CN105949209A - Synthesis method of triphenylene dodecyloxy bridged dodecyloxy phenyl porphyrin metal Zn complex - Google Patents

Abstract

The invention discloses a method for synthesizing triphenylene dodecyloxy bridged dodecyloxyphenyl porphyrin metal Zn complex. Its synthetic route is: the first part generates monohydroxy pentahexyloxytriphenylene; secondly synthesizes an alkoxytriphenylene containing an ω-bromo branch; the second part obtains porphyrinic acid; the third part is to combine the above two Part of the obtained intermediates are synthesized through a phase transfer catalytic reaction to synthesize alkoxy bridged porphyrin-triphenylene binary compounds and react with metal salts to obtain metal complexes. As a common material, triphenylene has the advantages of good photochemical and thermal stability, easy access to raw materials, and easy purification of products, while metalloporphyrin has strong absorption in the visible light region, good photochemical and thermal stability, and The synthesis method is mature. The diphenanthrene dodecyloxy-bridged dodecyloxyphenyl porphyrin metal Zn complex synthesized by the invention can be applied to molecular devices such as organic photovoltaic materials, liquid crystal materials, organic solar cells, and organic light-emitting diodes.

Description

Metal Zn complexes of triphenylene dodecyloxy bridged dodecyloxyphenylporphyrin method of synthesis

technical field

The invention relates to a synthesis method of triphenylene dodecyloxy bridged dodecyloxyphenyl porphyrin metal Zn complex.

Background technique

Porphyrins can be divided into symmetrical porphyrins and asymmetrical porphyrins. Whether they are symmetrical depends on whether the atoms and groups on the pyrrole ring and the middle carbon are consistent. According to the nature of whether it is soluble in water, porphyrins can be divided into water-soluble porphyrins and water-insoluble porphyrins. Water-soluble porphyrins refer to water-soluble porphyrins that can be dissolved in hydrophilic solvents such as water and methanol, rather than water-soluble porphyrins. Phyloline refers to lipophilic solvents that are soluble in dichloromethane, xylene, chloroform and benzene. Porphyrin is a kind of compound with good thermal stability, and its solution has a strong fluorescence effect. Porphyrin is a dark solid compound with high melting point. Most of them are insoluble in water and alkali, but soluble in inorganic acids. Structurally, there are four pairs of lone pairs of electrons on the four nitrogen atoms in the porphyrin ring, and the two hydrogen atoms connected to the nitrogen atoms are easily lost to obtain dianions, so porphyrin is easy to interact with positively charged metal ions Coordination to form metal complexes.

In discotic liquid crystals, triphenylene is a common material because of its good photochemical and thermal stability, easy availability of raw materials, easy purification of products, rich and varied structures, and high charge transfer rate on the vertical axis. and other advantages, so it is the preferred donor unit; and porphyrin has strong absorption in the visible light region, good photochemical and thermal stability, and the synthesis method is mature, and has good liquid crystal properties, so it can be used as a good acceptor unit. The present invention designs and synthesizes a discotic liquid crystal binary compound containing an electron donor (D)-bridge (B)-acceptor (A) structure, which can be used in organic photovoltaic materials, liquid crystal materials, organic solar cells, Molecular devices such as organic light-emitting diodes.

Contents of the invention

The object of the present invention is to provide a method for synthesizing triphenylene dodecyloxy bridged dodecyloxyphenyl porphyrin metal Zn complex.

The synthetic route of the present invention is divided into the following three parts: the first part, at first o-dihexyloxybenzene and 2-hexyloxyphenol are subjected to coupling reaction under the oxidation of ferric chloride to generate monohydroxy pentahexyloxy Triphenylene; secondly, synthesize alkoxytriphenylene containing an ω-bromo branched chain with monohydroxypentahexyloxytriphenylene and 1,12-dibromododecane as main raw materials; the second part is based on p-Hydroxybenzaldehyde and 1-bromododecane are used as main raw materials to synthesize p-dodecyloxybenzaldehyde, and then synthesize porphyrin ester with methyl p-formylbenzoate and pyrrole in xylene. Finally, the obtained porphyrin ester is hydrolyzed and acidified to obtain porphyrinic acid; the third part is to synthesize a series of alkoxy bridged porphyrin-triphenanthrene binary compounds through phase transfer catalytic reaction of the intermediates obtained in the above two parts .

