CN101215300B - Rhenium(I) tricarbonyl polypyridyl complex and its preparation method and use - Google Patents
Rhenium(I) tricarbonyl polypyridyl complex and its preparation method and use Download PDFInfo
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- CN101215300B CN101215300B CN2008100192186A CN200810019218A CN101215300B CN 101215300 B CN101215300 B CN 101215300B CN 2008100192186 A CN2008100192186 A CN 2008100192186A CN 200810019218 A CN200810019218 A CN 200810019218A CN 101215300 B CN101215300 B CN 101215300B
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- rhenium
- pyridine
- dioctyl phthalate
- methylene radical
- dithia cyclopentenes
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- FSXLZCNUCYUGCH-UHFFFAOYSA-N carbon monoxide;rhenium Chemical group [Re].[O+]#[C-].[O+]#[C-].[O+]#[C-] FSXLZCNUCYUGCH-UHFFFAOYSA-N 0.000 title 1
- 125000004424 polypyridyl Polymers 0.000 title 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 28
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 24
- OJNBAGCXFHUOIQ-UHFFFAOYSA-N [Re+] Chemical compound [Re+] OJNBAGCXFHUOIQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000005660 chlorination reaction Methods 0.000 claims description 28
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 26
- 206010070834 Sensitisation Diseases 0.000 claims description 20
- 230000008313 sensitization Effects 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003504 photosensitizing agent Substances 0.000 abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MVCMGJHKVHQNTE-UHFFFAOYSA-N O=C=[Re+] Chemical compound O=C=[Re+] MVCMGJHKVHQNTE-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- WCYJXDMUQGVQQS-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1 WCYJXDMUQGVQQS-UHFFFAOYSA-N 0.000 description 2
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UNVITNYJSYGVGQ-UHFFFAOYSA-N 2-hexyl-4,5-dimethyl-1H-imidazole Chemical class CC1=C(N=C(N1)CCCCCC)C UNVITNYJSYGVGQ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- CKQBSDUWDZEMJL-UHFFFAOYSA-N [W].[Br] Chemical compound [W].[Br] CKQBSDUWDZEMJL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- Pyridine Compounds (AREA)
Abstract
A complex of rhenium is chloridization tricarbonyl{4-[two (2-pyridine) methylene]-3, 5-dithiole-1,2- dicarboxylic acid} complex rhenium (I), which has the following structure formula: The complex of chloridization tricarbonyl{4-[two (2- pyridine) methylene]-3, 5-dithiole-1,2- dicarboxylic acid} complex rhenium (I) of the invention has simple synthesis, convenient purification, higher output and excellent stability in air. As dye photosensitizer, the photoelectrochemistry date which is measured in sensitized TiO 2 nanocrystalline solar photoelectric cell show that the complex of chloridizationtricarbonyl{4-[two (2- pyridine) methylene]-3, 5-dithiole-1,2- dicarboxylic acid} complex rhenium (I) has the property of dye photosensitizer, and has certain potential in the aspect of applying in dye sensitized solar cell. The invention discloses the preparation process.
Description
Technical field
The present invention relates to the title complex of rhenium, also relate to dye sensitization solar battery.
Background technology
Utilizing solar energy power generating is the focus of current energy utilization.Wherein, dye sensitization solar battery (Dye Sensitized Solar Cell, be called for short DSSC) have advantages such as theoretical electricity conversion is higher, with low cost, good stability, making is simple, environmentally friendly and have a extensive future, be subjected to the extensive concern of countries in the world.
