CN103351332A - Conjugate extension carboxyl dipyridyl ligand and synthetic method and application for ruthenium dye thereof - Google Patents

Conjugate extension carboxyl dipyridyl ligand and synthetic method and application for ruthenium dye thereof Download PDF

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CN103351332A
CN103351332A CN2013103098929A CN201310309892A CN103351332A CN 103351332 A CN103351332 A CN 103351332A CN 2013103098929 A CN2013103098929 A CN 2013103098929A CN 201310309892 A CN201310309892 A CN 201310309892A CN 103351332 A CN103351332 A CN 103351332A
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ruthenium
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孙花飞
孙元伟
张宪玺
杜玉昌
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Liaocheng University
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Abstract

The invention discloses a conjugate extension carboxyl dipyridyl ligand, synthesizes two new symmetric ruthenium dyes, namely L121 and L122, and two dissymmetric ruthenium dyes, namely L123 and L124, based the conjugate extension carboxyl dipyridyl ligand through one-pot method. Compared with the experiment data of N3 dye, visible absorption peak of L121-L122 emerge remarkable red shift, and the intensity of the absorption peak is increased accordingly. Therefore, the novel dye is provided with better light absorption when comparing with classical N3 dye, and has better application prospect in dye-sensitized solar cell.

Description

The synthetic method of Conjugate extended carboxyl bipyridine ligand and ruthenium based dye thereof and application
Technical field
The present invention relates to synthetic method and the application of a kind of Conjugate extended carboxyl bipyridine ligand and ruthenium based dye thereof, belong to the synthesising chemical technology field.
Background technology
In recent years, energy problem becomes one of significant problem of face of mankind nowadays.Can find the new forms of energy of effective substitute fossil fuels, be the key that solves energy problem.Therefore, countries in the world all tap a new source of energy making great efforts when saving energetically the existing energy.Among this, sun power is study hotspot in recent years.Carry out the opto-electronic conversion generating by solar cell and be considered to utilize the most effective approach of sun power, and solar cell is pollution-free, both can alleviate the energy-intensive problem, meets again the strategic objective of China's Sustainable development.
Silicon is that the solar cell characteristics are that transformation efficiency is relatively high, can reach more than 20%, but its preparation condition is relatively harsher, and complex process, cost is expensive, is difficult to popularize use.Comparatively speaking, dye-sensitized solar cells (DSSC) uses because the characteristics such as its preparation technology is simple, low cost, high-level efficiency are expected to realize popularize on a large scale, becomes the focus of present research.Both at home and abroad the investigator conducts in-depth research aspects such as the anodic-cathodic of DSSC, photosensitizer, electrolytes, improves the efficiency of conversion of battery.Sensitizing agent is important component part wherein, directly affects the efficiency of conversion of battery.Therefore, the efficient sensitizing agent of synthesizing new is of great significance the photovoltaic performance that improves dye-sensitized solar cells and the cost tool that reduces battery.
Ruthenium be title complex be in the dye-sensitized solar cells research the earliest, general also the most ripe most widely used a kind of sensitizing agent, take N3, N719 etc. as Typical Representative, its efficiency of conversion has reached 11%, and has tentatively dropped into production.Its shortcoming is the absorption region relative narrower, can not utilize well sunlight at Long wavelength region.The objective of the invention is by the wider sensitizing agent of conjugated degree acquisition absorption region of suitable raising ruthenium based dye bipyridine ligand, thereby can utilize better sunlight in order to overcome the deficiency of absorption region.
Summary of the invention
The objective of the invention is provides synthetic method and the application of a kind of Conjugate extended carboxyl bipyridine ligand and ruthenium based dye thereof for overcoming above-mentioned the deficiencies in the prior art.
For achieving the above object, the present invention adopts following technical proposals:
A kind of Conjugate extended carboxyl bipyridine ligand, its structural formula is as follows:
Figure BDA00003548450000011
R=-COOH wherein ,-CN.
The preparation method of above-mentioned Conjugate extended carboxyl bipyridine ligand, concrete grammar is as follows:
With 2,2'-dipyridyl-4,4'-dicarbaldehyde, propanedioic acid or cyanoacetic acid (general formula:
Figure BDA00003548450000021
R=-COOH,-CN), Pyrrolidine (Pyrrolidine) adds successively and fill in the reaction vessel of acetonitrile or ethanol, stirring and evenly mixing, 80～120 ℃ were refluxed 3～5 hours, left standstill 8～13 hours, vacuum filtration, acetonitrile or washing with alcohol and get final product, wherein, 2,2 '-dipyridyl-4, the ratio of the amount of substance of 4 '-dicarbaldehyde, propanedioic acid or cyanoacetic acid, Pyrrolidine, acetonitrile or ethanol is 1:3:0.35:160～240.
Based on the symmetrical ruthenium based dye of above-mentioned Conjugate extended carboxyl bipyridine ligand, its structural formula is as follows:
Figure BDA00003548450000023
R=-COOH wherein ,-CN.
The preparation method of above-mentioned symmetrical ruthenium based dye, concrete steps are as follows:
With described carboxyl bipyridine ligand and RuCl 3Join and fill DMF(N, dinethylformamide) reaction vessel in, stirring and evenly mixing, 140～180 ℃ were refluxed 3～5 hours, added NH 4NCS, 120～150 ℃ were refluxed 3～5 hours, and whole reaction process is carried out in nitrogen atmosphere; Leave standstill 8～13h, vacuum filtration, wash with water first 3～5 times, again with ether washing 3～5 times, vacuum-drying and get final product, wherein carboxyl bipyridine ligand, RuCl 3, NH 4The ratio of the amount of substance of NCS, DMF is 2:1:30:1300～2300.
Figure BDA00003548450000024
Based on the asymmetric ruthenium based dye of above-mentioned Conjugate extended carboxyl bipyridine ligand, its structural formula is as follows:
R=-COOH wherein ,-CN.
The preparation method of above-mentioned asymmetric ruthenium based dye, concrete steps are as follows:
With 4,4'-dimethyl-2,2'-dipyridyl, dichloro (p-cymene) ruthenium (II) dimer join in the reaction vessel that fills DMF, stir and make its mixing half an hour, and 60～90 ℃ were refluxed 3～5 hours.Then, add described carboxyl bipyridine ligand, refluxed 3～5 hours at 140～180 ℃, add NH 4NCS, 120～150 ℃ were refluxed 3～5 hours, whole reaction process is carried out in nitrogen atmosphere, left standstill 8～13 hours, vacuum filtration, wash with water first 3～5 times, again with ether washing 3～5 times, vacuum-drying and get final product, carboxyl bipyridine ligand, 4 wherein, 4'-dimethyl-2,2'-dipyridyl, dichloro (p-cymene) ruthenium (II) dimer, NH 4The ratio of the amount of substance of NCS is 2:2:1:30:4700～7800.
Figure BDA00003548450000032
Described Conjugate extended carboxyl bipyridyl ruthenium dye in dye-sensitized solar cells as the application of photosensitizer.
The present invention has designed two kinds of Novel Ligands, and on N3 dyestuff basis, by changing the group on the dipyridyl, design two symmetries with two asymmetric rutheniums be sensitizing agent: by carboxyl is changed over the propylene diacid, alpha-cyanoacrylate increases conjugation, has improved the molar extinction coefficient of dyestuff.The invention has the beneficial effects as follows, with the synthetic two kinds of Novel Ligands of one kettle way and four kinds of novel ruthenium based dyes (the ruthenium based dye L121 of two symmetries and L122, two asymmetric ruthenium based dye L123 and L124), the experimental data of the N3 dyestuff of crossing with bibliographical information is compared (position of the maximum wavelength absorption peak of the N3 of experiment report is at 532nm), obvious red shift (the L121:557nm of the maximum wavelength absorption peak of L121 and L122, L122:566nm), L123 and L124 form between 450-550nm and absorb platform, to the more abundant (see figure 3) of sunlight utilization.Therefore, this new dye has the better absorbing properties of N3 dyestuff than classics, has better application prospect in dye-sensitized solar cells.
Description of drawings
Fig. 1 is part a 1H-NMR figure;
Fig. 2 is part b 1H-NMR figure;
Fig. 3 is four kinds of new ruthenium based dyes and the ultraviolet-visible absorption spectroscopy of N3.
Embodiment
The present invention will be further elaborated below in conjunction with drawings and Examples, should be noted that following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment 1:
The synthetic method of part a and condition: 2,2 '-dipyridyl-4,4 '-dicarbaldehyde, propanedioic acid and Pyrrolidine be synthetic ligands a in ethanol;
