CN105859729B - A kind of porphyrin organic molecule cathode interface material and preparation method thereof - Google Patents

Abstract

The invention discloses a porphyrin organic small molecule cathode interface material, which takes the porphyrin ring as the core, and connects one group to the four middle positions of the porphyrin ring respectively, two of which are common polar groups. The yoke unit, two of which are aromatic substituents. The invention also discloses a preparation method of the above-mentioned porphyrin organic small molecule cathode interface material, using pyrrole as the initial reaction raw material, through a series of reactions, and finally coupling with different conjugated units with polar groups through palladium catalysis The porphyrin organic small molecule cathode interface material was obtained. Compared with the prior art, the porphyrin organic small molecule cathode interface material of the present invention improves the π-π stacking between molecules in the film-forming state of the material, thereby improving the electron transport performance; improving the solubility of the material in methanol , Utilizing the material of the present invention can further improve the photoelectric conversion efficiency of the solar cell.

Description

A kind of porphyrin organic small molecule cathode interface material and preparation method thereof

technical field

The invention relates to the field of organic photoelectric materials, in particular to a porphyrin organic small molecule cathode interface material and a preparation method thereof.

Background technique

With the development of society and economy, energy consumption is increasing, and traditional fossil energy is increasingly exhausted. The development of renewable energy has become an important research topic for current researchers. Solar energy is a renewable and clean energy with the advantages of large reserves and wide distribution. It is a huge energy treasure house. The development and utilization of solar energy has become a hot spot of widespread concern in various countries. Using photovoltaic cells to convert solar energy into electricity has become one of the most efficient technologies for utilizing solar energy.

The relatively mature photovoltaic cells developed at the beginning are mainly based on inorganic materials. Although they have been commercialized, their applications have been greatly limited due to their high processing costs. In contrast, solution-processable organic polymer and organic small molecule material solar cells have the characteristics of low cost, easy processing (such as spin coating, inkjet printing, etc.), and they are light in weight and capable of being made into large-area flexible cells. Potential advantages such as devices can well overcome the defects of inorganic photovoltaic cells, and thus have received extensive attention.

The structure of organic photovoltaic cells is relatively simple, that is, the photoactive material is sandwiched between two electrodes, and one of the electrodes is transparent, which is beneficial for light to pass through the electrode and be absorbed by the active layer, and then perform photoelectric conversion. In order to obtain a higher photoelectric conversion efficiency, a layer of interface material is generally inserted between the electrode and the active layer, which is divided into an anode interface material and a cathode interface material. For the cathode interface, the most widely used for a long time is water/alcohol soluble Polymer materials, this type of polymer is easy to form a film, but it is not easy to purify, and the molecular weight distribution is wide. Due to the difference in the molecular weight and distribution of the products synthesized in each batch, there are often differences in the efficiency of solar cells, while small organic molecules are not. These problems exist, so organic small molecules have their unique advantages in organic solar cells.

Porphyrin is obtained from natural products containing porphyrin compounds through extraction, separation, purification, etc. Its structure is similar to chlorophyll, with a large π-conjugated system, which is conducive to electron transport, and is easy to pass through peripheral groups and The physical and chemical properties of cavity metals are modified. Porphyrin and its derivatives are generally used as active layers in photovoltaic devices due to their high molar extinction coefficients. In recent years, porphyrin has also been gradually used in the cathode interface, but due to its structural rigidity and other characteristics, it is difficult to dissolve in polar solvents, and there are some problems when it is used as an interface material. Porphyrin has been modified to improve its solubility in polar solvents. The fly in the ointment is that so far, porphyrin-based materials have not played a very good role in interface modification.

Contents of the invention

In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the object of the present invention is to provide a porphyrin organic small molecule cathode interface material, which has very good solubility in polar solvents by modifying porphyrin, effectively significantly increase the electron transport performance of organic optoelectronic devices.

Another object of the present invention is to provide a method for preparing a porphyrin organic small molecule cathode interface material.

The purpose of the present invention is achieved through the following technical solutions: a porphyrin organic small molecule cathode interface material has the following chemical structure:

Among them, A is a conjugated unit with a polar group; M is a metal ion or hydrogen element; Ar is an aromatic substituent group;

A is one of the following structural units:

Wherein, R is an alkyl or alkoxy chain with a carbon number of 0 to 20 and a polar group.

