CN103709129A - Synthesis and application of diethylamino coumarin dye sensitizer - Google Patents
Synthesis and application of diethylamino coumarin dye sensitizer Download PDFInfo
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- CN103709129A CN103709129A CN201310667539.8A CN201310667539A CN103709129A CN 103709129 A CN103709129 A CN 103709129A CN 201310667539 A CN201310667539 A CN 201310667539A CN 103709129 A CN103709129 A CN 103709129A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- 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
- C09B57/02—Coumarine dyes
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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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- 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
Abstract
The invention discloses a kind of lignocaine coumarin kind compound and its preparation and application. The lignocaine coumarin kind compound such as formula (
) and formula (II) shown in, wherein Ar is preferably phenyl, xenyl and tolylthiophene base. Lignocaine coumarin kind compound of the present invention can be used as dye sensitizing agent applied to dye-sensitized solar cells, for dye sensitizing agent screening add it is new can applied material.
Description
Technical field
The present invention relates to a kind of synthetic and application of diethylin coumarins dye sensitizing agent.
Background technology
Dye sensitization solar battery (Dye Sensitized Solar Cell, DSSC) rely on its cost low, can the low light level Generate, Generation, Generator electricity transformation efficiency feature such as temperature influence not, the utmost point is hopeful substituted for silicon semiconductor optoelectronic converting member, becomes practical high performance solar cells of future generation.Dye sensitizing agent is the key structure material that determines visible absorption and photoelectric transformation efficiency in DSSC, has structure and easily designs the features such as modification and processing, cost are low, good stability.
The research of Chinese and foreign dyes sensitizing agent mainly divides two classes, and a class is organometallic complex, and typical structure is functional many pyridines ruthenium compound.This class dye sensitizing agent absorbs stronger in visible region, redox property is reversible, and oxidative stability is high, but ruthenium is higher as rare metal cost, and its dyestuff absorption spectrum is narrow.Equations of The Second Kind is nonmetal organic dye, has that molar absorptivity is high, an absorb light spectrum width and can produce the advantages such as good electric chemical property by structural modification modulation, is the study hotspot of dye sensitizing agent in recent years.Traditional general structure of nonmetal organic dye sensitized dose is " to body-pi-conjugated bridge-acceptor " (Donor-π Bridge-Acceptor, D-π-A), according to the difference of giving body, the nonmetal dye sensitizing agents such as existing coumarin type, indoline type, three arylamine types are able to design and development.Conventional acceptor is cyanoacetic acid and rhodanine acetic acid, and in order further to strengthen acceptor and TiO
2between binding ability, also have recently the dye sensitizing agent of some non-carboxylic acid acceptors to be in the news.
Tonka bean camphor and derivative thereof are as the electron transporting compound of conjugation in molecule, there is good fluorescence quantum efficiency, high molar absorptivity and large Stoke displacement, be widely used in the color fluorescence resin of coloring plastic, color fluorescence coating, solar collector, and the high-technology field such as sensitive materials, photochromics, video disc recording material.Due to high in visible region responsive, solar light irradiation stability inferior is good, coumarins dye molecule has been subject to extensive concern as the good dye sensitizing agent of a class development prospect.A series of coumarins dye sensitization agent molecules have been synthesized in the designs such as Hara, and photoelectric transformation efficiency is up to 8.2%; Nearest Kim etc. has reported take tonka bean camphor as the novel D-A-π-category-A amboceptor coumarine dye sensitizing agent molecule to body, and total efficiency is 5.97%; In great waves, design that to have synthesized novel 2D-π-category-A two to body note legumin dye sensitization agent molecule, its photoelectric transformation efficiency has reached 5.53%.These coumarine dye sensitizing agent molecules are generally used a pair of horses going side by side to have two nitrogenous heterocyclic tonka bean camphors as giving body, and its synthesis step is longer, and yield is not high.The present invention is usingd substituted cumarin that raw material is easy to get as to body, and containing the aromatic ring of benzene, as bridged bond, cyanoacetic acid or rhodanine acetic acid is as acceptor, has syntheticly obtained six diethylin coumarins dye sensitizing agents.At present, there is no the solar cell application of this structure of bibliographical information.