Part a(4,4'-two (2,2-dioctyl phthalate-1-vinyl)-2,2'-dipyridyl) synthetic route:
Figure BDA00003548450000041
Concrete steps are: with 0.25g(2.4mmol) 2,2'-dipyridyl-4,4'-dicarbaldehyde, 0.75g(7.2mmol) propanedioic acid and 0.08g Pyrrolidine add in the reaction flask that fills 30mL ethanol successively, stir and made its mixing in 0.5 hour, then refluxed 4 hours at 95 ℃, leave standstill 10h, vacuum filtration washs and get final product with acetonitrile.
Part a:1H-NMR (298K, 200MHz, δ in ppm) 7.7 (m, 2H), 7.8～7.9 (m, 2H), 8.1 (s, 2H), 8.8 (m, 2H), 9.1 (s, 2H) see Fig. 1.
Embodiment 2:
Part b synthetic method and condition: 4,4'-dicarbaldehyde-2,2'-dipyridyl, cyanoacetic acid and Pyrrolidine be synthetic ligands b in acetonitrile;
Part b(4,4'-two (2-cyano group-1-vinylformic acid)-2,2' – dipyridyl) synthetic route:
Figure BDA00003548450000042
Concrete steps are: with 0.25g(2.4mmol) 2,2'-dipyridyl-4,4'-dicarbaldehyde, 0.61g(7.2mmol) cyanoacetic acid and 0.08g Pyrrolidine add in the reaction flask that fills the 30mL acetonitrile successively, stir and made its mixing in 0.5 hour, then refluxed 5 hours at 105 ℃, leave standstill 9h, vacuum filtration washs and get final product with acetonitrile.
Part b:1H-NMR (298K, 200MHz, δ in ppm) 7.6～7.9 (m, 4H), 8.3 (m, 2H), 8.5～8.9 (m, 2H), 12.7 (s, 4H) see Fig. 2.
Embodiment 3:
Synthetic method based on the symmetrical ruthenium based dye L121 of part a: part a, RuCl 3, NH 4NCS is synthetic L121 in DMF;
(two (4,4'-two (2,2-dioctyl phthalate-1-vinyl)-2,2'-dipyridyls) (NCS) for the L121(ruthenium 2) synthetic route:
Figure BDA00003548450000051
Concrete steps are: with 0.058g(0.16mmol) part a, 0.017g(0.082mmol) RuCl 3Join among the 30mLDMF, stir and made its mixing in 0.5 hour, 160 ℃ were refluxed 4 hours, added 0.5g(6.57mmol) NH 4NCS, 130 ℃ were refluxed 4 hours, and whole reaction process is carried out in nitrogen atmosphere.Leave standstill 10h, vacuum filtration, wash with water first 3 times, again with ether washing 4 times.Vacuum-drying.
Embodiment 4:
Synthetic based on the symmetrical ruthenium based dye L122 of part b: part b, RuCl 3, NH 4NCS is synthetic L122 in DMF;
(4,4'-two (4,4'-two (2-cyano group-1-vinylformic acid)-2,2' – dipyridyl) (NCS) for L122(ruthenium two 2) synthetic route:
Figure BDA00003548450000052
Concrete steps are: with 0.056g(0.16mmol) part b, 0.017g(0.082mmol) RuCl 3Join among the 30mLDMF, stir and made its mixing in 0.5 hour, then refluxed 5 hours at 170 ℃, add 0.5g(6.57mmol) NH 4NCS, 140 ℃ were refluxed 5 hours, whole reaction process is carried out in nitrogen atmosphere, hold over night (11h), vacuum filtration and get final product, wash with water first 3 times, again with ether washing 3 times.Vacuum-drying and get final product.
Embodiment 5:
Synthetic based on the asymmetric ruthenium based dye L123 of part b;
(4,4'-two (4,4'-two (2-cyano group-1-vinylformic acid)-2,2' – dipyridyl) (4,4'-dimethyl-2,2'-dipyridyl) (NCS) for the L123(ruthenium 2) synthetic route:
Figure BDA00003548450000061
Concrete steps are: with 0.03g(0.16mmol) 4,4'-dimethyl-2,2'-dipyridyl, 0.05g(0.082mmol) dichloro (p-cymene) ruthenium (II) dimer joins DMF(50mL) in, stir and made its mixing in 0.5 hour, then refluxed 4 hours at 80 ℃, then add 0.056g(0.16mmol) part b, 160 ℃ were refluxed 4 hours, added 0.5g(6.57mmol) NH 4Then NCS refluxed 4 hours at 130 ℃.Whole reaction process is at N 2Carry out in the protection.Hold over night (8h), vacuum filtration, wash with water first 4 times, again with ether washing 4 times, vacuum-drying and get final product.
Embodiment 6:
Synthetic based on the asymmetric ruthenium based dye L124 of part b;
L124(ruthenium (4,4'-two (2,2-dioctyl phthalate-1-vinyl)-2,2'-dipyridyl) (4,4'-dimethyl-2,2'-dipyridyl) (NCS) 2) synthetic route:
Concrete steps are: with 0.03g(0.16mmol) 4,4'-dimethyl-2,2'-dipyridyl, 0.05g(0.082mmol) dichloro (p-cymene) ruthenium (II) dimer joins DMF(50mL) in, stir and make its mixing half an hour, then refluxed 3.5 hours at 60 ℃, then add 0.058g(0.16mmol) part a, refluxed 4.5 hours at 160 ℃, add 0.5g(6.57mmol) NH 4Then NCS refluxed 5 hours at 130 ℃, and whole reaction process is carried out in nitrogen atmosphere, hold over night (9h), vacuum filtration, wash with water first 5 times, again with ether washing 5 times, vacuum-drying and get final product.
Although above-mentionedly by reference to the accompanying drawings the specific embodiment of the present invention is described; but be not limiting the scope of the invention; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various modifications that creative work can make or distortion still in protection scope of the present invention.

