CN102653541A - Porphyrin compound as well as preparation method and application of porphyrin compound - Google Patents
Porphyrin compound as well as preparation method and application of porphyrin compound Download PDFInfo
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Abstract
The invention provides a novel porphyrin compound which has a chemical name of meso-tetrakis [p(3,4-dicyano)phenoxy]phenyl porphyrin and has a structure shown in the specification. The invention also provides a preparation method of the compound. The compound provided by the invention can be used for manufacturing organic solar batteries.
Description
Technical field
The present invention relates to a kind of novel porphyrin compound.
Background technology
Porphyrins has the photoelectric properties of many uniquenesses, good light and thermally stable property, and bigger molar absorptivity is arranged in visible-range, has therefore caused widely at numerous areas and has paid close attention to.For example porphyrin compound can be used as light absorption units, in biological photosynthetic quantity of photogenerated charge of simulation and energy transfer process, realization photoinduction chargeseparated [referring to: (a) Yfroah G.S.; Lidell P.A.Nature.1997; 385,239. (b) Yfroah G.S., Lidell P.A.et al.Nature.1998; 392,497.].But porphyrin compound analog cytochrome P-450 provides the cutting [referring to Meunier B.Chem.Rev.1992,92,1411.] of active oxygen catalyzed oxidation alkane, alkene, pure ether compound and dna fragmentation as catalyzer.In addition, porphyrin compound also is widely used in photodynamic therapy [referring to Dudkowiak A., Teslak E., Habdas J.J.Mol.Struct.2006,93; 792.], organic field effect tube [referring to Aramaki S., Sakai Y., Ono N.Appl.Phy.Lett.2004,84,2085.], optical drive molecular switch be [referring to Gosztola D.; Niemczyk M.P., Wasielewski M.R.J.Am.Chem.Soc.1998,120,5118.], molecular wire is [referring to Ishida T., Morisaki Y.; Chujo Y.Tetrahedron Lett.2006,47,5265.], organic solar batteries is [referring to Takechi K., Shiga T., et al.Sol.Energy Mater.Sol.Cells 2006; 90,1322.], organic electroluminescent is [referring to Baldo M.A., O ' Bren D.F., et al.Nature, 1998; 395,151.], nonlinear optics is [referring to Lidzey D.G., Bradley D.C., et al.Nature.1998,395; 53.], optical storage [referring to Liu Z.M., Amir A., et al.Science.2003,302 (28), 1543.], based on the chemical sensor of fluorescence [referring to de Silva A.P.; Gunaratne H.Q.N., et al.Chem.Rev.1997,97,1515.], the photosensitizers of tumour is [referring to Wang H.M., Jiang J.Q.; Et al.Chem-Biol Interact.2008,172,154.], malaria treatment is [referring to Robert A., Benoit-Vical F., et al.Pure Appl.Chem.2001; 73,1173.] and analytical chemistry [referring to Biesaga M., Pyrzynska K., Trojanowicz; M.Talanta, 2000,51,209.].
Research about porphyrin compound has developed into a new subject--the porphyrin chemistry.Design and synthesize new porphyrin molecule and study its application corresponding very important practical sense is arranged.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of novel porphyrin compound and compound method and application.
The invention provides a kind of porphyrin compound, its chemical name is meta-four [to (3, a 4-dicyano) phenoxy] phenyl porphyrin (TDPP), and its structural formula is following:
The present invention also provides the preparation method of above-mentioned meta-four [to (3, the 4-dicyano) phenoxy] phenyl porphyrin (TDPP), and this method may further comprise the steps:
(1) phthalic nitrile that electron-withdrawing group is arranged on meta-four (to hydroxyl) phenyl porphyrin (THPP), the 4-position and salt of wormwood are dissolved in the DMSO 99.8MIN. (DMSO), be heated to 60～100 ℃ under stirring, and isothermal reaction;
(2) add deionized water after the reaction product of step (1) is cooled to room temperature, filter and obtain filter cake;
(3) be that developping agent carries out column chromatography to above-mentioned filter cake with ethanol and/or methyl alcohol, remove unreacted raw material;
(4) with the volume ratio N: toluene=1～10: 1 mixed solvent is that developping agent carries out wash-out to chromatography column, collects the solution of purple colour band;
(5) solution of step (4) being collected revolves to steam to remove and desolvates, and is drying to obtain product.