Dye sensitization solar battery mainly is meant with dye sensitization porous nanometer structure TiO
2Film is light anodic one a based semiconductor photoelectrochemical cell, also useful in addition ZnO, SnO
2Deng as TiO
2The photoelectrochemical cell of film equivalent material.It combines the advantage of dyestuff photosensitizers and inorganic semiconductor, is a kind of solar cell of copying plant chlorophyll photosynthesis principle.Its research history can be traced back to the sixties in last century, Germany's Tributsch discovery is dye adsorption to produce electric current under certain condition on semi-conductor, for photoelectrochemistry has been established important foundation [referring to Dai Songyuan, Wang Kongjia, tungsten is high by the emperor himself etc., solar energy journal, 1997,18 (2), 228～232].Owing to the plate electrode that is that uses at first, specific surface area is very little, the efficiency of conversion of dye sensitization panel solar battery very low always (＜1%) but in fact.Up to 1991, the Gr of Switzerland
Tzel research group develops the TiO with carboxylic acid bipyridyl ruthenium (II) dye sensitization
2Nanocrystalline porous film has enlarged the specific surface area of semiconductor film as the solar photocell of photo cathode, has improved the adsorptive capacity of dyestuff, and its sun power total conversion efficiency surpasses 7%[at one stroke referring to O ' Regan, B.; Gr
Tzel, M.Nature 1991,353, and 737], the research of dye sensitization solar battery has just obtained breakthrough.After this, improving constantly of the design improvement of dye molecule and nanometer semiconductor technology makes dye sensitized nano crystal salar battery become and effectively utilizes a class solar cell that has potentiality in the sun power.
In the integral part of dye sensitization solar battery, be the electronics key factor that generates and inject wherein as the dye molecule of sensitizing agent.At present research more light-sensitive coloring agent comprises that mainly pyridine ruthenium organometallic complex is [referring to (a) Nazeeruddin, M.K.; Klein, C.; Liska, P.; Gr
Tzel, M.Coord.Chem.Rev.2005,249,1460; (b) Wang, P.; Klein, C.; Humphry-Baker, R.; Zakeeruddin, S.M.; Gr
Tzel, M.J.Am.Chem.Soc.2005,127,808; (c) Chen, C.-Y.; Lu, H.-C.; Wu, C.-G.; Chen, J.-G..; Ho, K.-C.Adv.Funct.Mater.2007,17,29], phthalocyanine and cyanines class series dyes be [referring to James, C.; Hideo, T.Journal ofApplied Phycology, 2000,12,207], porphyrin class dyestuff is [referring to (a) Antohe, S.; Tugulea, L.Phys.Stat.Sol (A), 1996,1153,581; (b) Takahashi K., KurayaN., et al.Solar Enegy Materials and Solar Cell, 2000,61,403] and natural dyestuff [referring to: Gr
Tzel, M.Journal of Sol-Gel Science and Technology, 2001,22,7] etc.The experiment proved that pyridine ruthenium organometallic complex sensitization TiO
2The best results of electrode.Wherein, two (isosulfocyanate radical)-two (4,4 '-dicarboxylic acid-2,2 '-dipyridyl) close ruthenium (II) (be called for short N3) [referring to Nazeeruddin, M.K.; Kay, A.; Rodicio, I.; Humphry-Baker, R.; M ü ller, E.; Liska, P.; Vlachopoulos, N.; Gr
Tzel, M.J.Am.Chem.Soc.1993,115,6382] be best up to now dye photoactivation agent, the titanium dioxide nanocrystalline electrode of its cis-isomeride sensitization (480-600nm) in the wavelength region of broad can produce the electricity conversion (IPCE) more than 80%, the sun power total conversion efficiency is 10～11%, and this efficiency of conversion can be that solar cell compares favourably with silicon, and cost only is 1/10～1/5 of a silicon photocell.Stability is also better, and its life-span has been stabilized in more than 15 years at present.