The polar group has one of the following structures: amine group, diethanolamine group, phosphate group, carboxyl group, quaternary ammonium salt, carboxylate group, sulfonate group, zwitterionic group.

The M is zinc ion, copper ion, magnesium ion, nickel ion or hydrogen ion.

The Ar has one of the following structural units:

Wherein, R ₁ is an alkyl or alkoxy group containing 0 to 20 carbons.

The preparation method of the porphyrin organic small molecule cathode interface material comprises the following steps:

Preparation by Suzuki coupling reaction: Dissolve 5,10-bisborate porphyrin and bromide in a reaction flask filled with 1,2-dimethoxyethane under argon atmosphere, add tetrakis(triphenyl base phosphorus) palladium, add alkali solution, heat and stir to react, after cooling, extract the target product with chloroform, purify by silica gel column chromatography and GPC, finally spin the solvent, and the product is dried under vacuum to obtain porphyrin organic small molecule cathode interface material;

The molar weight of the bromide is 3 to 6 times the molar weight of 5,10-bisboronic acid ester porphyrin, and the molar weight of the 1,2-dimethoxyethane is 5,10-bisboronic acid The total molar weight of the ester porphyrin and the bromide is 45-55 times, and the molar weight of the tetrakis(triphenylphosphine)palladium is 8-12% of the molar weight of the 5,10-bisborate porphyrin.

The preparation method of the porphyrin organic small molecule cathode interface material comprises the following steps:

Prepared by Sonogashira coupling reaction: under argon atmosphere, 5,10-diethynyl porphyrin and bromide were dissolved in a reaction flask filled with toluene and triethylamine, and tetrakis(triphenylphosphine)palladium and Cuprous iodide is heated and stirred for reaction, after cooling, the target product is extracted with chloroform, purified by silica gel column chromatography, and finally the solvent is spin-dried, and the product is dried under vacuum to obtain a porphyrin organic small molecule cathode interface material;

The molar weight of the bromide is 3 to 6 times the molar weight of the 5,10-diethynyl porphyrin, and the molar weight of the toluene is 45 times that of the total molar weight of the 5,10-diethynyl porphyrin and the bromide. ~55 times, the triethylamine is 1/3 of the amount of toluene, and the molar weight of tetrakis(triphenylphosphine)palladium is 8～12% of the molar weight of 5,10-diethynyl porphyrin, The molar weight of the cuprous iodide is 8-12% of the molar weight of the 5,10-diethynyl porphyrin.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The porphyrin organic small molecule cathode interface material of the present invention takes porphyrin as the core, and effectively increases the π-conjugated system and electron transport capacity of the molecule by connecting other conjugated groups; at the same time, by connecting polar groups Groups and other side chains, giving the molecule very good water/alcohol solubility.

(2) The porphyrin organic small molecule cathode interface material of the present invention is further adjusted by introducing different metal ions in the cavity of porphyrin, because different metal ions have different outer electron arrangements and electron-withdrawing capabilities. The HOMO and LUMO energy levels of the synthetic material enable the interface material to effectively reduce the work function of the metal electrode and further improve the photoelectric conversion efficiency of the photovoltaic device.

(3) The porphyrin organic small molecule cathode interface material of the present invention has narrow light absorption and is bluish. When using this material, the interface has good light permeability, so that sunlight is absorbed by the active layer to the maximum extent, thereby further improving Photoelectric conversion efficiency of photovoltaic devices.

Description of drawings

Fig. 1 is the ultraviolet-visible absorption spectrum of the dichloromethane solution of embodiment 1, 2 of the present invention.

Fig. 2 is the ultraviolet-visible absorption spectrum of the porphyrin organic small molecule interface materials in the film state of Examples 1 and 2 of the present invention.

Fig. 3 is a current-voltage curve diagram of photovoltaic cells prepared in Examples 1 and 2 of the present invention under AM 1.5, 100 mW/cm ² light.

Detailed ways

The present invention will be described in further detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto.