According to preparation method provided by the invention, wherein, there are the phthalic nitrile of electron-withdrawing group and the weight ratio of salt of wormwood to be 1: 1～4: 1～5 on meta-four (to hydroxyl) the phenyl porphyrin in the said step (1), the 4-position, be preferably 1: 1～2: 2～4.
According to preparation method provided by the invention; Wherein, There is the phthalic nitrile of electron-withdrawing group can be selected from 4-nitro phthalic nitrile, 4-chloro phthalic nitrile, 4-bromo phthalic nitrile and 4-iodo phthalic nitrile etc. on the said 4-position; Be preferably 4-nitro phthalic nitrile or 4-chloro phthalic nitrile, more preferably 4-nitro phthalic nitrile.
In preparation method of the present invention, the meta with respect to 100 milligrams-four (to hydroxyl) phenyl porphyrin, the consumption of DMSO 99.8MIN. can be 20～100 milliliters, is preferably 40～60 milliliters.
According to preparation method provided by the invention, wherein, the isothermal reaction time in the said step (1) can be 6～13 hours, is preferably 9～11 hours.Because carry out under this reaction needed oxygen free condition, the raw material adition process and the reaction process of step (1) are preferably all carried out under nitrogen protection.
In preparation method of the present invention, the meta with respect to 100 milligrams-four (to hydroxyl) phenyl porphyrin, the deionized water volume that adds in the said step (2) can be 50～150ml, is preferably 100～150ml.
Wherein, in order to improve the purity of final product, said step (2) can also comprise uses the deionized water wash filter cake, to remove unreacted salt of wormwood.Wash with the consumption of deionized water and can confirm according to the batch of reaction and the excessive degree of reaction raw materials, usually, the meta with respect to 100 milligrams-four (to hydroxyl) phenyl porphyrin, the consumption of deionized water can be 50～150ml.
Because reaction product is insoluble to ethanol and/or methyl alcohol, and reaction raw materials THPP can be dissolved in ethanol and/or methyl alcohol, so step (3) through with ethanol and/or methyl alcohol drip washing chromatography column unreacted raw material being separated with reaction product, is preferably used ethanol.According to preparation method provided by the invention, wherein, the consumption of ethanol and/or methyl alcohol occurs being as the criterion with the elution chromatography post no longer includes raw material in post colour band in the said step (3).Preferably, the meta with respect to 100 milligrams-four (to hydroxyl) phenyl porphyrin, the consumption of ethanol and/or methyl alcohol in the said step (3) (being the total amount of developping agent in the step (3)) can be 100～500ml, is preferably 200～300ml.With regard to the present invention, employed chromatography column there is not special qualification, as long as can reaction product be separated through the drip washing of different developping agents.Generally speaking, the chromatography column that is used for preparation method of the present invention can be the silicagel column of routine, and the particle size of silica gel is preferably 100～200 orders.
According to preparation method provided by the invention, wherein, the volume ratio of mixed solvent is preferably N in the said step (4): toluene=3～7: 1, most preferably be 5: 1.
Particularly, the main synthetic route of meta of the present invention-four [to (3, the 4-dicyano) phenoxy] phenyl porphyrin (TDPP) is shown below:
Use IR, UV-Vis,
1HNMR and mass-spectrometric technique characterize porphyrin compound of the present invention, and the result is following:
1, infrared spectrum characterization
Use the Perkin Elmer Spectrum One of company infrared spectrometric analyzer, adopt the KBr tabletting method to measure the ir spectra of product.Accompanying drawing 1 is the ir spectra of porphyrin compound of the present invention.Among Fig. 1,3320cm
-1, 967cm
-1The absorption peak at place belongs to N-H stretching vibration and flexural vibration absorption peak for the porphyrin part respectively, is the eigen vibration of porphyrin ring.2231cm
-1Be the charateristic avsorption band of cyanic acid, 1591cm
-1, 1485cm
-1It is the absorption peak of phenyl ring; 1281cm
-1, 1250cm
-1, 1208cm
-1, 1089cm
-1It is the eigen vibration absorption peak of C-O-C.Explain that meta-four (to hydroxyl) phenyl porphyrin has been converted into meta-four [to (3, the 4-dicyano) phenoxy] phenyl porphyrin.