Summary of the invention
The object of the present invention is to provide a kind of preparation of diethylin coumarin kind compound and be applied to dye sensitization solar battery.
Structural formula of the present invention is as follows:
Formula (I) and (II) in, Ar is for containing the C6-C18 aryl of phenyl ring, preferred Ar is
,
or
, particularly preferred Ar is
,
or
.
Of the present inventionly suc as formula the diethylin coumarin kind compound shown in (I) or formula (II), can prepare in accordance with the following methods:
Formula (III) compound, formula (IV) or formula V compound, organic solvent are mixed, under the effect of basic cpd, reflux stirring reaction 1 ~ 10 h, preferred 2-3h, after reacting completely, be spin-dried for solvent, resistates carries out silica gel column chromatography with eluent solvent, the coumarin kind compound shown in acquisition formula (I) or formula (II);
Wherein, the product that formula (IV) compound is corresponding is formula (I) compound, and the product that formula V compound is corresponding is formula (II) compound;
Described basic cpd is one or more in piperidines, pyridine, triethylamine or dimethylamine, preferably piperidines;
Described organic solvent is one or more in acetonitrile, chloroform, tetrahydrofuran (THF) or Isosorbide-5-Nitrae-dioxane, preferably acetonitrile and tetrahydrofuran (THF) (preferred proportion is v:v=1:2);
Described eluent solvent is the mixed solvent of (chloroform and/or methylene dichloride)+(methyl alcohol and/or ethanol)+acetic acid, is preferably the mixed solvent (preferred proportion is v:v:v=100:5:1) of methylene dichloride, methyl alcohol and acetic acid;
The ratio of the amount of substance of formula (III) compound and formula (IV) or formula V compound and basic cpd is: 1:1.0 ~ 3.0:0.1 ~ 0.3, and organic solvent volumetric usage is counted 10 ~ 30 mL/mmol with the amount of substance of formula (III) compound;
Described organic solvent is one or more in acetonitrile, chloroform, tetrahydrofuran (THF) or Isosorbide-5-Nitrae-dioxane, preferably acetonitrile and tetrahydrofuran (THF) (v:v=1:2);
Described basic cpd is one or more in piperidines, pyridine, triethylamine or dimethylamine, preferably piperidines;
The described reaction times is 1 ~ 10 h, is preferably 2 ~ 3 h;
Described eluent solvent is the mixed solvent of (chloroform and/or methylene dichloride)+(methyl alcohol and/or ethanol)+acetic acid, is preferably the mixed solvent (v:v:v=100:5:1) of methylene dichloride, methyl alcohol and acetic acid;
Described consumption of organic solvent is counted 10 ~ 30 mL/mmol with the amount of substance of formula (III) compound, preferably 20 mL/mmol.
Compound shown in formula (IIIa) can prepare in accordance with the following methods: formula (VI) compound, 4-formyl radical phenyl-boron dihydroxide (VII), tetra-triphenylphosphine palladium are dissolved in a certain amount of THF, add a certain amount of aqueous sodium carbonate, N
2the lower reflux of protection prepares.
Compound shown in formula (IIIb ~ IIIc) can prepare in accordance with the following methods: by formula (VIII)
Compound, 4-formyl radical phenyl-boron dihydroxide (VII) or (IX), tetra-triphenylphosphine palladium is dissolved in a certain amount of THF, adds a certain amount of aqueous sodium carbonate, N
2the lower reflux of protection prepares.
Above-mentioned being well known to a person skilled in the art preparation method.