Example 1

(1) Synthesis of 5,15-bis(3,4-bis(3,6-dioxoethylmethyl)benzene)porphyrin

In a 500mL three-neck round bottom flask, add 3,4-bis(3,6-dioxoethylmethyl)benzaldehyde (1.19g, 3.48mmol), bipyrromethane (508mg, 3.48mmol) and 350mL of dichloro Methane, blow with nitrogen for 30 minutes, then add 0.035mL of trifluoroacetic acid, stir the reaction at room temperature for 12 hours, then add 1.18g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), the stirring reaction was continued for 12 hours. After the reaction, the crude product was obtained by column chromatography on silica gel/(dichloromethane as eluent) and spin-dried, and then recrystallized by chloroform/methanol to obtain a dark red solid. ¹ H NMR (500MHz, CDCl ₃ ): δ10.30(s, 2H), 9.38(d, J=4.6Hz, 4H), 9.11(d, J=4.6Hz, 4H), 7.87(t, J=1.7 Hz, 2H), 7.79(d, J=8.1Hz, 2H), 7.34(d, J=8.1Hz, 2H), 4.51(dd, J=5.7, 4.5Hz, 4H), 4.40-4.34(m, 4H ), 4.11(dd, J=5.7, 4.5Hz, 4H), 3.99-3.94(m, 4H), 3.93-3.88(m, 4H), 3.80-3.74(m, 4H), 3.72-3.66(m, 4H ), 3.57-3.51(m, 4H), 3.49(s, 6H), 3.29(s, 6H), -3.10(s, 2H).

(2) Synthesis of 5,15-bisbromo-10,20-bis(3,4-bis(3,6-dioxoethylmethyl)phenyl)zinc porphyrin

Dissolve 5,15-bis(3,4-bis(3,6-dioxoethylmethyl)benzene)porphyrin (500mg, 0.54mmol) in 250mL of chloroform, add 2.5mL of pyridine, and keep well protected from light. After dissolving, bromosuccinimide (NBS) (211mg, 1.19mmol) was added, reacted at 0°C for 30 minutes, then continued to react overnight at room temperature, and finally quenched the reaction with acetone. After completion of the reaction, add water, extract with chloroform, dry over anhydrous sodium sulfate, spin dry and dissolve in 50 mL of chloroform solution, then add 10 mL of zinc acetate methanol solution (273 mg, 1.35 mmol of zinc acetate dissolved in 10 mL of methanol solvent ), and reflux for 2 hours in the dark. After the reaction was completed, it was washed with water, dried with anhydrous sodium sulfate, spin-dried to dry the solvent, and purified by silica gel column chromatography to obtain a bright red solid. ¹ H NMR (500MHz, CDCl ₃ ): δ9.69(d, J=4.5Hz, 4H), 8.95(d, J=4.5Hz, 4H), 7.68(d, J=5.9Hz, 2H), 7.63( t, J=7.3Hz, 2H), 7.12(dd, J=11.4, 8.0Hz, 2H), 4.24(d, J=6.0Hz, 4H), 4.10(d, J=21.8Hz, 4H), 3.76( t, J = 5.0 Hz, 4H), 3.70-3.53 (m, 8H), 3.50-3.36 (m, 8H), 3.32-3.16 (m, 10H), 3.07 (d, J = 21.6 Hz, 6H).

(3) Synthesis of 5,15-bis(trimethylsilylacetylene)-10,20-bis(3,4-bis(3,6-dioxoethylmethyl)benzene)zinc porphyrin

In a 100mL two-necked round-bottomed flask, add 5,15-bisbromo-10,20-bis(3,5-bis(dodecyloxy)benzene)zinc porphyrin (400mg, 0.346mmol), 40mL tetrahydrofuran and 20 mL of triethylamine, nitrogen gas for 30 minutes, then added bis(triphenylphosphine) palladium dichloride (25 mg, 0.036 mmol), cuprous iodide (CuI) (7.05 mg, 0.036 mmol) and trimethylsilyl acetylene (169mg, 1.73mmol), protected from light, the reaction was stirred at room temperature for three days. After the reaction was completed, it was extracted with chloroform, washed with water, dried over anhydrous sodium sulfate, and then subjected to column chromatography on silica gel/(dichloromethane/methanol=30/1 as eluent), and spin-dried to obtain a green solid. ¹ H NMR (500MHz, CDCl ₃ ): δ9.69 (dd, J=4.6, 1.6Hz, 4H), 8.93 (dd, J=4.5, 1.5Hz, 4H), 7.70 (dd, J=6.5, 2.0Hz , 2H), 7.65(m, 2H), 7.14(dd, J=11.5, 8.0Hz, 2H), 4.32-4.22(m, 4H), 4.15(d, J=22.1Hz, 4H), 3.83(d, J=6.6Hz, 4H), 3.71(d, J=29.2Hz, 4H), 3.61-3.64(m, 4H), 3.53-3.40(m, 8H), 3.33-3.21(m, 10H), 3.11(d , J=20.1Hz, 6H), 0.62(s, 18H).