Claims (7)

1. Conjugate extended carboxyl bipyridine ligand is characterized in that its structural formula is as follows:
Figure FDA00003548449900011
R=-COOH wherein ,-CN.
2. the preparation method of Conjugate extended carboxyl bipyridine ligand claimed in claim 1 is characterized in that concrete grammar is as follows:
With 2,2 '-dipyridyl-4,4 '-dicarbaldehyde, propanedioic acid or cyanoacetic acid, Pyrrolidine add in the reaction vessel that fills acetonitrile or ethanol successively, stirring and evenly mixing, 80～120 ℃ were refluxed 3～5 hours, left standstill vacuum filtration, acetonitrile or washing with alcohol and get final product 8～13 hours, wherein, 2,2 '-dipyridyl-4, the ratio of the amount of substance of 4 '-dicarbaldehyde, propanedioic acid or cyanoacetic acid, Pyrrolidine, acetonitrile or ethanol is 1:3:0.35:160～240.
3. based on the symmetrical ruthenium based dye of Conjugate extended carboxyl bipyridine ligand claimed in claim 1, it is characterized in that its structural formula is as follows:
Figure FDA00003548449900012
R=-COOH wherein ,-CN.
4. the preparation method of symmetrical ruthenium based dye claimed in claim 3 is characterized in that, concrete steps are as follows:
With described carboxyl bipyridine ligand and RuCl 3Join in the reaction vessel that fills DMF, stirring and evenly mixing, 140～180 ℃ were refluxed 3～5 hours, added NH 4NCS, 120～150 ℃ were refluxed 3～5 hours, and whole reaction process is carried out in nitrogen atmosphere; Leave standstill 8～13h, vacuum filtration, wash with water first 3～5 times, again with ether washing 3～5 times, vacuum-drying and get final product, wherein, carboxyl bipyridine ligand, RuCl 3, NH 4The ratio of the amount of substance of NCS, DMF is 2:1:30:1300～2300.
5. based on the asymmetric ruthenium based dye of Conjugate extended carboxyl bipyridine ligand claimed in claim 1, it is characterized in that its structural formula is as follows:
Figure FDA00003548449900021
R=-COOH wherein ,-CN.
6. the preparation method of asymmetric ruthenium based dye claimed in claim 5 is characterized in that, concrete steps are as follows:
With 4,4'-dimethyl-2,2'-dipyridyl, dichloro (p-cymene) ruthenium (II) dimer join in the reaction vessel that fills DMF, stir and make its mixing half an hour, and 60～90 ℃ were refluxed 3～5 hours; Then, add described carboxyl bipyridine ligand, refluxed 3～5 hours at 140～180 ℃, add NH 4NCS, 120～150 ℃ were refluxed 3～5 hours, whole reaction process is carried out in nitrogen atmosphere, leaves standstill vacuum filtration 8～13 hours, wash with water first 3～5 times, again with ether washing 3～5 times, vacuum-drying and get final product, wherein, carboxyl bipyridine ligand, 4,4'-dimethyl-2,2'-dipyridyl, dichloro (p-cymene) ruthenium (II) dimer, NH 4The ratio of the amount of substance of NCS is 2:2:1:30:4700～7800.
Claim 3,5 described Conjugate extended carboxyl bipyridyl ruthenium dye in dye-sensitized solar cells as the application of photosensitizer.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103617892A (en) * 2013-12-13 2014-03-05 福州大学 Flexible zinc-oxide quantum-dot solar battery adopting ruthenium-modified dye as sensitizer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101910322A (en) * 2007-12-26 2010-12-08 株式会社东进世美肯 Novel Ru-type sensitizers and method for the production thereof
CN102286212A (en) * 2010-06-17 2011-12-21 中央大学 Organic and inorganic photosensitive dyes
JP2013058424A (en) * 2011-09-09 2013-03-28 Sony Corp Photosensitizing dye, dye sensitized photoelectric conversion element, electronic apparatus and building

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101910322A (en) * 2007-12-26 2010-12-08 株式会社东进世美肯 Novel Ru-type sensitizers and method for the production thereof
CN102286212A (en) * 2010-06-17 2011-12-21 中央大学 Organic and inorganic photosensitive dyes
JP2013058424A (en) * 2011-09-09 2013-03-28 Sony Corp Photosensitizing dye, dye sensitized photoelectric conversion element, electronic apparatus and building

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103617892A (en) * 2013-12-13 2014-03-05 福州大学 Flexible zinc-oxide quantum-dot solar battery adopting ruthenium-modified dye as sensitizer

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