Diethylin coumarin kind compound of the present invention can be used as dye sensitizing agent, for the preparation of solar cell, concrete application examples as:
Diethylin coumarin kind compound is dissolved in to CH
3cN-DMSO(V:V=24:1), in mixed solvent, soak double-deck TiO
2film of nanoparticles optoelectronic pole 24 h.Load the TiO of diethylin coumarin kind compound
2electrode becomes sandwich structure with platinum to electrode assembling, and splashes into ionogen at edge, utilizes capillary penetration principle to introduce inside battery.In 100 mW/cm
2under light intensity is irradiated, measure photovoltage-current characteristics curve.Its result shows that the photoelectric transformation efficiency of this type of diethylin coumarin kind compound is 1.39-3.62%.
Diethylin coumarin kind compound beneficial effect prepared by the present invention is mainly reflected in: a kind of new diethylin coumarin kind compound is provided, preparation method is simple, the dye sensitization solar battery that this compound is assembled into as dye sensitizing agent has good photoelectric transformation efficiency, for the screening of dye sensitizing agent increased new can applied material.
Accompanying drawing explanation
The electric current of the DSSC that accompanying drawing 1. diethylin tonka bean camphor assemblings obtain
j-
vcurve
specific implementation method
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
7-diethylin-3-is to formyl radical phenyl tonka bean camphor
iIIasynthetic
By the bromo-7-diethylin of 3-tonka bean camphor
vI(1.18 g, 4 mmol), 4-formyl radical phenyl-boron dihydroxide
vII(0.75 g, 5mmol), tetra-triphenylphosphine palladium (462 mg, 0.4 mmol), be dissolved in dry THF 40 ml, adds aqueous sodium carbonate (2.8 ml, 2 M).N
2lower 8 h that reflux of protection, are cooled to room temperature, are spin-dried for after solvent separated yellow solid (690 mg), yield 54 % of obtaining of PE:EA=5:1 post.m.p.: 145-147 oC;
1H NMR δ (500 MHz, CDCl
3): 10.03 (s, 1H, C
HO), 7.93-7.89 (m, 4H, Ar-H), 7.82 (s, 1H, Ar-H), 7.35 (d,
J = 8.82 Hz, 1H, Ar-H), 6.63 (dd,
J = 2.38, 8.88 Hz, 1H, Ar-H), 6.53 (d,
J = 2.31 Hz, 1H, Ar-H), 3.45 (q,
J = 7.12 Hz, 4H, N(C
H 2CH
3)
2), 1.23 (t,
J = 7.12 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 344.1156 [M+Na]
+, calcd for C
20H
19NO
3Na: 344.3596.
2-cyano group-3-(4-(7-(diethylin)-tonka bean camphor-3-yl) phenyl) vinylformic acid
iasynthetic
7-diethylin-3-is to formyl radical phenyl tonka bean camphor
iIIa(0.032 g, 0.1 mmol) and cyanoacetic acid
iV(0.017 g, 0.2 mmol) is dissolved in 2 ml acetonitriles and 1ml THF mixed solvent, adds piperidines (0.001 ml, 0.01mmol), N
2protection is lower to reflux after 2 h, is spin-dried for solvent, HAc:MeOH:CH
2cl
2the red solid of=1:5:100 post separation (20 mg), yield 51 %.m.p.: > 300 oC;
1H NMR δ (500 MHz, DMSO-
d): 8.29 (s, 1H, Ar-H), 8.08 (t,
J = 8.58 Hz, 2H, Ar-H), 8.04 (s, 1H, Ar-H), 7.96 (d,
J = 8.54 Hz, 2H, Ar-H), 7.54 (d,
J = 8.98 Hz, 1H, Ar-H), 6.77 (dd,
J = 2.33, 9.00 Hz, 1H, Ar-H), 6.59 (d,
J = 2.31 Hz, 1H, Ar-H), 3.47 (q,
J = 7.04 Hz, 4H, N(C
H 2CH
3)
2), 1.15 (t,
J = 7.03 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 387.1357 [M-H]
-, calcd for C
23H
19N
2O
4: 387.4080.