Except pyridine ruthenium organometallic complex, another kind of transition metal complex---three many pyridines of carbonyl rhenium (I) title complexs are owing to have that stability is high, oxidation-reduction quality is good and characteristic such as optical physics and spectrochemical property be good, at aspects such as catalyzer, electrogen materials [referring to: (a) Sullivan, B.P.; Meyer, T.J.J.Chem.Soc., Chem.Commun.1984,1244; (b) Tsubaki, H.; Sekine, A.; Ohashi, Y.; Koike, K.; Takeda, H.; Ishitani, O.J.Am.Chem.Soc.2005,127,15544; (c) Lundin, N.; Blackman, A.; Gordon, K.; Officer, D.Angew.Chem., Int.Ed.2006,45,2582; (d) Yam, V.W.-W.; Wang, K.Z.; Wang, C.R.; Yang, Y.; Cheung, K.K.Organometallics 1998,17, and 2440; (e) Lam, M.H.W.; Lee, D.Y.K.; Man, K.W.; Lau, C.S.W.J.Mater.Chem.2000,10,1825] obtained using widely.Yet, up to now, bibliographical information can be few as three rhenium carbonyls (I) title complex of dyestuff photosensitizers.Simultaneously, consider as dye molecule to have adsorption group that because it not only plays a part the fixed dye molecule in semiconductor surface, dyestuff excited state transfer transport is to the passage of semi-conductor conduction band especially.And studies show that carboxyl more helps electric transmission as adsorption group.
Summary of the invention
The title complex that the purpose of this invention is to provide a kind of rhenium, it can be used to prepare dye sensitization solar battery.
Technical scheme of the present invention is as follows:
A kind of title complex of rhenium, it is that chlorination three carbonyls { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I), it has following structural formula:
A kind of method for preparing the title complex of above-mentioned rhenium, it is made up of the following step:
Step 1, under nitrogen protection; with 3; 4-dimethoxycarbonyl-2; 5-dithia cyclopentenes-3-alkene thioketones mixes with two (2-pyridine) ketone that waits amount of substance; reflux after adding toluene and triethoxy phosphorus; the amount that adds is per 4 mmoles 3,4-dimethoxycarbonyl-2, and 5-dithia cyclopentenes-3-alkene thioketones adds toluene 7-10 milliliter; per 4 mmoles 3; 4-dimethoxycarbonyl-2,5-dithia cyclopentenes-3-alkene thioketones adds triethoxy phosphine 5-7 milliliter, cooling; separate out red crystalline thing 4-[two (2-pyridine) methylene radical]-3; 5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters
Step 3, with yellow solid chlorination three carbonyls in the step 2 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters } close rhenium (I) and be dissolved in tetrahydrofuran (THF), add the KOH aqueous solution to the pH of reaction mixture be 9～10, at stirring at room 1h, (absolute pressure is 10～20KPa) to concentrating under reduced pressure, it is 3 that the adding Glacial acetic acid transfers to pH, obtain yellow mercury oxide, be chlorination three carbonyls of the present invention 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I).
The method of the title complex of the above-mentioned above-mentioned rhenium of preparation, in the described step 3 consumption of tetrahydrofuran (THF) be per 1.3 mmole chlorinations, three carbonyls 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters } close rhenium (I) and be dissolved in 80-100 milliliter tetrahydrofuran (THF).
The method of the title complex of the above-mentioned above-mentioned rhenium of preparation, in the described step 3, the concentration of the KOH aqueous solution is 1-2mol/L.
Chlorination three carbonyls of the present invention 4-[two (2-pyridine) methylene radical] and-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I) as the dyestuff photosensitizers, at the TiO of its sensitization
2In the nanocrystalline solar photocell, it is as follows to record the photoelectrochemistry data: open circuit voltage (V
Oc) be 0.36 V, short-circuit current (I
Sc) be 0.51mAcm
-2, packing factor (FF) is 0.53, sun power total conversion efficiency (η) is 0.1%.These results show: chlorination three carbonyls of the present invention 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1, the 2-dioctyl phthalate } close rhenium (I) title complex and have the performance of dyestuff photosensitizers, be applied to have certain potentiality aspect the dye sensitization solar battery.
With
1H-NMR, ultimate analysis (C, H, N), mass spectrum, infrared, ultraviolet characterizes and confirmed the structure that chlorination three carbonyls { 2-[two (2-pyridine) methylene radical]-1,3-dithia ring penta-4-alkene-4,5-dioctyl phthalate } close rhenium (I).Detecting used instrument is: Bruker DRX500 type nuclear magnetic resonance analyser, Perkin-Elmer 240C type elemental analyser, Bruker Autoflex II TOF/TOF spectrometer mass spectrum workstation, Vector22Bruker spectrophotometer (400-4000cm
-1) and UV-3100 type ultraviolet-visible spectrophotometer.
