I3 -) be easy to after immersion take off from nanometer titanium dioxide layer
Absorption leads to cell photoelectric decrease in efficiency, thus have impact on the stability of battery performance.Therefore, new strong of research and development
Absorbent-type electron acceptor has important theory and realistic meaning.
Content of the invention
It is an object of the invention to provide a kind of based on phenanthroline for electron acceptor organic photosensitive dyestuff and preparation method thereof.
Provided by the present invention based on phenanthroline for the organic photosensitive dyestuff of electron acceptor general structure shown in formula I：
In described Formulas I, π is selected from no any one in Formula II and structure shown in formula III of structure or π.
In described Formulas I, D is selected from any one in structure and structure shown in Formula IV shown in structure, Formula V shown in formula IV, its
In, R is alkyl or the alkoxyl of C1-C6, and the alkyl of described C1-C6 or alkoxyl are straight or branched.
It is furthermore preferred that 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 IV, and R is methyl；
D3:π is no structure；D is structure shown in Formula V, and R is hexyloxy.
Provided by the present invention as follows for the preparation method of the organic photosensitive dyestuff of electron acceptor based on phenanthroline：
Prepare any one that π is selected from Formula II and structure shown in formula III, and D is selected from shown in structure shown in formula IV and Formula V
Described in the Formulas I of any one in structure, the method for compound comprises the steps：
1) under Pd catalyst action, reactant 1, reactant 2 and alkaline matter are carried out in organic solvent be coupled instead
Should, obtain intermediate P1, wherein, described reactant 1 is selected from (the boric acid chemical combination of N, N- diethylaniline of compound shown in Formula VII
Thing) or compound shown in Formula VIII (replacing the boronic acid compounds of triphenylamine), described reactant 2 is selected from compound shown in Formula IX
(2- halogenated thiophene) or compound shown in Formula X (2- halo 1,4-Dithiapentalene)；
2) under aluminum trichloride catalyst effect, by described intermediate P1 and compound (oxalyl chloride) shown in Formula X I organic
Carry out friedel-crafts acylation reaction in solvent, obtain intermediate P2；
3) by described intermediate P2 and compound shown in Formula X II (5,6- diaminostilbene, 10- phenanthroline) in organic solvent
Carry out condensation reaction, obtain compound shown in Formulas I.
In described Formula VIII, the definition defining with R in Formulas I of R；A in Formula IX and Formula X is halogen atom, described halogen
Atom be specifically selected from following any one：Cl, Br or I.
In said method, step 1) in, described Pd catalyst is selected from least one as follows：Pd(Ph3)2Cl2、Pd(OAc)2
With Pd (PPh3)4, concretely Pd (PPh3)4.
Described alkaline matter is selected from least one as follows：K2CO3、Na2CO3, KOH and NaOH etc., concretely K2CO3.
Described Pd catalyst, the mol ratio of reactant 1, reactant 2 and alkaline matter are 1：(20-100)：(20-120)：
(40-200), concretely 1：66.7：66.7：100.
Described organic solvent is selected from as follows：At least one in toluene, dimethylbenzene, dioxane and oxolane or itself and
The mixed system of water, wherein, in described mixed system, organic solvent and the volume ratio of water are 3：(1-3), concretely tetrahydrochysene furan
The mixed system muttered with water.
Described reaction is in noble gases (such as：Nitrogen) back flow reaction that carries out under atmosphere.
The reaction temperature of described reaction is 100-140 DEG C, and the response time is 12-36h, specially 24h.
In said method, step 2) in, described aluminum chloride, intermediate P1 and the mol ratio of compound shown in Formula X I are
(1-1.5)：(1-1.2)：0.5, specially 1.2：1：0.5.
The reaction temperature of described friedel-crafts acylation reaction is 5-30 DEG C, specially 25 DEG C, and the response time is 5-20h, specifically
For 6h.
Organic solvent used by described friedel-crafts acylation reaction is at least one in dichloromethane and dichloroethanes, specifically
For dichloromethane.
In said method, step 3) in, the mol ratio of described intermediate P2 and compound shown in Formula X II is (1-2.0)：1,
It is specially 1：1.
The reaction temperature of described condensation reaction is 100-140 DEG C, and the response time is 12-36h.
Organic solvent used by described condensation reaction is at least one in glacial acetic acid and propanoic acid, specially glacial acetic acid.