Embodiment 2
5-(4-(7-(diethylin)-tonka bean camphor-3-yl) phenyl)-3-carboxymethyl rhodanine
iIasynthetic
7-diethylin-3-is to formyl radical phenyl tonka bean camphor
iIIa(0.032 g, 0.1 mmol) and rhodanine acetic acid
v(0.038 g, 0.2 mmol) is dissolved in 2 ml acetonitriles and 1ml THF, adds piperidines (0.001 ml, 0.01mmol), N
2protection is lower to reflux after 2 h, is spin-dried for solvent, HAc:MeOH:CH
2cl
2separated red solid (33 mg), yield 67 % of obtaining of=1:5:100 post.m.p.: > 300 oC;
1H NMR δ (500 MHz, DMSO-
d): 8.27 (s, 1H, Ar-H), 7.96 (t,
J = 8.48 Hz, 2H, Ar-H), 7.92 (s, 1H, Ar-H), 7.72 (d,
J = 8.49 Hz, 2H, Ar-H), 7.54 (d,
J = 8.92 Hz, 1H, Ar-H), 6.77 (dd,
J = 2.26, 8.99 Hz, 1H, Ar-H), 6.59 (d,
J = 2.15 Hz, 1H, Ar-H), 4.75 (s, 2H, C
H 2), 3.47 (q,
J = 7.03 Hz, 4H, N(C
H 2CH
3)
2), 1.16 (t,
J = 6.98 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 493.0899 [M-H]
-, calcd for C
25H
21N
2O
5S
2: 493.5747.
Embodiment 3
4 '-(7-(diethylin)-tonka bean camphor-3-yl)-[1,1'-xenyl]-4-aldehyde
iIIbsynthetic
7-diethylin-3-is to bromophenyl tonka bean camphor
vIII(1.4 g, 3.8 mmol), 4-formylphenylboronic acid
vII(0.69 g, 4.6 mmol), tetra-triphenylphosphine palladium (439 mg, 0.38 mmol) are dissolved in dry THF 40ml, add aqueous sodium carbonate (2.8 ml, 2 M), N
2lower 8 h that reflux of protection, are cooled to room temperature, are spin-dried for solvent.After the separation of PE:EA=5:1 post, obtain yellow solid (500 mg, 1.26 mmol), yield 33 %.m.p.: 240-242 oC;
1H NMR δ (500 MHz, CDCl
3): 10.08 (s, 1H, C
HO), 7.98 (d,
J = 8.09 Hz, 2H, Ar-H), 7.86-7.79 (m, 5H, Ar-H), 7.70 (d,
J = 8.23 Hz, 2H, Ar-H), 7.35 (d,
J = 8.77 Hz, 1H, Ar-H), 6.63 (dd,
J = 2.02, 8.82 Hz, 1H, Ar-H), 6.56 (s, 1H, Ar-H), 3.45 (q,
J = 7.08 Hz, 4H, N(C
H 2CH
3)
2), 1.24 (t,
J = 7.06 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 420.1515 [M+Na]
+, calcd for C
26H
23NO
3Na: 420.4555.
