CN106008929B - One kind closes Cd (II) oligometric comples dye sensitizing agent and preparation method thereof containing O-phenylene diamine derivatives - Google Patents
One kind closes Cd (II) oligometric comples dye sensitizing agent and preparation method thereof containing O-phenylene diamine derivatives Download PDFInfo
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- CN106008929B CN106008929B CN201610510212.3A CN201610510212A CN106008929B CN 106008929 B CN106008929 B CN 106008929B CN 201610510212 A CN201610510212 A CN 201610510212A CN 106008929 B CN106008929 B CN 106008929B
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Abstract
The invention discloses a kind of D A ' π A types Cd (II) oligometric comples dye sensitizing agent PIDT NCd and preparation method thereof are closed containing O-phenylene diamine derivatives.The dye sensitizing agent is with indacene 1,4-Dithiapentalene（IDT）Derivative is electron donor（D）, Cd (II) complexs are closed as auxiliary electron acceptor using O-phenylene diamine derivatives（A’）, Cd (II) 8-hydroxyquinoline derivative of assistant ligand 8 is π bridges, cyano group（‑CN）And carboxyl（‑COOH）For main electron acceptor（A）And anchoring group, reacted by yamamoto and oligometric comples dye sensitizing agent PIDT NCd are prepared in indacene 1,4-Dithiapentalene derivative and Cd (II) complex polymerisation.DSSC photovoltaic performance test of the experiment using PIDT NCd as dye sensitizing agent shows preferable effect：Electricity conversion（PCE）Reach 6.43%, dyestuff heat endurance is high, and its heat decomposition temperature has reached 338 DEG C, can meet the needs of photovoltaic material.
Description
Technical field
Closed the present invention relates to a kind of for DSSC photoelectric sensitization material containing O-phenylene diamine derivatives
Cd (II) oligometric comples dye sensitizing agent and preparation method thereof, the field of photovoltaic materials belonged in new material.
Background technology
Gr tzel and O ' Regan reported DSSC first in 1991（DSSCs）Afterwards, DSSCs just by
It is considered most potential photovoltaic cell, becomes the focus in renewable and clean energy resource research and development field.And dye sensitizing agent exists
Played in DSSCs and solar photon is transformed into electronics and makes electronics in intramolecular transfer and is injected into electrode TiO2On crucial work
With by the most extensive research and application and development.In substantial amounts of research report and invention at present, organic dyestuff is quick
Agent is mostly D-A and D- π-A types（That is electron donor D is connected with acceptor A by a pi-conjugated system）.And in nearest, appearance
With organic diazosulfide（BTH）Deng for aid in electron acceptor（A’）D-A '-π-A types（I.e. between donor and pi-conjugated system again
Connect an acceptor）High-performance dye-sensitized molecules are reported；The dyestuff of this structure is compared to D- π-A type dyes, because effectively
Reduce charge recombination, add the electron transfer efficiency and stability of dyestuff, so as to which larger improves the dye sensitization sun
The electricity conversion of energy battery（PCE）Deng photovoltaic performance.Based on this, the present invention has been researched and developed with stability and electrophilic
Transition metal Cd (II) complexs of function admirable are as auxiliary electron acceptor（A’）, and invent and be prepared for a kind of new D-
A '-π-A polymer-metal complex dye sensitizing agents.
The content of the invention
It is an object of the invention to provide be prepared for one kind with indacene 1,4-Dithiapentalene（IDT）For donor（D）, with adjacent benzene two
Amine derivative closes Cd (II) complex as auxiliary electron acceptor（A’）, Cd (II) auxiliary is π bridges with 8-hydroxyquinoline, cyano group（-
CN）And carboxyl（-COOH）For main electron acceptor（A）With the D-A '-π-A types of anchoring group Cd (II) is closed containing O-phenylene diamine derivatives
Oligometric comples dye sensitizing agent PIDT-NCd.Applied to making dye sensitizing agent in DSSC, have compared with
High electricity conversion and high heat endurance, its general structure are as follows：
The oligometric comples PIDT-NCd of formula 1 structure.