Prepare π be selected from Formula II and structure shown in formula III in any one, and D be selected from the Formulas I of structure shown in Formula IV described in
The method of compound comprises the steps：
A) under Cu catalyst existence condition, by compound shown in Formula X III, described reactant 2, part and alkaline matter
Reacted in organic solvent, obtained intermediate P3, wherein, described reactant 2 is selected from (the 2- halo thiophene of compound shown in Formula IX
Fen) or compound shown in Formula X (2- halo 1,4-Dithiapentalene), described part is selected from least one as follows：4,7- dimethyl-phenanthrene is coughed up
Quinoline, the bromo- phenanthroline of 3,8- bis- and 1,10- phenanthroline；
B) under aluminum chloride effect, by described intermediate P3 and compound (oxalyl chloride) shown in Formula X I in organic solvent
Carry out friedel-crafts acylation reaction, obtain intermediate P4；
C) by described intermediate P4 and compound shown in Formula X II (5,6- diaminostilbene, 10- phenanthroline) in organic solvent
Carry out condensation reaction, obtain compound shown in Formulas I.
In described Formula X III, the definition defining with R in Formulas I of R.
In said method, in step a), described Cu catalyst is selected from least one as follows：CuCl, CuBr and CuI, specifically
Can be CuI.
Described alkaline matter is selected from least one as follows：K2CO3、Na2CO3, KOH and NaOH etc., concretely KOH.
Described part concretely 1,10- phenanthroline.
Described Cu catalyst, part, the mol ratio of reactant 2, compounds X III and alkaline matter are 1：(2-4)：(30-
100)：(20-100)：(20-100), concretely 1：2：80：66.7：100.
Described organic solvent is selected from as follows：At least one in toluene, dimethylbenzene and trimethylbenzene or the mixture of itself and water
System, the concretely mixed system of dimethylbenzene and water.
Described reaction is in noble gases (such as：Nitrogen) back flow reaction that carries out under atmosphere.
The reaction temperature of described reaction is 100-150 DEG C, and the response time is 12-36h, specially 24h.
In said method, in step b), described aluminum chloride, intermediate P3 and the mol ratio of compound shown in Formula X I are
(1-1.5)：(1-1.2)：0.5.
The reaction temperature of described friedel-crafts acylation reaction is 5-30 DEG C, and the response time is 5-20h.
Organic solvent used by described friedel-crafts acylation reaction is at least one in dichloromethane and dichloroethanes, specifically
For dichloromethane.
In said method, in step c), the mol ratio of described intermediate P4 and compound shown in Formula X II is (1-2.0)：1.
The reaction temperature of described condensation reaction is 100-140 DEG C, and the response time is 12-36h.
Organic solvent used by described condensation reaction is at least one in glacial acetic acid and propanoic acid, specially glacial acetic acid.
Preparation π is selected from no structure, and D is any in structure and structure shown in Formula IV shown in structure, Formula V shown in formula IV
Described in a kind of Formulas I, the method for compound comprises the steps：
I) under aluminum chloride effect, compound (oxalyl chloride) shown in reactant 3 and Formula X I is carried out in organic solvent
Friedel-crafts acylation reaction, obtains intermediate P5, and described reactant 3 is selected from compound shown in compound, Formula VIII shown in Formula VII
With any one in compound shown in Formula X III；
II) by described intermediate P5 and compound shown in Formula X II (5,6- diaminostilbene, 10- phenanthroline) in organic solvent
In carry out condensation reaction, obtain compound shown in Formulas I.
In said method, step I) in, the mol ratio of described aluminum chloride, reactant 3 and compound shown in Formula X I is (1-
1.5)：(1-1.2)：0.5.
The reaction temperature of described friedel-crafts acylation reaction is 5-30 DEG C, and the response time is 5-20h.
Organic solvent used by described friedel-crafts acylation reaction is at least one in dichloromethane and dichloroethanes, specifically
For dichloromethane.
In said method, step II) in, the mol ratio of described intermediate P5 and compound shown in Formula X II is (1-2.0)：
1.
The reaction temperature of described condensation reaction is 100-140 DEG C, and the response time is 12-36h.
Organic solvent used by described condensation reaction is at least one in glacial acetic acid and propanoic acid, specially glacial acetic acid.