As a common material, triphenylene has the advantages of good photochemical and thermal stability, easy availability of raw materials, easy purification of products, rich and varied structures, and high charge transfer rate on the vertical axis, while porphyrin It has strong absorption in the visible light region, good photochemical and thermal stability, and the synthesis method is mature, and has good liquid crystal properties. The present invention designs and synthesizes a structure containing electron donor (D)-bridge (B)-acceptor (A) The discotic liquid crystal binary compounds can be used in molecular devices such as organic photovoltaic materials, liquid crystal materials, organic solar cells, and organic light-emitting diodes.

Description of drawings

Fig. 1 is the structural formula of triphenylene dodecyloxy bridged dodecyloxyphenyl porphyrin metal Zn complex of the present invention.

Fig. 2 is the chemical reaction equation of the synthetic route of the present invention.

In the figure: R=C ₆ H ₁₃ , R ₁ =C ₁₂ H ₂₅ .

detailed description

Example:

All chemical reagents and solvents used in the examples are analytically pure.

(1) Synthesis of o-hexyloxyphenol (compound 1):

20 grams of catechol, 89.9 grams of 1-bromo-n-hexane, 73.5 grams of anhydrous potassium carbonate, 6.0 grams of potassium iodide and 250 milliliters of absolute ethanol were refluxed at 85°C for 60 hours, then suction filtered at room temperature, and the filtrate was After the solvent was removed by the rotary evaporator, the fraction at 84° C. was collected under reduced pressure distillation at 0.5 mmHg to obtain 48 g of compound 1 as a colorless oily liquid with a yield of 96%. Bp: 106±3℃, IR(KBr)ν _max (cm ^-1 ): 1260,930; ¹ H NMR (300MHz, CDCl ₃ )δ: 6.89(s, 4H), 3.99(t, J＝6.9Hz, 4H), 1.83-1.76(m, J=6.9Hz, 4H), 1.49-1.31(m, 12H), 0.9(t, J=6.9Hz, 6H).

(2) Synthesis of o-dihexyloxybenzene (compound 2):

Take 50 grams of catechol, 75 grams of 1-bromo-n-hexane, 100 grams of anhydrous potassium carbonate, 3.8 grams of potassium iodide and 500 milliliters of absolute ethanol, and after reflux reaction at 85 ° C for 12 hours, suction filtration at room temperature, the filtrate was rotated After the solvent was removed by the evaporator, the fraction at 140-143° C. was collected under a vacuum distillation of 0.5 mmHg to obtain 25.5 g of a colorless oily liquid, compound 2, with a yield of 29%. Bp 255±3℃, IR(KBr)ν _max (cm ^-1 ): 1250,939; ¹ H NMR (300MHz, CDCl ₃ )δ: 6.95-6.82(m,4H), 5.68(s,1H), 4.02 (t, J = 6.9Hz, 2H), 1.83-1.76 (m, 2H), 1.48-1.31 (m, 6H), 0.91 (t, J = 6.9Hz, 3H).

(3) Synthesis of monohydroxyl-pentahexyloxytriphenylene (compound 3):

Get 4.44 grams of compound 1 and 1.56 grams of compound 2 and dissolve in 60 milliliters of dichloromethane solution and add dropwise to 80 milliliters of dichloromethane solution containing 12.96 grams of anhydrous ferric chloride and 8 milliliters of nitromethane through a constant pressure dropping funnel In 30 minutes, the dropwise addition was completed; then the temperature of the reaction was kept in the range of 0°C-3°C for a constant temperature reaction for 3 hours, and 50 ml of anhydrous methanol and 25 ml of water were added to terminate the reaction, and the reaction mixture was mixed with 15 ml of 2mol /L dilute hydrochloric acid washed twice, washed once with 15 ml of saturated brine, separated the organic layer, added anhydrous sodium sulfate to dry and remove water, and removed the solvent through a rotary evaporator, and the obtained crude product was washed with a 200-300 mesh silica gel column Chromatographic purification (eluent: ethyl acetate/petroleum ether volume ratio 1:30-1:15) yielded 2.14 g of compound 3 as a tan solid with a yield of 36%. Mp 47.7-50.1℃, IR(KBr)ν _max (cm ^-1 ):3040,1240,837; ¹ HNMR(400MHz, CDCl ₃ )δ:7.96(s,1H),7.83(s,3H),7.82( s,1H),7.77(s,1H),5.91(s,1H),4.31-4.19(m,10H),1.98-1.90(m,10H),1.59-1.40(m,30H),0.96-0.92( m,15H).