(4) Synthesis of 5,15-bis(acetylene)-10,20-bis(3,4-bis(3,6-dioxoethylmethyl)benzene)zinc porphyrin

Dissolve 5,15-bis(trimethylsilylacetylene)-10,20-bis(3,5-bis(dodecyloxy)phenyl)zinc porphyrin (165 mg, 0.14 mmol) in 20 mL of tetrahydrofuran solution , tetrabutylammonium fluoride (0.3 mL, 1M in THF) was added, the reaction was stirred at room temperature for 5 minutes, and water was added to quench the reaction. It was extracted with chloroform, dried over anhydrous sodium sulfate, and spin-dried. The impurities were separated through a gel column, and a green solid was obtained by spin-drying. ¹ H NMR (500MHz, CDCl ₃ ): δ9.71(dd, J=4.7, 1.2Hz, 4H), 8.96(dd, J=4.6, 1.1Hz, 4H), 7.73(t, J=2.6Hz, 2H ), 7.67(dd, J=7.8, 2.9Hz, 2H), 7.19(t, J=7.2Hz, 2H), 4.35(s, 4H), 4.18(d, J=9.4Hz, 4H), 3.91(d , J=9.9Hz, 4H), 3.76(d, J=31.8Hz, 8H), 3.56(d, J=26.9Hz, 8H), 3.39-3.31(m, 12H), 3.16(d, J=13.5Hz , 6H).

(5) Synthesis of 2-bromo-9,9-bis(3'-(N,N-dimethylamino)propyl)fluorene

Under the protection of argon, 2-bromofluorene (2.94g, 12mmol) was dissolved in 60ml dimethylsulfoxide (DMSO), then 80mg tetrabutylammonium bromide was added, followed by 8ml sodium hydroxide solution (50wt%) After stirring for a while, 3-(N,N-dimethyl)amino-1-chloropropane hydrochloride (5g, 32mmol) was dissolved in 20mlDMSO, added dropwise to the system, and the reaction was continued at room temperature after the addition 6h. After the reaction, 50ml of water was added to dissolve the salt in the system, extracted with ether, washed with sodium hydroxide solution, water, and saturated brine successively, dried over anhydrous magnesium sulfate, spin-dried, and recrystallized several times to obtain a white solid at room temperature. viscous liquid. ¹ HNMR (500MHz, DMSO-d ₆ ): δ7.67-7.63(m, 1H), 7.54(d, J=8.1Hz, 1H), 7.48(d, J=1.8Hz, 1H), 7.44(dd, J=8.0, 1.8Hz, 1H), 7.36-7.28(m, 3H), 2.08-1.92(m, 20H), 0.84-0.68(m, 4H).

(6) 5,15-bis(9,9-bis(3'-(N,N-dimethylamino)propyl)fluorene-2-acetylene)-10,20-bis(3,4-bis Synthesis of (3,6-Dioxyethylmethyl)phenyl)zinc Porphyrin