The present invention is preparation-obtained a kind of to prepare solar energy based on phenanthroline for the organic photosensitive dyestuff of electron acceptor
Application in battery falls within protection scope of the present invention.
Described solaode is nanometer titanium dioxide titanium solar battery.
Because phenanthroline class formation has extensively in transition metal-catalyzed and organic photoelectrical material field as a bidentate ligand
Application.Two nitrogen-atoms in phenanthroline structure can form stronger Coordinative Chemistry key with various metals, and (event is prepared to be obtained
To higher adsorptivity is had for the organic photosensitive dyestuff of electron acceptor based on phenanthroline), and phenanthroline molecular skeleton is one
Individual three ring conjugated structure systems, have good electronic conduction ability, are excellent electron acceptor candidate structure units, this
Invention is firstly introduced phenanthroline construction unit as electron acceptor, has synthesized and has had electron donor electronic relay electron acceptor knot
The organic dyestuff of structure, this kind of dyestuff has good absorption in the visible of solar spectrum and IR regions；The present invention is organic
Dye molecule has big delocalized pi-bond, and photo-excited electron passes through π-π antibonding transition, thus has higher absorptance, in phase
In half guided membrane of stack pile, higher to the absorption rate of light；With carboxyl for the dye molecule of electron acceptor compared with, structure letter
Single, novel, there is higher photoelectric transformation efficiency, and other non-carboxy group acceptor dyestuffs, such as：Pyridine, hydroxyquinoline or nitro etc.
Compare, photoelectric transformation efficiency is quite or more preferable.
Brief description
Fig. 1 be the present invention based on phenanthroline for the organic photosensitive dyestuff of electron acceptor preparation flow figure.
Specific embodiment
Below by specific embodiment, the method for the present invention is illustrated, but the invention is not limited in this, all this
Any modification, equivalent and improvement made within the spirit of invention and principle etc., should be included in the protection model of the present invention
Within enclosing.
Experimental technique described in following embodiments, if no special instructions, is conventional method；Described reagent and material, such as
No specified otherwise, all commercially obtains.
As shown in Figure 1 for the preparation flow figure of the organic photosensitive dyestuff of electron acceptor based on phenanthroline.
Embodiment 1, based on the preparation for the organic photosensitive dyestuff D1 of electron acceptor for the phenanthroline, (wherein, in Formulas I, π is Formula II
Shown structure, D is structure shown in formula IV)：
1) 4- (N, N- lignocaine)-phenylboric acid (1.93g, 10mmol), Pd (PPh3)4(187mg, 0.15mmol),
K2CO3(2.07g, 15mmol), the bromo- thiophene of 2- (1.63g, 10mmol), water (7mL) and oxolane (20mL) are in nitrogen atmosphere
Under, back flow reaction 24 hours at 80 DEG C.Reactant liquor is poured in dichloromethane (50mL), washing, collects organic faciess, anhydrous slufuric acid
Sodium is dried, and removes solvent under reduced pressure, residue crosses silicagel column, and mobile phase is volume ratio 1:3 dichloromethane and petroleum ether mixing are molten
Agent, obtains intermediate P1；
2) step 1) made intermediate P1 (2.31g, 10mmol) is dissolved in dry methylene chloride (50mL), at 0 DEG C point
Criticize and add aluminum trichloride (anhydrous) (1.6g, 12mmol).After stirring 20 minutes, it is slowly added dropwise the dichloromethane of oxalyl chloride (5mmol)
(10mL) solution.Drip and finish, be warmed to room temperature continuation stirring 6 hours.Reaction is finished, to reactant liquor Deca 10% aqueous hydrochloric acid solution
(10mL).Collect organic faciess, respectively with saturated sodium bicarbonate solution and washing, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, residual
Excess crosses silicagel column, and mobile phase is volume ratio 1:1 dichloromethane and petroleum ether mixed solvent, obtain intermediate P2；
3) 5,6- diaminostilbene, 10- phenanthroline A (2.10g, 10mmol), intermediate P2 (10mmol) and glacial acetic acid
(40mL), back flow reaction 24 hours at 120 DEG C.It is down to room temperature, remove solvent under reduced pressure.Residue, with chloroform extraction, is used respectively
10% sodium bicarbonate solution and saturated common salt washing, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, residue crosses silicagel column, stream