2, ultraviolet-visible spectrum characterizes
Use the Perkin Elmer Lambda of company 950 ultraviolets/visible spectrophotometer porphyrin compound of the present invention to be carried out the analysis of ultraviolet-visible spectrum.With DMF is solvent, and ultraviolet spectrogram is seen accompanying drawing 2.From figure, can see that this product has 5 charateristic avsorption bands, be respectively the Soret band of 420nm, the Q band of 515nm, 550nm, 591nm and 646nm.This result and raw material contrast, blue shift has all taken place in all absorption peaks, explains to have generated new porphyrin compound.
3, nucleus magnetic resonance characterizes
Use the 300MHz NMR testing product of Bruker company, its detected result is seen accompanying drawing 3.
1HNMR (CDCl
3) δ: 8.69-8.66 (8H, pyrroles), 8.62 (8H, 2,5-phthalic nitriles), 7.95-7.98 (4H, 6-phthalic nitrile), 7.64-7.74 (16H, the benzene in the porphyrin ring) ,-2.83 (2H N-H).Through the sign of nucleus magnetic hydrogen spectrum, further proved the generation of title product.
4, mass spectral characteristi
Use the Autoflex III MALDI-TOF-MS mass spectrograph of Bruker company to carry out mass spectrometric detection.The mass spectrum of product is seen accompanying drawing 4.Detected result is M/Z 1183.6 (M+2).Its estimating of molecular weight value of porphyrin compound of the present invention is 1181.6.Therefore can know that by the mass spectrometric detection result compound that synthesizes is a target compound.
Through above ir spectra, ultraviolet-visible spectrum, nuclear-magnetism and mass spectral sign, explain that the present invention has made aforesaid meta-four [to (3, the 4-dicyano) phenoxy] phenyl porphyrin.
According to another aspect of the present invention, the application of porphyrin compound in organic solar batteries that porphyrin compound of the present invention also is provided or has made according to method of the present invention.
The electrochemistry energy level of porphyrin compound provided by the invention is E
HOMO=-5.52eV, E
LUMO=-3.66eV, electrochemistry band gap E
gBe 1.86eV.Its method of calculation are at first to obtain the initial oxidation reduction potential of compound through the test of cyclic voltammetric character, according to formula E
HOMO=-(E
Ox, onset+ 4.4), E
LUMO=-(E
Red, onset+ 4.4) respectively the energy level of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) is calculated with initial oxidation current potential and initial reduction potential.But by uv-absorbing spectrogram knowledge capital invention porphyrin compound absorption is preferably arranged at 400～650nm place, and lower band gap (1.86eV) is arranged, thereby can be used for photovoltaic device.
Description of drawings
Below, specify embodiment of the present invention in conjunction with accompanying drawing, wherein:
Fig. 1 is the infrared spectrogram of porphyrin compound of the present invention;
Fig. 2 is the ultraviolet spectrogram of porphyrin compound of the present invention;
Fig. 3 is the nmr spectrum of porphyrin compound of the present invention;
Fig. 4 is the mass spectrum of porphyrin compound of the present invention;
The TDPP/PCBM photovoltaic device structural representation that Fig. 5 makes for embodiment 4;
Current density-the voltage curve of the photovoltaic device that Fig. 6 makes for embodiment 4.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, the embodiment that provides has been merely and has illustrated the present invention, rather than in order to limit scope of the present invention.
Embodiment 1
Present embodiment is used to explain porphyrin compound provided by the invention and preparation method thereof.
(1) under the nitrogen protection, in three mouthfuls of round-bottomed flasks of 150ml, with 100mg meta-four (to hydroxyl) phenyl porphyrin, 150mg 4-nitro phthalic nitrile and 280mg K
2CO
3Dissolve in successively through among the 50ml DMSO of drying treatment, be heated to 80 ℃, constant temperature successive reaction 10 hours under stirring.
(2) be cooled to room temperature after, the reaction product of step (1) is poured in the 100ml deionized water, after the filtration again with 100ml deionized water wash filter cake to remove excessive K
2CO
3
(3) be that developping agent carries out column chromatography to filter cake with 250ml ethanol, remove unreacted raw material.
(4) with volume ratio DMF: the mixed solvent of toluene=5: 1 carries out wash-out as developping agent, collects the solution of purple colour band.
(5) revolve steaming except that desolvating, get meta-four [to (3, the 4-dicyano) phenoxy] phenyl porphyrin product 162mg, yield 92.8% after the drying.