(4) Synthesis of Bromododecyloxy-Pentahexyloxytriphenylene (Compound 4):

Add 1.0 g of compound 3, 2.63 g of 1,12-dibromododecane, 0.43 g of potassium hydroxide, and 0.16 g of tetrabutylammonium bromide into a mixture of 10 ml of dichloromethane and 6.5 ml of water under a nitrogen atmosphere Stir at room temperature for 24 hours, wash twice with 30 ml of water, once with 15 ml of saturated brine, separate the organic layer, add anhydrous sodium sulfate to dry and remove water, remove the solvent by rotary evaporator, and use 200-300 mesh Purified by silica gel column chromatography (the eluent is ethyl acetate/petroleum ether volume ratio of 1:30-1:10), to obtain 1.19 g of light yellow liquid, namely compound 4, with a yield of 90%; Bp>300°C, IR( KBr) ν _max (cm ^{-1 )} : 1260,836. ¹ H NMR (400MHz, CDCl ₃ ) δ: 7.84(s, 6H), 4.23(t, J=6.8Hz, 12H), 3.40(t, J= 6.8Hz, 2H), 1.98-1.81(m, 14H), 1.64-1.50(m, 12H), 1.47-1.20(m, 34H), 0.93(t, J=6.8Hz, 15H).

(5) Synthesis of p-dodecyloxybenzaldehyde (compound 5):

Add 2.44 g of p-hydroxybenzaldehyde, 6.725 g of bromododecane and 5.52 _g of anhydrous potassium carbonate to a 100 ml single-necked flask after drying for 1 hour, and finally add 20 ml of N,N-dimethyl Formamide (DMF) solvent, the device reacted at 80°C for 12 hours in a nitrogen atmosphere, added 200 ml of water and 20 ml of dichloromethane to extract three times, dried with anhydrous sodium sulfate, removed the solvent by a rotary evaporator, and used 200- Purified by 300-mesh silica gel column chromatography (the eluent is dichloromethane/petroleum ether with a volume ratio of 1:5-1:2) to obtain 5.75 g of light yellow liquid, compound 5, with a yield of 98%. Bp>300℃, IR(KBr)ν _max (cm ^-1) : 1610, 1380, 1260, 841; ¹ H NMR (300MHz, CDCl ₃ ) δ: 9.87(s, H), 7.68(t, J＝6.8 Hz, 2H), 6.89(d, J=8.6Hz, 2H), 3.99(t, J=6.9Hz, 2H), 1.83-1.76(m, J=6.9Hz, 4H), 0.96-1.31(m, J =5.6Hz, 10H).

(6) Synthesis of 5-p-benzoic acid methyl group-10,15,20-tri-dodecyloxyphenyl porphyrin (compound 6):

Take 5.88 grams of compound 5, 1.198 grams of methyl p-acylbenzoate and 1.8495 grams of m-nitrobenzoic acid, fully dissolve it with 32 milliliters of xylene solution, and add 1.91 grams of it diluted with 32 milliliters of xylene dropwise through a constant pressure dropping funnel. Pyrrole for 10 minutes, reflux reaction at 140°C for 3.5 hours. After the reaction, the solvent xylene was distilled off to obtain a black viscous substance, which was purified by 200-300 mesh silica gel column chromatography (the eluent was dichloromethane/petroleum ether volume ratio of 1:2-1:1), and dichloromethane Methane/anhydrous methanol = 1:1 recrystallized to obtain a purple solid compound, compound 6, with a yield of 32.3%. Mp 125.1-126.2℃, IR(KBr)ν _max (cm ^-1 ): 1720, 1350, 1240, 803; ¹ H NMR (400MHz, CDCl ₃ ) δ8.90 (d, J＝6.2Hz, 6H), 8.76 (d, J=4.7Hz, 2H), 8.44(d, J=8.2Hz, 2H), 8.30(d, J=8.1Hz, 2H), 8.16-8.05(m, 6H), 7.29(d, J= 8.5Hz, 6H), 4.15(d, J=5.6Hz, 6H), 4.11(s, 3H), 1.93(dt, J=6.1Hz, 3H), 1.77-1.54(m, 12H), 1.51-1.35( m, 12H), 1.06 (dd, 9H), 1.00 (t, J=6.8Hz, 9H), -2.74 (s, 2H).