Chlorination three carbonyls of the present invention { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I) dyestuff and compare with multi-joint pyridine ruthenium dye, and solar energy converting efficient is lower.But can be used for dye sensitization solar battery seldom in the title complex of synthetic three rhenium carbonyls (I) at present, this a series of title complex of most of report does not have the performance as the dyestuff photosensitizers.Chlorination three carbonyls of the present invention 4-[two (2-pyridine) methylene radical] and-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close the part replacement inflexible bipyridine ligand that adopts non-dipyridyl in rhenium (I) title complex, make whole molecular structure have more flexibility, be beneficial to distortion.Simultaneously, compare with the pyridine ruthenium complexe, three carbonyls are arranged (fac-[Re (CO) for the face formula in three rhenium carbonyls (I) title complex
3]), this configuration makes molecule be easier to the directed TiO that invests
2Nanocrystal surface.Moreover, it is synthetic simple that chlorination three carbonyls of the present invention { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I) title complex, is beneficial to purification, and productive rate is higher, and property stable in the air is good; We can update the physicochemical property of this class three rhenium carbonyls (I) title complex by the modification of part, provide possibility for optimizing its photoelectric converting function.They are with a wide range of applications at aspects such as dye sensitization solar battery, photoelectric conversion material, organic electroluminescent, optical storage and bioprobes.
Description of drawings
Fig. 1 is the uv-visible absorption spectra of title complex C of the present invention;
Fig. 2 is the fluorogram of title complex C of the present invention;
Fig. 3 is the redox potential figure of title complex C of the present invention;
Fig. 4 is the density of photocurrent-voltage spectrogram of title complex C of the present invention as the nano-crystalline solar battery of dye sensitizing agent sensitization;
Embodiment
Embodiment one: the preparation that chlorination three carbonyls { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I)
Two 1.4-[(2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1, the preparation of 2-dioctyl phthalate methyl esters (A):
A. feeding under the condition of nitrogen gas, 3,4-dimethoxycarbonyl-2,5-dithia cyclopentenes-3-alkene thioketones (1.00g, 4mmol) and two (2-pyridine) ketone (0.74g adds 7ml toluene and 5ml triethoxy phosphine in mixture 4mmol), refluxed 6 hours.Behind the stopped reaction, be cooled to-20 ℃, filter, the ether washing obtains red crystals 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters 0.83g, productive rate 53.7%.The compound warp
1H-NMR, ultimate analysis, mass spectrum, the infrared checking, the result shows that structure is correct, data are as follows:
1H-NMR(500MHz，CDCl
3，δ)：
8.79(d，J＝3.6Hz，2H)?7.72(t，2H)7.22(t，2H)7.17(d，J＝7.9Hz，2H)3.87(s，6H)
Results of elemental analyses: calculated value: C (%): 55.95 H (%): 3.65 N (%): 7.25
Measured value: C (%): 55.78 H (%): 3.41 N (%): 6.95
MS(MALDI-TOF)：m/z：387.1(M
+)
IR(KBr)(v
max，cm
-1)：1722.10，1700.14(C＝O)
B. use 10ml toluene and 7ml triethoxy phosphine instead, the constant identical result that obtains of other condition.
2. chlorination three carbonyls { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters } close rhenium (I) preparation (B):
A. feeding under the condition of nitrogen gas, 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters (A) (116mg, (108mg 0.3mmol) mixes 0.3mmol) to close rhenium (I) with the chlorination pentacarbonyl, add 15ml toluene, refluxed 1.5 hours.Cold filtration, normal hexane washing obtains yellow solid chlorination three carbonyls { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters } and closes rhenium (I) 175mg, productive rate 84%.The compound warp
1H-NMR, ultimate analysis, mass spectrum, the infrared checking, the result shows that structure is correct, data are as follows:
1H-NMR(500MHz，CDCl
3，δ)：
9.15(d，J＝5.2Hz，2H) 7.93(d，J＝7.1Hz，2H) 7.79(d，J＝7.6Hz，2H) 7.40(t，2H) 3.88(s，6H)
Results of elemental analyses: calculated value: C (%): 36.44 H (%): 2.04 N (%): 4.05
Measured value: C (%): 36.15 H (%): 1.57 N (%): 4.03
MS(MALDI-TOF)：m/z：657.1([M-Cl]
+)
IR(KBr)(v
max，cm
-1)：2019.99，1928.77，1896.39(C≡O)；1730.72(C＝O)