Under the protection of argon, add 5,15-bis(acetylene)-10,20-bis(3,4-bis(3,6-dioxoethylmethyl)benzene) into a 50mL two-neck round bottom flask Zinc porphyrin (133mg, 0.13mmol), 2-bromo-9,9-bis(3'-(N,N-dimethylamino)propyl)fluorene (158mg, 0.38mmol), anhydrous toluene (20mL ), triethylamine (10mL), cuprous iodide (2.5mg, 0.01mmol) and tetrakis(triphenylphosphine)palladium (14.6mg, 0.01mmol), the reaction system was protected from light, and the reaction was stirred at 80°C for three days . The reaction was completed, cooled to room temperature, quenched with water, extracted with chloroform, washed with water, dried over anhydrous sodium sulfate, spin-dried, and separated the crude product through a silica gel column (eluent: dichloromethane/methanol/triethylamine=10/1 /0.5), followed by gel permeation chromatography (Gel Permeation Chromatography, GPC) column chromatography (tetrahydrofuran as eluent), to obtain a dark green solid. Mass (MALDI-TOF): Obs. 1713.6; Calcd. for C ₁₀₂ H ₁₂₀ N ₈ O ₁₂ Zn, 1712.8.

The porphyrin organic small molecule interface material prepared in this example was dissolved in dichloromethane, and the ultraviolet-visible absorption spectrum of the obtained dichloromethane solution is shown in FIG. 1 .

The porphyrin organic small molecule interface material prepared in this example was prepared into a thin film, and its ultraviolet-visible absorption spectrum is shown in FIG. 2 .

The current-voltage curve of the photovoltaic cell prepared by using the porphyrin organic small molecule interface material of this example under the light of AM 1.5 and 100mW/ ^cm2 is shown in Figure 3. The device structure: ITO/PEDOT:PSS/PTB7:PC ₇₁ BM/ Interface/Al. The figure also shows a battery without a cathode interface layer and a typical cathode interface material poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2 , 7-(9,9-dioctylfluorene)] (PFN) is the cathode modification layer of the battery for comparison.

Example 2

5,15-bis(9,9-bis(3'-(N,N-dimethylamino)propyl)fluorene)-10,20-bis(3,5-di-tert-butylphenyl)zinc Synthesis of porphyrin

Under the protection of argon, add 5,15-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-10 into a 25mL single-necked round bottom flask, 20-bis(3,5-bis-tert-butylphenyl)zinc porphyrin (40mg, 0.04mmol), 2-bromo-9,9-bis(3'-(N,N-dimethylamino)propyl ) fluorene (50 mg, 0.12 mmol), barium hydroxide octahydrate (27 mg, 0.08 mmol), tetrakis(triphenylphosphine) palladium (9.6 mg, 0.008 mmol), freshly distilled 1,2-dimethoxyethane (3mL) and water (0.1mL), followed by freeze-pump-thaw (freeze-pump-thaw) cycle three times to remove the oxygen in the system, and then argon was introduced, protected from light, and the reaction was stirred at 90°C for 72 Hour. The reaction was completed, cooled to room temperature, quenched with water, extracted with chloroform, washed with water, dried over anhydrous sodium sulfate, spin-dried, and separated the crude product through a silica gel column (eluent: dichloromethane/methanol/triethylamine=100/1 /1), followed by gel permeation chromatography (GPC) column chromatography (tetrahydrofuran as eluent), to obtain a purple-red solid. Mass ₍ MALDI-TOF): Obs. 1417.8; Calcd. _{for C94H112N8Zn} , 1416.8.

The porphyrin organic small molecule interface material prepared in this example was dissolved in dichloromethane, and the ultraviolet-visible absorption spectrum of the obtained dichloromethane solution is shown in FIG. 1 .

The porphyrin organic small molecule interface material prepared in this example was prepared into a thin film, and its ultraviolet-visible absorption spectrum is shown in FIG. 2 .

The current-voltage curve of the photovoltaic cell prepared by using the porphyrin organic small molecule interface material of this example under the light of AM 1.5 and 100mW/ ^cm2 is shown in Figure 3. The device structure: ITO/PEDOT:PSS/PTB7:PC ₇₁ BM/ Interface/Al.