(7) Synthesis of 5-p-benzoyl-10,15,20-tri-dodecyloxyphenylporphyrin (compound 7):

Take 1.4 g of compound 6 and 5 ml of an aqueous solution containing 1.79 g of potassium hydroxide, fully dissolve them in 25 ml of tetrahydrofuran, add 5 ml of anhydrous methanol, reflux at 70°C for 3 hours, cool to room temperature, and add commercially available concentrated The pH was adjusted to 2-3 with hydrochloric acid, and the green solid compound 7 was obtained by suction filtration with a yield of 65%. Mp 176.3-177.5℃; IR(KBr)ν _max (cm ^-1 ): 1710, 1490, 1260, 801. ¹ H NMR (400MHz, CDCl ₃ ) δ8.90 (d, J＝6.2Hz, 6H), 8.76 (d, J=4.7Hz, 2H), 8.44(d, J=8.2Hz, 2H), 8.30(d, J=8.1Hz, 2H), 8.16-8.05(m, 6H), 7.29(d, J= 8.5Hz, 6H), 4.15(d, J=5.6Hz, 6H), 4.11(s, 1H), 1.93(dt, J=6.1Hz, 3H), 1.77-1.54(m, 12H), 1.51-1.35( m, 12H), 1.06 (dd, 9H), 1.00 (t, J=6.8Hz, 9H), -2.74 (s, 2H).

(8) Synthesis of triphenylene dodecyloxy bridged dodecyloxyphenylporphyrin (compound 8):

Take 0.1 gram of compound 7, 0.117 gram of compound 4, 0.039 gram of potassium carbonate and 0.16 gram of tetrabutylammonium bromide, add them to a mixture of 6 milliliters of chloroform and 12 milliliters of water, and react under reflux at 80 ° C for 36 hours, and use three Chloromethane extracts and separates the water layer and the organic layer. After the organic layer is dried over anhydrous sodium sulfate, the solvent is removed by a rotary evaporator, and purified by 200-300 mesh silica gel column chromatography (eluent is ethyl acetate/petroleum ether volume The ratio is 1:30-1:20), and 0.093 g of red solid, compound 8, was obtained with a yield of 52%. Mp 48.5±3℃, IR(KBr)ν _max (cm ^-1 ): 1720, 1380, 1240, 800; ¹ H NMR (400MHz, CDCl ₃ ) δ8.89 (d, J＝6.9Hz, 6H), 8.77 (d,J=4.6Hz,2H),8.44(d,J=8.1Hz,2H),8.30(d,J=8.1Hz,2H),8.10(dt,J=14.6,7.4Hz,6H),7.82 (s,6H),7.42-7.26(m,6H),4.51(t,J＝6.6Hz,2H),4.42-3.93(m,18H),2.10-1.86(m,18H),1.70-1.54(m ,22H),1.51-1.12(m,72H),0.91(dt,J＝14.1,7.0Hz,20H),-2.75(s,2H).Elemental analysis calcd for C ₁₄₁ H ₁₉₆ N ₄ O ₁₁ (2121.45) : C, 79.73; H, 9.27; N, 2.66 Found: C, 79.76, H, 9.27, N, 2.67.

(9) Synthesis of triphenylene dodecyloxy bridged dodecyloxyphenyl porphyrin metal Zn complex (compound 9):

0.1 g of compound 8 and 0.03 g of zinc chloride were added to a mixture of 15 ml of N,N-dimethylformamide and 10 ml of chloroform, stirred and reacted at 65°C for 3 hours in a nitrogen atmosphere, and the reaction was completed. The organic layer was separated by extraction with chloroform, dried by anhydrous sodium sulfate to remove water, and then the solvent was removed by rotary evaporation, and purified by 200-300 mesh silica gel column chromatography (the eluent was ethyl acetate/petroleum ether volume ratio of 1: 10-1:5), to obtain 0.087 g of purple solid compound 9, yield 85%; IR (KBr) ν _max (cm ^-1 ): 1720, 1360, 1240, 824; ¹ H NMR (400MHz, CDCl ₃ ) δ8.89(d, J=6.9Hz, 6H), 8.77(d, J=4.6Hz, 2H), 8.44(d, J=8.1Hz, 2H), 8.30(d, J=8.1Hz, 2H), 8.10(dt,J=14.6,7.4Hz,6H),7.82(s,6H),7.42-7.26(m,6H),4.51(t,J=6.6Hz,2H),4.42-3.93(m,18H) , 2.10-1.86 (m, 18H), 1.70-1.54 (m, 22H), 1.51-1.12 (m, 72H), 0.91 (dt, J=14.1, 7.0Hz, 20H).