One kind closes Cd (II) oligometric comples dye sensitizing agent PIDT-NCd synthetic method containing O-phenylene diamine derivatives.
（1）The preparation of part N, N '-bis- (4- bromines benzals) -1,2- phenylenediamines：
The ethanol solution of 4- bromobenzaldehydes in three-neck flask is warming up to 50 DEG C -80 DEG C, stirring is lower slowly to drip dropwise
Add o-phenylenediamine ethanol solution, and add a small amount of anhydrous ZnCl2Isothermal reaction 2-8 h afterwards.Cool down, subtract after the completion of reaction
Press rotary distillation to remove a greater part of solvent, be placed in refrigerator, at 0-10 DEG C overnight, crystallized product is used into absolute ethyl alcohol again
Recrystallization, obtains part N, N '-bis- (4- bromines benzals) -1,2- phenylenediamines, product is white powder crystal.
（2）Cd (II) complex（NCd）Synthesis：
By a certain amount of part N, N '-bis- (4- bromines benzal) -1,2- phenylenediamines and 2- cyano group -3-（8-hydroxyquinoline -5-
Base）Acrylic acid is dissolved in the tetrahydrofuran of three-neck flask（THF）In, Cd (CH are added dropwise with dropping funel under agitation3COO)2•
2H2O absolute methanol solutions, 6-24h is reacted after being warming up to backflow, crystallisation by cooling after having reacted, crystal is tied again with absolute methanol
Twice, the O-phenylene diamine derivatives 8-hydroxyquinoline derivative for obtaining yellow powder closes cadmium (II) complex NCd to crystalline substance.
（3）Oligometric comples PIDT-NCd synthesis：
Under nitrogen protection will be upper（2）It is the step obtained complex NCd of synthesis and monomer indacene and dibromo thiophene, double（Three
Phenylphosphine）Nickel chloride, triphenylphosphine and 2,2 '-bipyridyl are dissolved in the DMF solvent of single neck flask, are warming up to 80-100oC,
Reaction 36~72 hours.Reaction is poured into a large amount of ethanol solutions after terminating, cold filtration, and washs to obtain with absolute ethyl alcohol
Yellow solid O-phenylene diamine derivatives close Cd (II) oligometric comples dye sensitizing agent PIDT-NCd.
One kind closes Cd (II) oligometric comples PIDT-NCd purposes containing O-phenylene diamine derivatives：In the dye sensitization sun
It is used as absorbing sunshine in energy battery and produces and transmit the dye sensitization agent material of electronics.
The positive technological progress effect of the present invention is：（1）Invention is a kind of to close the poly- of Cd (II) containing O-phenylene diamine derivatives
Close complex thing be using normal transition metal Cd (II) complex for aid in electron acceptor A ' new polymers D-A '-π-
A type dye sensitizers, the push-and-pull electronic equilibrium in dye molecule can be effectively adjusted, increase the conjugate property of molecule, accelerate electricity
Transmission speed of the son from electron donor to acceptor, and expand dyestuff in the absorption region of visual field and absorption intensity etc., thus table
Reveal the photovoltaic performances such as preferable photoelectric transformation efficiency；（2）There is high light and heat stability；（3）Raw material is easy to get, preparation method phase
To simple, the specific demand such as no high temperature and high pressure, cost is low.