2-cyano group-3-[4 '-(7-(diethylin)-tonka bean camphor-3-yl)-(1,1'-biphenyl)-4-yl] vinylformic acid
ibsynthetic
iIIb(0.040 g, 0.1 mmol) and cyanoacetic acid
iV(0.017 g, 0.2 mmol) is dissolved in 2 ml acetonitriles and 1ml THF, adds piperidines (0.001 ml, 0.01mmol), N
2lower 2 h that reflux of protection, are cooled to room temperature, are spin-dried for solvent.HAc:MeOH:CH
2cl
2separated red solid (22 mg), yield 47 % of obtaining of=1:5:100 post.m.p.: > 300 oC;
1H NMR δ (500 MHz, DMSO-
d): 8.38 (s, 1H, Ar-H), 8.19 (s, 1H, Ar-H), 8.16 (d,
J = 8.54 Hz, 2H, Ar-H), 7.97 (d,
J = 8.47 Hz, 2H, Ar-H), 7.89-7.85 (m, 4H, Ar-H), 7.53 (d,
J = 8.89 Hz, 1H, Ar-H), 6.75 (dd,
J = 2.31, 8.95 Hz, 1H, Ar-H), 6.57 (d,
J = 2.21 Hz, 1H, Ar-H), 3.46 (q,
J = 7.01 Hz, 4H, N(C
H 2CH
3)
2), 1.16 (t,
J = 7.01 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 463.1660 [M-H]
-, calcd for C
29H
23N
2O
4: 463.5040.
Embodiment 4
5-[4 '-(7-(diethylin)-tonka bean camphor-3-yl)-(1,1'-biphenyl)-4-yl]-3-carboxymethyl rhodanine
iIbsynthetic
iIIb(0.040 g, 0.1 mmol) and rhodanine acetic acid
v(0.038 g, 0.2 mmol) is dissolved in 2 ml acetonitriles and 1ml THF, adds piperidines (0.001 ml, 0.01mmol), N
2protection is lower to reflux after 2 h, is spin-dried for solvent, HAc:MeOH:CH
2cl
2separated red solid (31 mg), yield 55 % of obtaining of=1:5:100 post.m.p.: > 300 oC;
1H NMR δ (500 MHz, DMSO-
d): 8.18 (s, 1H, Ar-H), 7.95 (t,
J = 4.3 Hz, 3H, Ar-H), 7.83 (q,
J = 8.56 Hz, 4H, Ar-H), 7.78 (d,
J = 8.40 Hz, 2H, Ar-H), 7.53 (d,
J = 8.83 Hz, 1H, Ar-H), 6.75 (dd,
J = 2.05, 8.92 Hz, 1H, Ar-H), 6.57 (d,
J = 1.92 Hz, 1H, Ar-H), 4.75 (s, 2H, C
H 2), 3.46 (q,
J = 7.01 Hz, 4H, N(C
H 2CH
3)
2), 1.16 (t,
J = 6.97 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 569.1213 [M-H]
-, calcd for C
31H
25N
2O
5S
2: 569.6707.
Embodiment 5
5-(4-(7-(diethylin)-tonka bean camphor-3-yl)-phenyl)-2 thiophene carboxaldehyde
iIIcsynthetic
7-diethylin-3-is to bromophenyl tonka bean camphor
vIII(1.4 g, 3.8 mmol), 5-formyl radical thienyl boric acid
iX(0.72 g, 4.6 mmol) and tetra-triphenylphosphine palladium (439 mg, 0.38mmol) are dissolved in the dry THF of 40 ml, add aqueous sodium carbonate (2.8 ml, 2 M), N
2protection is lower to reflux after 8 h, is cooled to room temperature, is spin-dried for solvent.Separated yellow solid (560 mg), the yield 37% of obtaining of PE:EA=5:1 post.m.p.: 247-248 oC;
1H NMR δ (500 MHz, CDCl
3): 9.92 (s, 1H, C
HO), 7.82 (d,
J = 8.44 Hz, 2H, Ar-H), 7.78-7.77 (m, 2H, Ar-H), 7.73 (d,
J = 8.41 Hz, 2H, Ar-H), 7.45 (d,
J = 3.96 Hz, 1H, Ar-H), 7.36 (d,
J = 8.81 Hz, 1H, Ar-H), 6.63 (dd,
J = 2.38, 8.79 Hz, 1H, Ar-H), 6.56 (s, 1H, Ar-H), 3.47 (q,
J = 7.11 Hz, 4H, N(C
H 2CH
3)
2), 1.24 (t,
J = 7.08 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 426.1114 [M+Na]
+, calcd for C
24H
21NO
3SNa: 426.4832.