Claims (1)

1. a synthetic method for benzophenanthrene dodecyloxy bridging dodecyloxy phenyl porphyrin metal Zn coordination compound, its feature It is to concretely comprise the following steps:

(1) the adjacent own alkoxy phenol i.e. synthesis of compound 1:

By 20 grams of catechols, 89.9 grams of 1-bromo normal hexane, 73.5 grams of Anhydrous potassium carbonates, 6.0 grams of potassium iodide and 250 milliliters Dehydrated alcohol, at 85 DEG C, back flow reaction is after 60 hours, sucking filtration under room temperature, after the rotated evaporimeter of filtrate removes solvent, Collecting the fraction of 84 DEG C in the case of the decompression distillation of 0.5mmHg, obtain 48 grams of colourless oil liquids i.e. compound 1, productivity is 96%；Bp:106±3℃,IR(KBr)ν_max(cm^-1):1260,930；¹H NMR(300MHz,CDCl₃)δ:6.89(s,4H), 3.99 (t, J=6.9Hz, 4H), 1.83-1.76 (m, J=6.9Hz, 4H), 1.49-1.31 (m, 12H), 0.9 (t, J=6.9Hz, 6 H)；

(2) the adjacent two own alkoxy benzenes i.e. synthesis of compound 2:

Take 50 grams of catechols, 75 grams of 1-bromo normal hexane, 100 grams of Anhydrous potassium carbonates, 3.8 grams of potassium iodide and 500 milliliters of nothings Water-ethanol, 85 DEG C of back flow reaction are after 12 hours, sucking filtration under room temperature, after the rotated evaporimeter of filtrate removes solvent, 0.5mmHg Decompression distillation in the case of collect the fraction of 140-143 DEG C, obtain 25.5 grams of colourless oil liquids i.e. compound 2, productivity is 29%； Bp 255±3℃,IR(KBr)ν_max(cm^-1):1250,939；¹H NMR(300MHz,CDCl₃)δ:6.95-6.82(m,4H), 5.68 (s, 1H), 4.02 (t, J=6.9Hz, 2H), 1.83-1.76 (m, 2H), 1.48-1.31 (m, 6H), 0.91 (t, J=6.9Hz, 3H)；

(3) monohydroxy-five hexyloxy benzophenanthrene i.e. synthesis of compound 3:

Take 4.44 g of compound 1 and 1.56 g of compound 2 to be dissolved in 60 milliliters of dichloromethane solutions through constant pressure funnel dropping To 80 milliliters of dichloromethane solutions containing 12.96 grams of anhydrous ferric trichlorides and 8 milliliters of nitromethanes, dropping in 30 minutes is complete； Then, in the range of the temperature of reaction being maintained at 0 DEG C-3 DEG C after isothermal reaction 3 hours, 50 milliliters of absolute methanols and 25 milliliters are added Water terminates reaction, and the mixture of reaction is that 2mol/L dilute hydrochloric acid washes twice by 15 milliliters of concentration, with 15 milliliters of saturated common salts Water washed once, and separates organic layer, and after addition anhydrous sodium sulfate is dried except water, rotated evaporimeter removes solvent, and obtain is thick Product with 200-300 mesh silica gel column chromatography purify, leacheate be ethyl acetate/petroleum ether volume ratio be 1:30-1:15, obtain 2.14 Gram brown yellow solid i.e. compound 3, productivity is 36%；Mp 47.7-50.1℃,IR(KBr)ν_max(cm^-1):3040,1240,837；¹H NMR(400MHz,CDCl₃)δ:7.96(s,1H),7.83(s,3H),7.82(s,1H),7.77(s,1H),5.91(s,1H), 4.31-4.19(m,10H),1.98-1.90(m,10H),1.59-1.40(m,30H),0.96-0.92(m,15H)；

(4) bromododecane epoxide-five hexyloxy benzophenanthrene i.e. synthesis of compound 4:

By 1.0 g of compound 3,2.63 gram 1,12-dibromo-dodecane, 0.43 gram of potassium hydroxide and 0.16 gram of tetrabutyl ammonium bromide, Join in the mixture of 10 milliliters of dichloromethane and 6.5 milliliters of water, be stirred at room temperature under nitrogen atmosphere 24 hours, with 30 milliliters Water washes twice, and washed once with 15 milliliters of saturated aqueous common salts, separates organic layer, after addition anhydrous sodium sulfate is dried except water, and warp Rotary Evaporators removes solvent, purifies with 200-300 mesh silica gel column chromatography, and leacheate is that ethyl acetate/petroleum ether volume ratio is 1:30-1:10, obtaining weak yellow liquid 1.19 grams is compound 4, productivity 90%；Bp>300℃,IR(KBr)ν_max(cm^-1):1260, 836.¹H NMR(400MHz,CDCl₃) δ: 7.84 (s, 6H), 4.23 (t, J=6.8Hz, 12H), 3.40 (t, J=6.8Hz, 2 H), 1.98-1.81 (m, 14H), 1.64-1.50 (m, 12H), 1.47-1.20 (m, 34H), 0.93 (t, J=6.8Hz, 15H)；

(5) to the dodecyloxy benzaldehyde i.e. synthesis of compound 5:

Take 100 milliliters of single port flasks after dry 1 hour and be separately added into 2.44 grams of hydroxy benzaldehydes, 6.725 grams of bromos 12 Alkane and 5.52 grams of Anhydrous potassium carbonates, be eventually adding 20 milliliters through CaH₂DMF (DMF) solvent being dried, dress After putting in nitrogen atmosphere 80 DEG C of reactions 12 hours, adds 200 milliliters of water and 20 milliliters of dichloromethane extractions three times, with anhydrous Sodium sulfate is dried, and rotated evaporimeter removes solvent, purifies with 200-300 mesh silica gel column chromatography, and leacheate is dichloromethane Alkane/petroleum ether volume ratio is 1:5-1:2, obtains 5.75 grams of weak yellow liquids i.e. compound 5, and productivity is 98%；Bp>300℃, IR(KBr)ν_max(cm^-1):1610,1380,1260,841；¹H NMR(300MHz,CDCl₃) δ: 9.87 (s, H), 7.68 (t, J= 6.8Hz, 2H), 6.89 (d, J=8.6Hz, 2H), 3.99 (t, J=6.9Hz, 2H), 1.83-1.76 (m, J=6.9Hz, 4H), 0.96-1.31 (m, J=5.6Hz, 10H)；

(6) 5-para Toluic Acid carbomethoxy-10,15,20-three is to the dodecyloxy phenyl porphyrin i.e. synthesis of compound 6:

Take 5.88 g of compound 5,1.198 grams to acyl group essence of Niobe and 1.8495 grams of m-Carboxynitrobenzenes, with 32 milliliter two After toluene solution fully dissolves, by constant pressure funnel dropping through 1.91 grams of pyrroles 10 minutes of 32 milliliters of dimethylbenzene dilution, Back flow reaction 3.5 hours at 140 DEG C；Solvent xylene is distilled off after reaction, obtains dark thick material, use 200-300 mesh Silica gel column chromatography purifies, leacheate be dichloromethane/petroleum ether volume ratio be 1:2-1:1, with dichloromethane/absolute methanol=1:1 weight Crystallization, obtains violet solid i.e. compound 6, and productivity is 32.3%；Mp 125.1-126.2℃,IR(KBr)ν_max(cm^-1): 1720,1350,1240,803；¹H NMR(400MHz,CDCl₃) δ 8.90 (d, J=6.2Hz, 6H), 8.76 (d, J=4.7Hz, 2H), 8.44 (d, J=8.2Hz, 2H), 8.30 (d, J=8.1Hz, 2H), 8.16-8.05 (m, 6H), 7.29 (d, J=8.5Hz, 6H), 4.15 (d, J=5.6Hz, 6H), 4.11 (s, 3H), 1.93 (dt, J=6.1Hz, 3H), 1.77-1.54 (m, 12H), 1.51-1.35 (m, 12H), 1.06 (dd, 9H), 1.00 (t, J=6.8Hz, 9H) ,-2.74 (s, 2H)；

(7) 5-para Toluic Acid base-10,15,20-three is to the dodecyloxy phenyl porphyrin i.e. synthesis of compound 7:

Take the aqueous solution of 1.4 6 and 5 milliliters of 1.79 grams of potassium hydroxide of g of compound, after fully dissolving with the oxolane of 25 milliliters, Add the absolute methanol of 5 milliliters, back flow reaction 3 hours at 70 DEG C, add commercially available concentrated hydrochloric acid regulation pH after being cooled to room temperature extremely Between 2-3, sucking filtration obtains the solid i.e. compound 7 of green, productivity 65%；Mp 176.3-177.5℃；IR(KBr)ν_max (cm^-1):1710,1490,1260,801.¹H NMR(400MHz,CDCl₃) δ 8.90 (d, J=6.2Hz, 6H), 8.76 (d, J= 4.7Hz, 2H), 8.44 (d, J=8.2Hz, 2H), 8.30 (d, J=8.1Hz, 2H), 8.16-8.05 (m, 6H), 7.29 (d, J=8.5 Hz, 6H), 4.15 (d, J=5.6Hz, 6H), 4.11 (s, 1H), 1.93 (dt, J=6.1Hz, 3H), 1.77-1.54 (m, 12H), 1.51-1.35 (m, 12H), 1.06 (dd, 9H), 1.00 (t, J=6.8Hz, 9H) ,-2.74 (s, 2H)；

(8) the benzophenanthrene dodecyloxy bridging dodecyloxy phenyl porphyrin i.e. synthesis of compound 8:

Take 0.1 4,0.039 gram of potassium carbonate of g of compound 7,0.117 g of compound and 0.16 gram of four butyl bromation amine, join 6 In the mixture of milliliter chloroform and 12 milliliters of water, back flow reaction 36 hours at 80 DEG C, carry out extraction with chloroform and separate Water layer and organic layer, organic layer is dried through anhydrous sodium sulfate, and rotated evaporimeter removes solvent, with 200-300 mesh silicagel column Chromatographic purification, leacheate be ethyl acetate/petroleum ether volume ratio be 1:30-1:20, obtain 0.093 gram of red solid i.e. compound 8, Productivity is 52%；Mp 48.5±3℃,IR(KBr)ν_max(cm^-1):1720,1380,1240,800；¹H NMR(400MHz, CDCl₃) δ 8.89 (d, J=6.9Hz, 6H), 8.77 (d, J=4.6Hz, 2H), 8.44 (d, J=8.1Hz, 2H), 8.30 (d, J=8.1 Hz, 2H), 8.10 (dt, J=14.6,7.4Hz, 6H), 7.82 (s, 6H), 7.42-7.26 (m, 6H), 4.51 (t, J=6.6Hz, 2H), 4.42-3.93 (m, 18H), 2.10-1.86 (m, 18H), 1.70-1.54 (m, 22H), 1.51-1.12 (m, 72H), 0.91 (dt, J=14.1, 7.0Hz,20H),-2.75(s,2H).Elemental analysis calcd for C₁₄₁H₁₉₆N₄O₁₁(2121.45):C,79.73；H, 9.27；N,2.66Found:C,79.76,H,9.27,N,2.67；

(9) synthesis of the i.e. compound 9 of benzophenanthrene dodecyloxy bridging dodecyloxy phenyl porphyrin metal Zn coordination compound:

Take 0.1 g of compound 8 and 0.03 gram of zinc chloride, join 15 milliliters of DMFs and 10 milliliter of three chloromethane In the mixture of alkane, react after nitrogen atmosphere stirring reaction 3 hours at 65 DEG C and terminate；Organic layer is separated with chloroform extraction, After anhydrous sodium sulfate is dried except water, rotary evaporation removes solvent, purifies with 200-300 mesh silica gel column chromatography, and leacheate is acetic acid Ethyl ester/petroleum ether volume ratio is 1:10-1:5, obtains 0.087 gram of violet solid i.e. compound 9, productivity 85%；IR(KBr)ν_max (cm^-1):1720,1360,1240,824；¹H NMR(400MHz,CDCl₃) δ 8.89 (d, J=6.9Hz, 6H), 8.77 (d, J= 4.6Hz, 2H), 8.44 (d, J=8.1Hz, 2H), 8.30 (d, J=8.1Hz, 2H), 8.10 (dt, J=14.6,7.4Hz, 6H), 7.82 (s, 6H), 7.42-7.26 (m, 6H), 4.51 (t, J=6.6Hz, 2H), 4.42-3.93 (m, 18H), 2.10-1.86 (m, 18H), 1.70-1.54 (m, 22H), 1.51-1.12 (m, 72H), 0.91 (dt, J=14.1,7.0Hz, 20H)；

Described chemical reagent and solvent are analytical pure.