Brief description of the drawings
The nucleus magnetic hydrogen spectrum of part N, N '-bis- (4- bromines benzals) -1,2- phenylenediamines of Fig. 1 embodiment of the present invention synthesis
（1HNMR)（400MHz, CDCl3, TMS）；
The infrared spectrum (IR) for the compound N Cd that Fig. 2 embodiment of the present invention obtains（KBr crystal tablettings, 4000 ~ 400
cm-1）；
The infrared spectrum (IR) for the compound PIDT-NCd that Fig. 3 embodiment of the present invention obtains（KBr crystal tablettings, 4000 ~
400 cm-1）；
The thermogravimetric analysis of oligometric comples PIDT-NCd synthesized by Fig. 4 embodiment of the present invention（TGA）Curve；
The uv-visible absorption spectroscopy of oligometric comples PIDT-NCd synthesized by Fig. 5 embodiment of the present invention（UV-
vis)；
The DSSC electric current of oligometric comples PIDT-NCd synthesized by Fig. 6 embodiment of the present invention is close
Degree-voltage（J-V）Curve；
The DSSC external quantum efficiency of compound PIDT-NCd synthesized by Fig. 7 embodiment of the present invention
（IPCE）Curve.
Embodiment
The reaction mechanism of compound of the present invention is：
With reference to specific embodiment, the present invention is described further.
Embodiment 1：
One kind closes Cd (II) oligometric comples PIDT-NCd containing O-phenylene diamine derivatives.
Oligometric comples PIDT-NCd molecular structural formula is as follows：
Above-mentioned oligometric comples PIDT-NCd preparation method is as follows.
A. part N, N '-bis- (4- bromines benzal) -1,2- phenylenediamines synthesis：Weigh 6.1 g（33 mmol）4- bromobenzene first
Then aldehyde adds 50 mL absolute ethyl alcohols, stirring makes fully to dissolve, then is slowly ramped to 60 DEG C in 250 mL three-necked flasks
Afterwards, by 1.62 g（15 mmol）O-phenylenediamine is dissolved in absolute ethyl alcohol（10 mL）In, and be slowly dropped into constant pressure funnel
System is stated, a small amount of anhydrous ZnCl is added after being added dropwise2Continue after reacting 4 h, wait it to be cooled to decompression rotation after room temperature and go to part
Solvent, refrigerator overnight is placed in, produces white crude, white crude is filtered, fully washed with absolute ethyl alcohol, and use nothing
Water methanol is recrystallized, and 4.05 g white solid products are obtained after vacuum drying（Yield 61%, 1HNMR characterize as shown in Figure 1）.
m.p. 196-198℃. FT-IR (KBr, cm-1): 3089 (=C-H), 1640 (C=C), 1570 (C=N), 786
(C-Br). 1H NMR (CDCl3, ppm): 8.32 (s, 2H), 7.30-7.46 (m, 4H), 7.17-7.19(d,
4H) 6.82 (s, 4H)。
B. Cd (II) complex（NCd）Synthesis：1.32 g are weighed respectively（4 mmol）Part N, N '-bis- (4- bromine benzal
Base) -1,2- phenylenediamines and 0.96 g（4 mmol）2- cyano group -3-（8-hydroxyquinoline -5- bases）Acrylic acid, then it is added respectively
Enter into 250 mL three neck round bottom flask, then measure 100 mL tetrahydrofurans（THF）Solvent is added in reaction system, stirring
The lower 1.17g that will be weighed（4.4 mmol）Cd(CH3COO)2•2H2O passes through constant pressure addition with after 30 mL absolute methanol dissolving