2-cyano group-3-(5-(4-(7-(diethylin)-tonka bean camphor-3-yl)-phenyl)-thiophene-2-yl) vinylformic acid
icsynthetic
iIIc(40 mg, 0.1 mmol) and cyanoacetic acid
iV(17 mg, 0.2 mmol) is dissolved in 2 ml acetonitriles and 1 ml THF, adds piperidines (0.001 ml, 0.01mmol), N
2protection is lower to reflux after 2 h, is spin-dried for solvent.HAc:MeOH:CH
2cl
2separated red solid (24 mg, 0.05 mmol), yield 50 % of obtaining of=1:5:100 post.m.p.: > 300 oC;
1H NMR δ (500 MHz, DMSO-
d): 8.49 (s, 1H, Ar-H), 8.21 (s, 1H, Ar-H), 8.03 (d,
J = 4.00 Hz, 1H, Ar-H), 7.89-7.83 (m, 5H, Ar-H), 7.55 (d,
J = 8.89 Hz, 1H, Ar-H), 6.76 (dd,
J = 2.22, 8.93 Hz, 1H, Ar-H), 6.59 (d,
J = 2.09 Hz, 1H, Ar-H), 3.47 (q,
J = 7.02 Hz, 4H, N(C
H 2CH
3)
2), 1.16 (t,
J = 6.97 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 469.1220 [M-H]
-, calcd for C
27H
21N
2O
4S: 469.5317.
Embodiment 6
5-(5-(4-(7-(diethylin)-tonka bean camphor-3-yl)-phenyl)-thiophene-2-yl)-3-carboxymethyl rhodanine
iIcsynthetic
iIIc(40 mg, 0.1 mmol) and rhodanine acetic acid
v(0.038 g, 0.2 mmol) is dissolved in 2 ml acetonitriles and 1ml THF, adds piperidines (0.001 ml, 0.01mmol), N
2protection is lower to reflux after 2 h, is spin-dried for solvent.HAc:MeOH:CH
2cl
2separated red solid (31 mg), yield 54 % of obtaining of=1:5:100 post.m.p.: > 300 oC;
1H NMR δ (500 MHz, DMSO-
d): 8.22 (s, 1H, Ar-H), 8.19 (s, 1H, Ar-H), 7.89-7.85 (m, 6H, Ar-H), 7.55 (d,
J = 8.94 Hz, 1H, Ar-H), 6.76 (dd,
J = 1.90, 8.98 Hz, 1H, Ar-H), 6.59 (d,
J = 1.70 Hz, 1H, Ar-H), 4.75 (s, 2H, C
H 2), 3.47 (q,
J = 7.02 Hz, 4H, N(C
H 2CH
3)
2), 1.16 (t,
J = 6.92 Hz, 6H, N(CH
2C
H 3)
2); HREIMS m/z 575.0779 [M-H]
-, calcd for C
29H
23N
2O
5S
3: 575.6984.