Dynamic is mutually volume ratio 1:1 dichloromethane and ethyl acetate mixed solvent, obtain organic photosensitive dyestuff D1, yield 62%,1HNMR
(CDCl3):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, based on the preparation for the organic photosensitive dyestuff D2 of electron acceptor for the phenanthroline, (wherein, in Formulas I, π is formula III
Shown structure, D is structure shown in Formula IV, and R=methyl therein)：
1) under nitrogen atmosphere, 4,4 '-dimethyl diphenylamines (1.97g, 10mmol), CuI (28.5mg, 0.15mmol), 1,
10- phenanthroline (54mg, 0.3mmol), potassium hydroxide (1.12g, 15mmol), the iodo- 1,4-Dithiapentalene of 2- (3.16g, 12mmol), water
(7mL) react 24 hours at 130 DEG C with dimethylbenzene (20mL), be down to room temperature, reactant liquor is poured in dichloromethane (100mL),
Washing, collects organic faciess, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, residue crosses silicagel column, mobile phase is volume ratio 1:3
Dichloromethane and petroleum ether mixed solvent, obtain intermediate P3；
2) step 1) made intermediate P3 (3.35g, 10mmol) is dissolved in dry methylene chloride (50mL), at 0 DEG C point
Criticize and add aluminum trichloride (anhydrous) (1.6g, 12mmol), after stirring 20 minutes, be slowly added dropwise the dichloromethane of oxalyl chloride (5mmol)
(10mL) solution, drips and finishes, and is warmed to room temperature continuation stirring 6 hours, reaction is finished, to reactant liquor Deca 10% aqueous hydrochloric acid solution
(10mL), collect organic faciess, respectively with saturated sodium bicarbonate solution and washing, anhydrous sodium sulfate drying, remove solvent under reduced pressure, residual
Excess crosses silicagel column, and mobile phase is volume ratio 1:1 dichloromethane and petroleum ether mixed solvent, 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, are down to room temperature, remove solvent under reduced pressure, and residue, with chloroform extraction, is used respectively
10% sodium bicarbonate solution and saturated common salt washing, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, residue crosses silicagel column, stream
Dynamic is mutually volume ratio 1:1 dichloromethane and ethyl acetate mixed solvent, obtain organic photosensitive dyestuff D2, yield 56%,1HNMR
(CDCl3):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, based on the preparation for the organic photosensitive dyestuff D3 of electron acceptor for the phenanthroline, (wherein, in Formulas I, π is no D
Structure shown in Formula V, and R=hexyloxy therein)：
1) N, N- (4- Hexyloxy-phenyl)-aniline (2.23g, 5mmol) are dissolved in dry methylene chloride (50mL), in 0 DEG C
Under be dividedly in some parts aluminum trichloride (anhydrous) (0.80g, 6mmol), after stirring 20 minutes, be slowly added dropwise the two of oxalyl chloride (2.5mmol)
Chloromethanes (10mL) solution, drips and finishes, and is warmed to room temperature continuation stirring 6 hours, reaction is finished, to reactant liquor Deca 10% aqueous hydrochloric acid solution
(10mL), collect organic faciess, respectively with saturated sodium bicarbonate solution and washing, anhydrous sodium sulfate drying, remove solvent under reduced pressure, residual
Excess crosses silicagel column, and mobile phase is volume ratio 1:1 dichloromethane and petroleum ether mixed solvent, 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, are down to room temperature, remove solvent under reduced pressure, and residue, with chloroform extraction, is used respectively
10% sodium bicarbonate solution and saturated common salt washing, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, residue crosses silicagel column, stream
Dynamic is mutually volume ratio 1:1 dichloromethane and ethyl acetate mixed solvent, obtain organic photosensitive dyestuff D3, yield 67%,1HNMR
(CDCl3):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).
Embodiment 4, the preparation of solar cell device and performance measurement：
1) preparation process：FTO glass is used respectively water and washing with alcohol, O3/ UV is processed 18 minutes, and then one layer of coating is received
Rice TiO2Colloid (nano-TiO2Colloid is purchased from Wuhan Guang Jing Science and Technology Ltd.), heat 30 minutes at 500 DEG C, be cooled to room
12 hours, wherein, electrolysis are kept in the ethanol solution of organic photosensitive dyestuff D1, D2 or D3 immersing 0.5mmol/L after temperature
Dielectric substrate content in liquid is the N- methyl-N-butylimidazolium salt of 0.6M, the I of 0.05M2, 0.1M LiI and 0.5M tertiary fourth
Yl pyridines, the solvent in electrolyte is 1 for volume ratio：1 second cyanogen and penta cyanogen mixed solvent, then form sandwich with platinum to electrode
Solar cell device D1, D2 and D3 of structure.