Embodiment 2
Present embodiment is used to explain porphyrin compound provided by the invention and preparation method thereof.
(1) under the nitrogen protection, in three mouthfuls of round-bottomed flasks of 150ml, with 100mg meta-four (to hydroxyl) phenyl porphyrin, 130mg 4-chloro phthalic nitrile and 280mg K
2CO
3Dissolve in successively through among the 50ml DMSO of drying treatment, be heated to 90 ℃, constant temperature successive reaction 8 hours under stirring.
(2) be cooled to room temperature after, the reaction product of step (1) is poured in the 100ml deionized water, after the filtration again with 100ml deionized water wash filter cake to remove excessive K
2CO
3
(3) be that developping agent carries out column chromatography to filter cake with 250ml methyl alcohol, remove unreacted raw material.
(4) with volume ratio DMF: the mixed solvent of toluene=4: 1 carries out wash-out as developping agent, collects the solution of purple colour band.
(5) revolve steaming except that desolvating, get meta-four [to (3, the 4-dicyano) phenoxy] phenyl porphyrin product 155mg, yield 88.7% after the drying.
Embodiment 3
Present embodiment is used to explain porphyrin compound provided by the invention and preparation method thereof.
(1) under the nitrogen protection, in three mouthfuls of round-bottomed flasks of 150ml, with 100mg meta-four (to hydroxyl) phenyl porphyrin, 165mg 4-bromo phthalic nitrile and 280mg K
2CO
3Dissolve in successively through among the 50ml DMSO of drying treatment, be heated to 85 ℃, constant temperature successive reaction 9 hours under stirring.
(2) be cooled to room temperature after, the reaction product of step (1) is poured in the 100ml deionized water, after the filtration again with 100ml deionized water wash filter cake to remove excessive K
2CO
3
(3) mixed solvent with 100ml ethanol and 100ml methyl alcohol is that developping agent carries out column chromatography to filter cake, removes unreacted raw material.
(4) with volume ratio DMF: the mixed solvent of toluene=6: 1 carries out wash-out as developping agent, collects the solution of purple colour band.
(5) revolve steaming except that desolvating, get meta-four [to (3, the 4-dicyano) phenoxy] phenyl porphyrin product 147mg, yield 84.1% after the drying.
Embodiment 4
Present embodiment is used to explain the application of porphyrin compound of the present invention (TDPP) as organic solar battery material.
(1) through cleaning and tin indium oxide (ITO) glass substrate of surperficial ozonize on the DMF solution of spin coating TDPP and the chloroformic solution of [6,6]-phenyl-C61-methyl-butyrate (PCBM) successively.Wherein, the thickness of ITO is 25nm, and square resistance is 60 Ω/; The strength of solution of TDPP and PCBM is 10mgmL
-1, gave body/acceptor weight ratio 1: 1.
(2) under 150 ℃, this device of thermal treatment 10 minutes.
(3) using vacuum plating unit is 1 * 10 in vacuum tightness
-3Under the Pa at device surface evaporating Al layer.Use the useful area of mask plate control device to be 0.1cm
2
The TDPP/PCBM photovoltaic device structural representation that Fig. 5 makes for present embodiment.
The current voltage characteristic of device is to utilize computer-controlled Keithley 2410 digital source tables to measure, and light source is the 150W xenon source, and the unit surface light intensity is 80mW/cm
2The current value that voltage records when being zero is short-circuit current (J
Sc), the magnitude of voltage that electric current records when being zero is open circuit voltage (V
Oc).The product of two parameters is an organic solar batteries peak power output in theory.Packing factor (FF) is the actual peak power output of device and the ratio of solar cell ideal peak power output, and its calculation formula does
The photoelectric transformation efficiency of solar cell (η) is the peak power output (P of solar cell unit's light-receiving area
m) and incident solar energy metric density (P
In) ratio.