Embodiment 7
Diethylin coumarin kind compound is as the application of dye sensitizing agent
The double-deck TiO that utilizes silk screen printing to prepare
2film of nanoparticles is as optoelectronic pole: the TiO that first prints 20 nm that one deck 12 μ m are thick on conductive glass FTO
2particle, calcining 30 min in retort furnace under 450 oC.Before contaminating material, burned film is immersed to 0.04 molL
-1tiCl
4the aqueous solution 70 oC pre-treatment 30 min, then distinguish water and alcohol flushing, and hair dryer dries up.Under retort furnace 450 oC, again calcine after 30 min, immerse 3 * 10 after being cooled to 80 oC
-4molL
-1the acetonitrile of dyestuff and the 24 h sensitizations of DMSO solution room temperature.Preparation to electrode: adopt method for printing screen, by certain density H
2ptCl
6solution is printed on FTO conductive glass, then 400 oC retort furnace sintering 20 min.The TiO of absorbing dye
2electrode becomes sandwich structure with platinum to electrode assembling, and at edge, splashes into ionogen (containing 0.07 mM/L I
-), utilize capillary penetration principle to introduce inside battery.In 100 mW/cm
2under light intensity is irradiated, measure photovoltage-current characteristics curve.Its result is as shown in accompanying drawing 1 and table 1:
table 1the DSSC performance perameter that the assembling of diethylin tonka bean camphor obtains
| Com.p.d | Jsc (mA·cm -2) | Voc (mV) | ff | η % |
| Ia | 5.63 | 0.66 | 0.70 | 2.60 |
| IIa | 3.33 | 0.58 | 0.73 | 1.41 |
| Ib | 5.79 | 0.69 | 0.70 | 2.80 |
| IIb | 4.03 | 0.60 | 0.73 | 1.77 |
| Ic | 7.72 | 0.66 | 0.71 | 3.62 |
| IIc | 3.41 | 0.56 | 0.73 | 1.39 |
Claims (6)
1. structure is suc as formula the diethylin coumarin kind compound shown in (I) or formula (II),
In formula (I) and formula (II): Ar is the C6-C18 aryl containing phenyl ring.
2. diethylin coumarin kind compound as claimed in claim 1, is characterized in that in formula (I) and formula (II), Ar is
,
or
.
3. diethylin coumarin kind compound as claimed in claim 1, is characterized in that in formula (I) and formula (II), Ar is
,
or
.
4. a method of preparing the coumarin kind compound described in claim 1-3 any one, it comprises the steps: formula (III) compound, formula (IV) or formula V compound, organic solvent to mix, under the effect of basic cpd, reflux stirring reaction 1 ~ 10 h, after reacting completely, be spin-dried for solvent, resistates carries out silica gel column chromatography with eluent solvent, the coumarin kind compound shown in acquisition formula (I) or formula (II);
Wherein, the product that formula (IV) compound is corresponding is formula (I) compound, and the product that formula V compound is corresponding is formula (II) compound;
Described basic cpd is one or more in piperidines, pyridine, triethylamine or dimethylamine;
Described organic solvent is a kind of or many in acetonitrile, chloroform, tetrahydrofuran (THF) or Isosorbide-5-Nitrae-dioxane
Kind;
Described eluent solvent is the mixed solvent of (chloroform and/or methylene dichloride)+(methyl alcohol and/or ethanol)+acetic acid;
The ratio of the amount of substance of formula (III) compound and formula (IV) or formula V compound and basic cpd is: 1:1.0 ~ 3.0:0.1 ~ 0.3, and organic solvent volumetric usage is counted 10 ~ 30 mL/mmol with the amount of substance of formula (III) compound;
In formula III compound, Ar is as the definition in claim 1-3 any one.
5. the diethylin coumarin kind compound described in claim 1-3 any one is as the application of dye sensitizing agent.