Funnel is slowly dropped in reaction system, and heating makes the h of back flow reaction 12, reaction be cooled to room temperature after terminating, and will
Filtration of crude product, crude product is washed twice with deionized water and absolute ethyl alcohol respectively, then, with absolute methanol recrystallization twice
Drying obtains 1.33 g yellow solids after a few days under vacuum condition（Yield 51%, IR characterize as shown in Figure 2）.FT-IR (KBr,
cm−1): 3440 (-OH), 3052 (=C-H), 2223 (C≡N), 1681 (C=O), 1596 (C=C), 1535 (C=
N), 1126 (C=N-M), 521 (N-M). Anal. Calcd. for [C35H24Br2N4O5Cd]: C, 49.29; H,
2.84; N, 6.57%. Found: C, 49.52; H, 2.92; N, 6.83%。
C. polymer-metal complex（PIDT-NCd）Synthesis：Weigh 0.34 g（0.4 mmol）Cd (II) complex
NCd, 0.26 g（0.4 mmol）It is double（Triphenylphosphine）Nickel Chloride, 0.42g（0.4 mmol）Monomer indacene 1,4-Dithiapentalene is spread out
Biology, 0.13 g（2 mmol）Zinc powder, 0.21 g（0.8 mmol）Triphenyl phosphorus and 0.006 g（0.38 mmol）2,2 '-connection
Pyridine sequentially adds single necked round bottom flask（50 mL）In, and add 15 mL DMF solution（DMF）Make molten
Agent.Then vacuumize, and be passed through nitrogen protection, continue to react 48 h after being warming up to 90 DEG C.After terminating Deng reaction, reactant is taken advantage of
Heat filtering after standing overnight, is filtered out, and fully washed and done with absolute ethyl alcohol enter in a large amount of ethanol solutions
It is dry, it is final to obtain the g of yellow solid product 0.35（Yield 55%, IR characterize as shown in Figure 3）.FT-IR (KBr, cm-1): 3432
(-OH), 2932, 2856 (C-H), 2210 (C≡N), 1660 (C=O), 1685 (C=C), 1526 (C=N),
1112 (C=N-M), 503 (N-M). Anal. Calcd. for [C99H96N4O5S2Cd]: C, 74.39; H, 6.05;
N, 3.51; S, 4.01%. Found: C, 74.65; H, 6.14; N, 3.61; S, 3.93%. Mn=11.6×103
g/mol, PDI=1.93。
Embodiment 2：
A kind of thermogravimetric curve for the oligometric comples dyestuff PIDT-NCd that Cd (II) is closed containing O-phenylene diamine derivatives of measure
(TGA).Method：Q50 thermogravimetric analyzers, N2Tested under protection with 25 DEG C/min programming rate, its related thermal weight loss and
Thermal decomposition performance result such as accompanying drawing 4.
Embodiment 3：
Controlled and measured by computer with the SourceMete of Computer-programmed Keithley 2611, Solar
Simulator (Oriel, 91160-1000 91192, Perccell Technologies) is light source（500-W Xe, AM
1.5 G）, the effective area of battery-active electrode is 0.25cm2, determine respectively using polymer-metal complex dyestuff PIDT-NCd as
The performance parameter of the DSSC of dye sensitizing agent, its Cell current density-voltage（J-V）Curve such as Fig. 6, outside
Quantum efficiency（IPCE）Such as Fig. 7.Its photovoltaic performance result such as table one：
The photovoltaic performance parameter of the polymeric dye of table one
Claims (3)
1. one kind closes Cd (II) oligometric comples dye sensitizing agent containing O-phenylene diamine derivatives, its structural formula is as follows：
untitled.GIF
The oligometric comples PIDT-NCd of formula 1 structure.