Above-mentioned " organic photosensitive dyestuff D1, D2 or D3 " is changed into current efficiency best " ruthenium dye N3 ", and outward, remaining is then complete
The process that is entirely prepared as described above prepares solar cell device, solar cell device as a comparison.
N3 dyestuff is the maker post type molecule generally acknowledged in field of dye-sensitized solar cells, but it also has its own shortcoming,
As：As：Expensive, be difficult to prepare on a large scale using rare metal, synthesizing and purifying process complexity etc..
2) performance measurement：By preparation-obtained solar cell device D1, solar cell device D2, solaode
Device D3 and contrast solar cell device carry out photoelectric properties test under the xenon lamp for 300W for the light source, test result such as table 1
Shown：
1 three kinds of organic dyestuff of table and the experimental data table of N3 dyestuff
| Dyestuff | Jsc(mA/cm2) | Voc(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 |
Jsc：Short circuit current Voc：Open-circuit voltage FF：Injection efficiency η：Transformation efficiency, η=Jsc×Voc×FF.
Can learn from table 1：With the solar cell device D1 obtained by dyestuff D1, D2, D3 and ruthenium dye N3, solar-electricity
The electricity conversion of pond device D2, solar cell device D3 and contrast solar cell device respectively 3.61%,
4.06% and 5.03%, two kinds of dyestuff D1 and D2 have good absorption in visible and near infrared spectrum, with traditional metal network
Compound dyestuff is compared (such as：Ruthenium dye N3), (molar absorption coefficient of absworption peak is respectively D1 to have higher absorptance：4.2
×104L·mol-1·cm-1；D2：6.1×104L·mol-1·cm-1；D3：6.5×104L·mol-1·cm-1；Ruthenium dye N3's
Absorptance is N3：1.8×104L·mol-1·cm-1).Both dyestuffs can successfully adsorb in TiO2Semi-conducting electrode
On, it is difficult De contamination, higher electricity conversion (D1 can be produced:3.61%, D2:4.06%, D3:3.90%), have
Application prospect as sensitizing dyestuff in dye-sensitized nanocrystalline titanium dioxide solaode.
Claims (9)
1. compound shown in Formulas I：
In described Formulas I, π is selected from any one in Formula II and structure shown in formula III；
In described Formulas I, D is selected from any one in structure and structure shown in Formula IV shown in structure, Formula V shown in formula IV, wherein, R
Alkyl for C1-C6 or alkoxyl, the alkyl of described C1-C6 or alkoxyl are straight or branched；
2. compound shown in Formulas I according to claim 1 it is characterised in that：Compound shown in Formulas I is selected from any one as follows
Kind：
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 IV, and R is methyl.
3. prepare any one that π is selected from Formula II and structure shown in formula III, and D is selected from knot shown in structure shown in formula IV and Formula V
The method of the compound shown in the Formulas I described in the claim 1 of any one in structure, comprises the steps：
1) under Pd catalyst action, reactant 1, reactant 2 and alkaline matter are carried out coupling reaction in organic solvent, obtains
To intermediate P1, wherein, described reactant 1 is selected from compound shown in Formula VII or compound shown in Formula VIII, described reactant 2
Selected from compound shown in Formula IX or compound shown in Formula X；
2) under aluminum chloride effect, described intermediate P1 and compound shown in Formula X I are carried out friedel-craft acyl in organic solvent
Glycosylation reaction, obtains intermediate P2；
3) described intermediate P2 and compound shown in Formula X II are carried out condensation reaction in organic solvent, obtain chemical combination shown in Formulas I
Thing,
In described Formula VIII, the definition defining with R in Formulas I of R；A in Formula IX and Formula X is halogen atom, described halogen atom
Selected from following any one：Cl, Br or I.