6. the application of the diethylin coumarin kind compound described in claim 1-3 any one in preparing solar cell.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936729A (en) * | 2014-04-16 | 2014-07-23 | 浙江工业大学 | Synthesis method and application of N-butyl carbazole dye sensitizer |
| CN104311543A (en) * | 2014-09-25 | 2015-01-28 | 浙江工业大学 | Synthesis and application of coumarin-containing triarylamine dye sensitizing agent |
| CN104610251A (en) * | 2015-01-29 | 2015-05-13 | 浙江工业大学 | Coumarin compound as well as preparation method and application thereof |
| CN107915727A (en) * | 2017-10-11 | 2018-04-17 | 浙江工业大学 | A kind of phenothiazine compound and its preparation method and application |
| CN115417846A (en) * | 2022-09-21 | 2022-12-02 | 安徽科技学院 | Coumarin-based two-state high-fluorescence material and synthesis method and application thereof |
| CN116217560A (en) * | 2022-12-30 | 2023-06-06 | 浙江工业大学 | N, N-diethylaminocoumarin compound and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005209359A (en) * | 2004-01-20 | 2005-08-04 | Konica Minolta Holdings Inc | Semiconductor for photoelectric conversion material, photoelectric conversion device and solar cell |
| JP2006278112A (en) * | 2005-03-29 | 2006-10-12 | Sharp Corp | Dye-sensitized solar cell and dye-sensitized solar cell module |
| WO2012053779A2 (en) * | 2010-10-19 | 2012-04-26 | 주식회사 동진쎄미켐 | High efficiency dye-sensitized solar cells and manufacturing method thereof |
| CN103087051A (en) * | 2013-01-17 | 2013-05-08 | 浙江工业大学 | Synthesis and application of coumarin type dye sensitizer |
-
2013
- 2013-12-11 CN CN201310667539.8A patent/CN103709129A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005209359A (en) * | 2004-01-20 | 2005-08-04 | Konica Minolta Holdings Inc | Semiconductor for photoelectric conversion material, photoelectric conversion device and solar cell |
| JP2006278112A (en) * | 2005-03-29 | 2006-10-12 | Sharp Corp | Dye-sensitized solar cell and dye-sensitized solar cell module |
| WO2012053779A2 (en) * | 2010-10-19 | 2012-04-26 | 주식회사 동진쎄미켐 | High efficiency dye-sensitized solar cells and manufacturing method thereof |
| CN103087051A (en) * | 2013-01-17 | 2013-05-08 | 浙江工业大学 | Synthesis and application of coumarin type dye sensitizer |
Non-Patent Citations (2)
| Title |
|---|
| KANG DEUK SEO ET AL.,: "Coumarin dyes containing low-band-gap chromophores for dye-sensitised solar cells", 《DYES AND PIGMENTS》, vol. 90, no. 3, 27 January 2011 (2011-01-27), pages 304 - 310 * |
| KANG DEUK SEO ET AL.,: "Novel D-A-∏-A coumarin dyes containing low band-gap chromophores for dye-sensitised solar cells", 《DYES AND PIGMENTS》, vol. 94, no. 3, 3 March 2012 (2012-03-03), pages 469 - 474 * |
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| CN103936729A (en) * | 2014-04-16 | 2014-07-23 | 浙江工业大学 | Synthesis method and application of N-butyl carbazole dye sensitizer |
| CN103936729B (en) * | 2014-04-16 | 2017-01-04 | 浙江工业大学 | The synthesis of a kind of N-butyl carbazoles dye sensitizing agent and application |
| CN104311543A (en) * | 2014-09-25 | 2015-01-28 | 浙江工业大学 | Synthesis and application of coumarin-containing triarylamine dye sensitizing agent |
| CN104610251A (en) * | 2015-01-29 | 2015-05-13 | 浙江工业大学 | Coumarin compound as well as preparation method and application thereof |
| CN107915727A (en) * | 2017-10-11 | 2018-04-17 | 浙江工业大学 | A kind of phenothiazine compound and its preparation method and application |
| CN107915727B (en) * | 2017-10-11 | 2019-11-12 | 浙江工业大学 | A kind of phenothiazine compound and its preparation method and application |
| CN115417846A (en) * | 2022-09-21 | 2022-12-02 | 安徽科技学院 | Coumarin-based two-state high-fluorescence material and synthesis method and application thereof |
| CN115417846B (en) * | 2022-09-21 | 2023-05-26 | 安徽科技学院 | Coumarin-based bimodal high-fluorescence material and synthesis method and application thereof |
| CN116217560A (en) * | 2022-12-30 | 2023-06-06 | 浙江工业大学 | N, N-diethylaminocoumarin compound and preparation method and application thereof |
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