What present embodiment was made is the mensuration that the photovoltaic device of active coating carries out current density-voltage curve (J-V curve) with TDPP/PCBM, and the result is shown in accompanying drawing 6.Can see from the J-V curve, dark current (unglazed according to the time, by the unidirectional current that flows through in the photovoltaic cell under the external voltage effect, see the curve D among Fig. 6) very little, and TDPP and PCBM can form P-N and tie.When illumination, this device has obtained than higher current density (photoelectric current is seen the curve L among Fig. 6) under positive bias, and this this photovoltaic cell of explanation has tangible diode effect.And, as AM 1.5 (light is 1.5 times of SEQUENCING VERTICAL thickness through atmospheric actual range) simulated solar irradiation 80mW/cm
2The irradiation light intensity under, the photoelectric transformation efficiency of this device (η) is 0.19%, open circuit voltage (V
Oc) be 0.53V, short-circuit current (I
Sc) be 0.98mA/cm
2, packing factor (FF) is 29.3%.
Can prove that by above-mentioned experimental result porphyrin compound of the present invention can be used as donor material, be applied in and make in the p-n heterojunction organic solar batteries.
Claims (10)
1. porphyrin compound, its chemical name is meta-four [to (3, a 4-dicyano) phenoxy] phenyl porphyrin, its structural formula is following:
2. the preparation method of the said compound of claim 1, this method may further comprise the steps:
(1) meta-four (to hydroxyl) phenyl porphyrin, 4-nitro phthalic nitrile and salt of wormwood are dissolved in the DMSO 99.8MIN., be heated to 60～100 ℃ under stirring, and isothermal reaction;
(2) add deionized water after the reaction product of step (1) is cooled to room temperature, filter and obtain filter cake;
(3) be that developping agent carries out column chromatography to above-mentioned filter cake with ethanol and/or methyl alcohol, remove unreacted raw material;
(4) with the volume ratio N: toluene=1～10: 1 mixed solvent is that developping agent carries out wash-out to chromatography column, collects the solution of purple colour band;
(5) solution of step (4) being collected revolves to steam to remove and desolvates, and is drying to obtain product.
3. preparation method according to claim 2, wherein, on meta-four (to hydroxyl) the phenyl porphyrin in the said step (1), the 4-position phthalic nitrile of electron-withdrawing group and the weight ratio of salt of wormwood being arranged is 1: 1～4: 1～5, be preferably 1: 1～2: 2～4.
4. according to claim 2 or 3 described preparing methods; Wherein, There is the phthalic nitrile of electron-withdrawing group to be selected from 4-nitro phthalic nitrile, 4-chloro phthalic nitrile, 4-bromo phthalic nitrile and 4-iodo phthalic nitrile on the said 4-position; Be preferably 4-nitro phthalic nitrile or 4-chloro phthalic nitrile, more preferably 4-nitro phthalic nitrile.
5. according to each described preparation method in the claim 2 to 4, wherein, the meta with respect to 100 milligrams-four (to hydroxyl) phenyl porphyrin, the consumption of DMSO 99.8MIN. is 20～100 milliliters, is preferably 40～60 milliliters.
6. according to each described preparation method in the claim 2 to 5, wherein, the isothermal reaction time in the said step (1) is 6～13 hours, is preferably 9～11 hours.
7. according to each described preparation method in the claim 2 to 6, wherein, the meta with respect to 100 milligrams-four (to hydroxyl) phenyl porphyrin, the deionized water volume that adds in the said step (2) is 50～150ml, is preferably 100～150ml.
8. according to each described preparation method in the claim 2 to 7, wherein, the meta with respect to 100 milligrams-four (to hydroxyl) phenyl porphyrin, the consumption of ethanol and/or methyl alcohol is 100～500ml in the said step (3), is preferably 200～300ml.
9. according to each described preparation method in the claim 2 to 8, wherein, the volume ratio N of mixed solvent in the said step (4): toluene=3～7: 1, be preferably 5: 1.
10. described porphyrin compound of claim 1 or the application of porphyrin compound in organic solar batteries that make according to each said method in the claim 2 to 9.
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| WO2003017846A1 (en) * | 2001-08-22 | 2003-03-06 | Montana State University-Bozeman | Porphyrins with enhanced multi-photon absorption cross-sections for photodynamic therapy |
| WO2003020309A2 (en) * | 2001-08-30 | 2003-03-13 | Pci Biotech As | Compound |
| CN1631890A (en) * | 2004-12-10 | 2005-06-29 | 吉林大学 | Tetraphenyl porphyrin derivative and its application in organic electroluminescent device |
| CN1911929A (en) * | 2005-08-10 | 2007-02-14 | 南京大学 | Meso position-tetra phenyl tetra phenanthro porphyrin derivetive and its preparation method |
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