B. use 10ml toluene instead, other condition is constant, obtains identical result.
3. chlorination three carbonyls { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I) preparation (C):
A. with yellow solid chlorination three carbonyls 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters } close (B) (90mg of rhenium (I), 0.13mmol) be dissolved in the tetrahydrofuran (THF) (10ml), add the KOH aqueous solution (2M) adjust pH to 9～10, stirred 1 hour under the room temperature, solution decompression is concentrated, and (absolute pressure is the pH value to 3 that 10～20KPa) to 3～5ml adding Glacial acetic acid are regulated this mixture, separate out product chlorination three carbonyls 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1, the 2-dioctyl phthalate } close rhenium (I) 68mg, productive rate 79%.The compound warp
1H-NMR, ultimate analysis, mass spectrum, infrared, ultraviolet verify that the result shows that structure is correct, and data are as follows:
1H-NMR(500MHz，DMSO-d
6，δ)：
8.89(d，J＝4.5Hz，2H) 8.16(t，2H) 8.03(d，J＝7.5Hz，2H)7.59(d，J＝5.5Hz，2H)
Results of elemental analyses: calculated value: C (%): 34.36 H (%): 1.52 N (%): 4.22
Measured value: C (%): 34.12 H (%): 1.35 N (%): 4.06
MS(MALDI-TOF)：m/z：629.1([M-Cl]
+)
IR(KBr)(v
max，cm
-1)：2019.14，1910.72，1894.26(C≡O)
UV-Vis (CH
3OH): λ
Max/ nm (ε/M
-1Cm
-1)=327 (2842); λ
Max/ nm (ε/M
-1Cm
-1)=404 (4060) (seeing accompanying drawing 1).
B. use the 8ml tetrahydrofuran (THF) instead, the KOH solution of 1mol/L concentration obtains identical result.
Embodiment two: the fluorescence that chlorination three carbonyls of the present invention { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I) characterizes
Testing tool is AMINCO Bowman Series 2 luminoscopes.Title complex C of the present invention is dissolved in mensuration (5 * 10 in the methyl alcohol
-4M).At ambient temperature, excite peak value λ
ExBe 356nm and 440nm, emission peak λ
EmBe 483nm (seeing accompanying drawing 2).
Embodiment three: the electrochemical Characterization that chlorination three carbonyls of the present invention { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I)
Testing tool is the CHI660b electrochemical workstation.With glass-carbon electrode, platinum wire electrode, Ag/Ag
+Respectively as working electrode, counter electrode and reference electrode.Title complex C of the present invention is dissolved among the DMF (5 * 10
-4M), with 0.1Mn-Bu
4NClO
4Be supporting electrolyte, sweep velocity is 100mV s
-1Test result shows a pair of redox peak, and the half-wave potential value is 0.82V, and this current potential is the redox potential (see accompanying drawing 3) of rhenium metal from positive monovalence to positive divalence.
Embodiment four: chlorination three carbonyls of the present invention { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close the effect that rhenium (I) is applied to dye sensitization solar battery
Title complex C of the present invention is dissolved in the ethanol (HPLC) (5 * 10
-4M), make the TiO of its sensitization
2Nano-crystalline solar battery.Provide 620W/m by the 150W bromine tungsten filament lamp
2Photovoltaic is in this test battery surface, and ionogen is a dimethyl hexyl imidazoles (0.5mmol/L), I2 (20mmol/L), and LiI (40mmol/L) and tert .-butylpyridine (500mmol/L) are dissolved in the mixing solutions of acetonitrile.