Example 3

5,15-bis(9,9-bis(3'-(N,N-dimethylamino)propyl)fluorene)-10,20-bis(3,4-bis(3,6-dioxo Synthesis of ethylmethyl)phenyl)zinc porphyrin

Under the protection of argon, add 5,15-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-10 into a 25mL single-necked round bottom flask, 20-bis(3,4-bis(3,6-dioxoethylmethyl)phenyl)zinc porphyrin (41mg, 0.04mmol), 2-bromo-9,9-bis(3'-(N,N -Dimethylamino)propyl)fluorene (50mg, 0.12mmol), barium hydroxide octahydrate (27mg, 0.08mmol), tetrakis(triphenylphosphine)palladium (9.6mg, 0.008mmol), freshly distilled 1 , 2-dimethoxyethane (3mL) and water (0.1mL), and then freeze-pump-thaw (freeze-pump-thaw) cycle three times to remove the oxygen in the system, and then pass in argon, avoiding light , and the reaction was stirred at 90 °C for 72 hours. The reaction was completed, cooled to room temperature, quenched with water, extracted with chloroform, washed with water, dried over anhydrous sodium sulfate, spin-dried, and separated the crude product through a silica gel column (eluent: dichloromethane/methanol/triethylamine=100/1 /1), followed by gel permeation chromatography (Gel Permeation Chromatography, GPC) column chromatography (tetrahydrofuran as eluent), to obtain a purple-red solid. Mass (MALDI-TOF): Calcd. for C ₉₈ H ₁₂₀ N ₈ O ₁₂ Zn, 1667.4, Obs. 1667.8.

The small molecule interface material of the present invention has the following chemical structure:

A can also be other conjugated units, and there are many kinds of polar groups connected to it. M can also be copper ions, magnesium ions, nickel ions, etc. Ar can also be other aromatic substituent groups. The preparation principle and The performance is similar to the embodiment given in the present invention, so no further description is given here.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the embodiment, and any other changes, modifications, substitutions and combinations made without departing from the spirit and principle of the present invention , simplification, all should be equivalent replacement methods, and are all included in the protection scope of the present invention.

Claims (4)

1. a kind of porphyrin organic molecule cathode interface material, which is characterized in that there is following chemical constitution：

Wherein, M is zinc ion, copper ion, magnesium ion or nickel ion；

A is following structural unit：

The Ar structures are with lower structure：

Wherein, R₁It is containing the alkyl that carbon number is 0 to 20.

2. a kind of porphyrin organic molecule cathode interface material, which is characterized in that there is one kind in following chemical constitution：

3. the preparation method of claim 1~2 any one of them porphyrin organic molecule cathode interface material, feature exist In including the following steps：

It is prepared using Suzuki coupling reactions：The bis- borate porphyrins of 5,10-, bromide are dissolved in and fill 1 under an argon atmosphere, It in the reaction bulb of 2- dimethoxy-ethanes, adding in four (triphenyl phosphorus) and closes palladium, add in aqueous slkali, heating stirring is reacted, after cooling, Target product is extracted with chloroform, is purified by silica gel column chromatography and GPC, is finally spin-dried for solvent, product is dried under vacuum, and obtains To porphyrin organic molecule cathode interface material；

3~6 times of mole for the bis- borate porphyrins of 5,10- of the mole of the bromide, 1, the 2- dimethoxys second The mole of alkane is 45~55 times of the bis- borate porphyrins of 5,10- and bromide integral molar quantity, and four (triphenyl phosphorus) close palladium Mole be the bis- borate porphyrin moles of 5,10- 8~12%.

4. the preparation method of claim 1~2 any one of them porphyrin organic molecule cathode interface material, feature exist In including the following steps：

It is prepared using Sonogashira coupling reactions：The bis- ethynyl porphyrins of 5,10-, bromide are dissolved under an argon atmosphere In the reaction bulb for filling toluene and triethylamine, add in four (triphenyl phosphorus) and close palladium and cuprous iodide, heating stirring reaction, cooling Afterwards, target product is extracted with chloroform, is purified by silica gel column chromatography, be finally spin-dried for solvent, product is dried under vacuum, and obtains Porphyrin organic molecule cathode interface material；

The mole of the bromide is 3~6 times of the mole of the bis- ethynyl porphyrins of 5,10-, and the mole of the toluene is 45~55 times of 5,10- bis- ethynyl porphyrins and bromide integral molar quantity, the triethylamine is 1/3rd of toluene amount, described The mole that four (triphenyl phosphorus) close palladium is the 8~12% of the bis- ethynyl porphyrins moles of 5,10-, mole of the cuprous iodide Measure 8~12% for the bis- ethynyl porphyrins moles of 5,10-.