4. method according to claim 3 it is characterised in that：Step 1) in, described pd catalyst is selected from following at least one
Kind：Pd(Ph3)2Cl2、Pd(OAc)2With Pd (PPh3)4；
Described alkaline matter is selected from least one as follows：K2CO3、Na2CO3, KOH and NaOH；
Described pd catalyst, the mol ratio of reactant 1, reactant 2 and alkaline matter are 1：(20-100)：(20-120)：(40-
200)；
Described organic solvent is selected from as follows：At least one in toluene, dimethylbenzene, dioxane and oxolane or itself and water
Mixed system, wherein, in described mixed system, organic solvent and the volume ratio of water are 3：(1-3)；
Described reaction is the back flow reaction carrying out under inert gas atmosphere；
The reaction temperature of described reaction is 100-140 DEG C, and the response time is 12-36h.
5. the method according to claim 3 or 4 it is characterised in that：Step 2) in, described aluminum chloride, intermediate P1 and
The mol ratio of compound shown in Formula X I is (1-1.5)：(1-1.2)：0.5；
The reaction temperature of described friedel-crafts acylation reaction is 5-30 DEG C, and the response time is 5-20h；
Step 2) in, organic solvent used by described friedel-crafts acylation reaction is at least one in dichloromethane and dichloroethanes；
Step 3) in, the mol ratio of described intermediate P2 and compound shown in Formula X II is (1-2.0)：1；
The reaction temperature of described condensation reaction is 100-140 DEG C, and the response time is 12-36h；
Step 3) in, organic solvent used by described condensation reaction is at least one in glacial acetic acid and propanoic acid.
6. prepare π be selected from Formula II and structure shown in formula III in any one, and D be selected from structure shown in Formula IV claim 1
Shown in described Formulas I, the method for compound, comprises the steps：
A) under Cu catalyst existence condition, compound shown in Formula X III, described reactant 2, part and alkaline matter are being had
Reacted in machine solvent, obtained intermediate P3, described reactant 2 is selected from compound or right shown in Formula IX in claim 3
Require compound shown in Formula X in 3, described part is selected from least one as follows：4,7- dimethyl-phenanthroline, the bromo- phenanthrene of 3,8- bis- are coughed up
Quinoline and 1,10- phenanthroline；
B) under aluminum chloride effect, by described intermediate P3 and compound shown in claim 3 Chinese style XI in organic solvent
Carry out friedel-crafts acylation reaction, obtain intermediate P4；
C) described intermediate P4 and compound shown in claim 3 Chinese style XII are carried out condensation reaction in organic solvent, obtain
Compound shown in Formulas I；
In described Formula X III, the definition defining with R in Formulas I of R.
7. method according to claim 6 it is characterised in that：In step a), described Cu catalyst is selected from following at least one
Kind：CuCl, CuBr and CuI；
Described alkaline matter is selected from least one as follows：K2CO3、Na2CO3, KOH and NaOH；
Described part is selected from 1,10- phenanthroline；
Described Cu catalyst, part, the mol ratio of reactant 2, compounds X III and alkaline matter are 1：(2-4)：(30-100)：
(20-100)：(20-100)；
Described reaction is the back flow reaction carrying out under inert gas atmosphere；
The reaction temperature of described reaction is 100-150 DEG C, and the response time is 12-36h；
Described organic solvent is selected from as follows：At least one in toluene, dimethylbenzene and trimethylbenzene or the mixed system of itself and water.
8. the method according to claim 6 or 7 it is characterised in that：In step b), described aluminum chloride, intermediate P3 and
The mol ratio of compound shown in Formula X I is (1-1.5)：(1-1.2)：0.5；
The reaction temperature of described friedel-crafts acylation reaction is 5-30 DEG C, and the response time is 5-20h；
In step b), organic solvent used by described friedel-crafts acylation reaction is at least one in dichloromethane and dichloroethanes；
In step c), the mol ratio of described intermediate P4 and compound shown in Formula X II is (1-2.0)：1；
The reaction temperature of described condensation reaction is 100-140 DEG C, and the response time is 12-36h；
In step c), organic solvent used by described condensation reaction is at least one in glacial acetic acid and propanoic acid.
9. application in preparing solaode for the compound shown in the Formulas I described in claim 1 or 2 it is characterised in that：Described
Solaode is nanometer titanium dioxide titanium solar battery.
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| 有机太阳能电池材料研究新进展;张天慧等;《有机化学》;20111231;第31卷(第2期);第260-272页 * |
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