2. a kind of oligometric comples dye sensitizing agent that Cd (II) is closed containing O-phenylene diamine derivatives according to claim 1,
Its preparation method is：
（1）The preparation of part N, N '-bis- (4- bromines benzals) -1,2- phenylenediamines：
The ethanol solution of 4- bromobenzaldehydes in three-neck flask is warming up to 50 DEG C -80 DEG C, it is adjacent to stir lower slow dropwise addition dropwise
Phenylenediamine ethanol solution, and adding a small amount of anhydrous ZnCl2Isothermal reaction 2-8 h afterwards；
Cooled down after the completion of reaction, decompression rotary distillation removes a greater part of solvent, is placed in refrigerator at 0-10 DEG C overnight, to tie
Brilliant product is recrystallized with absolute ethyl alcohol again, obtains part N, N '-bis- (4- bromines benzals) -1,2- phenylenediamines, and product is white
Powder crystal；
（2）Cd (II) complex（NCd）Synthesis：
By a certain amount of part N, N '-bis- (4- bromines benzal) -1,2- phenylenediamines and 2- cyano group -3-（8-hydroxyquinoline -5- bases）
Acrylic acid is dissolved in the tetrahydrofuran of three-neck flask（THF）In, Cd (CH are added dropwise with dropping funel under agitation3COO)2•2H2O without
Water beetle alcoholic solution, back flow reaction 6-24h is warming up to, crystallisation by cooling after having reacted, crystal is recrystallized twice with absolute methanol, is obtained
O-phenylene diamine derivatives 8-hydroxyquinoline derivative to yellow powder closes cadmium (II) complex NCd；
（3）Oligometric comples PIDT-NCd synthesis：
Under nitrogen protection will be upper（2）It is the step obtained complex NCd of synthesis and monomer indacene and dibromo thiophene, double（Triphenyl
Phosphine）Nickel chloride, triphenylphosphine and 2,2 '-bipyridyl are dissolved in the DMF solvent of single neck flask, are warming up to 80-100oC, reaction
36~72 hours, reaction was poured into a large amount of ethanol solutions after terminating, cold filtration, and was washed with absolute ethyl alcohol to obtain yellow
Solid O-phenylene diamine derivatives close Cd (II) oligometric comples dye sensitizing agent PIDT-NCd.
3. a kind of oligometric comples dye sensitizing agent that Cd (II) is closed containing O-phenylene diamine derivatives according to claim 1,
Its purposes is to be used as dye sensitizing agent in DSSC.
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| CN108084448B (en) * | 2017-11-30 | 2020-10-30 | 湘潭大学 | Cadmium polymerization complex containing 4, 5-dimethyl-1, 2-phenylenediamine derivative and preparation method and application thereof |
| CN111943965B (en) * | 2019-05-16 | 2022-09-06 | 湘潭大学 | Pyridine imine derivative and 8-hydroxyquinoline derivative cadmium complex dye sensitizer (BDTT-im-Cd) and preparation method and application thereof |
| CN112279870B (en) * | 2019-07-25 | 2023-05-23 | 湘潭大学 | Dye sensitizer of imine derivative and 8-hydroxyquinoline derivative cadmium complex, and preparation method and application thereof |
| CN114196035B (en) * | 2021-12-17 | 2022-12-09 | 湘潭大学 | Four polymerization complexes using phenanthroline derivative as ligand, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539804A (en) * | 2013-10-31 | 2014-01-29 | 湘潭大学 | Phenothiazine-containing polymerization metal complex as well as preparation method and application thereof |
| EP2700641A1 (en) * | 2012-08-22 | 2014-02-26 | Solvay SA | Azulenocyanine analogue compounds comprising anchoring group, method of making the same, and their use as dye for dye-sensitized solar cells |
| CN105294558A (en) * | 2015-11-06 | 2016-02-03 | 湘潭大学 | 2-cyano-3-(8-hydroxyquinoline-5-yl)acrylic acid, and preparation method and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2700641A1 (en) * | 2012-08-22 | 2014-02-26 | Solvay SA | Azulenocyanine analogue compounds comprising anchoring group, method of making the same, and their use as dye for dye-sensitized solar cells |
| CN103539804A (en) * | 2013-10-31 | 2014-01-29 | 湘潭大学 | Phenothiazine-containing polymerization metal complex as well as preparation method and application thereof |
| CN105294558A (en) * | 2015-11-06 | 2016-02-03 | 湘潭大学 | 2-cyano-3-(8-hydroxyquinoline-5-yl)acrylic acid, and preparation method and applications thereof |
Non-Patent Citations (1)
| Title |
|---|
| Novel D–p–A dye sensitizers of polymeric metal complexes based on Cd(II) with salicylaldehyde and diaminomaleonitrile: synthesis, characterization，and photovoltaic performance for dye-sensitized solar cells;Jiaomei Hu et al.;《Res Chem Intermed》;20150101;第41卷;8327-8342 * |
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