This test voltage and current data are after Keithley model 236 digital source meter standardizations, and its photoelectrochemistry data (seeing accompanying drawing 4) are as follows: open circuit voltage (V
Oc) be 0.36V, short-circuit current (I
Sc) be 0.51mAcm
-2, packing factor (FF) is 0.53, sun power total conversion efficiency (η) is 0.1%.These results show that three many pyridines of carbonyl rhenium (I) title complexs of the present invention have the performance of dyestuff photosensitizers, are being applied to have certain potentiality aspect the dye sensitization solar battery.
Claims (6)
1. the title complex of a rhenium is characterized in that: it is that chlorination three carbonyls { 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I), and it has following structural formula:
2. method for preparing the title complex of the described rhenium of claim 1 is characterized in that it is made up of the following step:
Step 1, under nitrogen protection; with 3; 4-dimethoxycarbonyl-2; 5-dithia cyclopentenes-3-alkene thioketones mixes with two (2-pyridine) ketone that waits amount of substance; reflux after adding toluene and triethoxy phosphine; the amount that adds is per 4 mmoles 3,4-dimethoxycarbonyl-2, and 5-dithia cyclopentenes-3-alkene thioketones adds toluene 7-10 milliliter; per 4 mmoles 3; 4-dimethoxycarbonyl-2,5-dithia cyclopentenes-3-alkene thioketones adds triethoxy phosphine 5-7 milliliter, cooling; separate out red crystalline thing 4-[two (2-pyridine) methylene radical]-3; 5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters
Step 2, under nitrogen protection; 4-[two (2-pyridine) methylene radical with gained in the step 1]-3; 5-dithia cyclopentenes-1; 2-dioctyl phthalate methyl esters closes rhenium (I) with the chlorination pentacarbonyl that waits amount of substance to be mixed; reflux after adding toluene; the amount that adds is per 3 mmole 4-[two (2-pyridine) methylene radical]-3; 5-dithia cyclopentenes-1; 2-dioctyl phthalate methyl esters adds toluene 100-150 milliliter; cold filtration, obtain yellow solid chlorination three carbonyls 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1; 2-dioctyl phthalate methyl esters } close rhenium (I)
Step 3, with yellow solid chlorination three carbonyls in the step 2 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters } close rhenium (I) and be dissolved in tetrahydrofuran (THF), adding the KOH aqueous solution to pH value of solution is 9～10, at stirring at room 1h, concentrating under reduced pressure, adding Glacial acetic acid, to transfer to pH be 3, obtains yellow mercury oxide, be chlorination three carbonyls 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate } close rhenium (I).
3. the method for the title complex of preparation rhenium according to claim 2, it is characterized in that: in the described step 3 consumption of tetrahydrofuran (THF) be per 1.3 mmole chlorinations, three carbonyls 4-[two (2-pyridine) methylene radical]-3,5-dithia cyclopentenes-1,2-dioctyl phthalate methyl esters } close rhenium (I) and be dissolved in 80-100 milliliter tetrahydrofuran (THF).
4. the method for the title complex of preparation rhenium according to claim 2 is characterized in that: in the described step 3, the concentration of the KOH aqueous solution is 1-2mol/L.
5. the method for the title complex of preparation rhenium according to claim 2 is characterized in that: in the described step 3, concentrating under reduced pressure is to carry out under 10-20Kpa pressure.
6. the application of the title complex of rhenium according to claim 1 in the preparation dye sensitization solar battery.
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| Kazuyuki Takahashi, et al..An abrupt spin transition based on short S...S contacts in anovel Fe(II) complex whose ligand contains a 1,3-dithiole ring.CHEM. COMMUN..2003,2374-2375, 全文. * |
| 孙世国 等.太阳能电池用联吡啶铼光敏染料研究.大连理工大学学报44 4.2004,44(4),498-501, 全文. |
| 孙世国等.太阳能电池用联吡啶铼光敏染料研究.大连理工大学学报44 4.2004,44(4),498-501, 全文. * |
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