KR910008259B1 - Polycyanamid-tetraphenylporphyrin - Google Patents

Abstract

A metal complex of formula (I) is produced by diazotizing polycyanamide of formula (II) in the thick sulfuric acid, coupling the mixed soln. with tetraphenyl porphyrine of formula (III) to produce polycyanamide- tetraphenyl porphyrine of formula (IV), and forming a complex of (IV) and metal ion. In eht formulas, M is Zn, Mg, Cu, Co, Fe, Ni or Mn; x is 5-30; Y is N2 in the low temp.; n is 500-3000. The metal complex is useful as an conductive polymeric material.

Description

Metal complex compound of polycyanamide-tetraphenyl porphyrin and preparation method thereof

1 is an IR spectrum of polycyanamide-tetraphenylporphyrin which is an intermediate compound of the present invention.

2 is an IR spectrum of the polycyanamide-tetraphenylporphyrin zinc complex compound in the target compound of the present invention.

The present invention relates to a metal complex compound of the following structural formula (I) polycyanamide-tetraphenylporphyrin useful as an organic polymer compound for generating a photocurrent, in particular a conductive polymer material for generating a photocurrent, and a method for preparing the same.

Wherein M is zinc, magnesium, copper, cobalt, iron, nickel or manganese, X is an integer between 5 and 30, and Y is N ₂ at low temperatures when diazotized polycyanamide and then combined with tetraphenylporphyrin Is present and N ₂ is not present at high temperatures.

Recently, as the concern about energy depletion has gradually intensified, researches for developing petroleum substitute energy have been actively conducted, and one of the technologies developed as a result of this research effort is a polymer material for generating photocurrent.

Already, conductive polymers (eg, polyacetylene, poly (p-phenylene), poly (p-phenylene sulfide, etc.) have been developed in known new materials, but these materials generate photocurrents because they do not have light-sensitive groups. Can not.

In general, the atoms constituting the polymer are simply single bonds with each other or double bonds or benzene nuclei between single bonds. Atoms that form the backbone of a polymeric material are bonded to each other by a pair of electrons. These pairs are ubiquitous in the valence bonds of each atom, so they can't move in a molecule. have.

However, the conductive polymer material has an electron arrangement completely different from that described above, and the atoms constituting the conductive polymer material alternately appear as double bonds or triple bonds with single bonds.

That is, the foreign substances are composed of conjugated double bonds or conjugated triple bonds, or cumulative bonds.

Among these materials, even if carbonyl, benzene rings or lone pairs are located between conjugated double bonds or conjugated triple bonds, the properties of the conductive polymer materials are not lost.

In other words, the conductive polymers with conjugated double bonds have Ⅱ electron orbitals overlapping each other, so the Ⅱ electron cloud is considered to be delocalized throughout the organic polymer, but in reality, all Ⅱ bonds in the organic polymer are in one plane. Only when placed is the cloud of Ⅱ electrons delocalized throughout the organic polymer and becomes conductive.

In addition, Adler (J. polymer sci., Part c, No. 29, 73-79) suggests that the coupling of porphyrin-based compounds to organic polymers can result in superconductor properties and other electromagnetic properties. : 1970), but has not yet reached an industrially useful stage.

Accordingly, an object of the present invention is to combine a polycyanamide having conductivity and tetraphenylporphyrin which absorbs visible light to generate a photocurrent, and then forms a complex with a metal atom such as zinc, thereby providing an optoelectronic material. The present invention provides a metal complex compound of polycyanamide-tetraphenylporphyrin useful for the same and a method for producing the same.

Hereinafter, the present invention will be described in detail.

The present invention is a metal complex compound of polycyanamide-tetraphenylporphyrin represented by the following structural formula (I).

Wherein M is zinc, magnesium, copper, cobalt, iron, nickel or manganese, X is an integer between 5 and 30, and Y is N ₂ at low temperature when diazotized polycyanamide and then combined with tetraphenylporphyrin Is present and N ₂ is not present at high temperatures.

In addition, the present invention is diazotized polycyanamide represented by the following structural formula (II) in concentrated sulfuric acid, and selected by low temperature or high temperature and coupled with tetraphenylporphyrin represented by the following structural formula (III) Next, the polycyanamide-tetraphenylporphyrin metal represented by the above-mentioned structural formula (I), which is prepared by forming a polycyanamide-tetraphenylporphyrin represented by the following structural formula (IV) as a complex with a metal ion It is a method for producing a complex compound.

In the above formula, X and Y are as described above, n is an integer of 500 to 3000.

Hereinafter, the present invention will be described in more detail according to the production method as follows.

The metal complex of polycyanamide-tetraphenylporphyrin, which is the target compound of the present invention, is prepared from two starting materials, namely polycyanamide and tetraphenylporphyrin.

First, polycyanamide, which is the first starting material, is an organic polymer material having a conjugated double bond as shown in the above formula (II), and can be prepared from melamine by the following method as is known.

Wherein n is as described above.

Next, the polycyanamide is diazotized in concentrated sulfuric acid, where the presence of the primary amino group in the structure of the polycyanamide is not only determined by IR, but also by the N ₂ gas generated during the diazotization reaction. It is confirmed.

In this way, the polycyanamide is diazotized, and then a second starting material, tetraphenylporphyrin, is dissolved in concentrated sulfuric acid, where N ₂ is bonded at low temperature and N ₂ is absent at high temperature. to be. This yields a polycyanamide-tetraphenylporphyrin of formula (IV) in which the polycyanamide and tetraphenylporphyrin are coupled.

In the present invention, the polycyanamide-tetraphenylporphyrin of the above formula (IV), which is an intermediate compound, has not only the generation of photocurrent by visible light but also conductivity, and can be usefully used as a photovoltaic material. In order to further enhance the effect of the invention, the present invention is completed by allowing tetraphenylporphyrin, which is a part of receiving visible light, to form a complex with a metal atom.

According to the present invention, since the metal complex compound of tetraphenylporphyrin is longer than the lifetime of tetraphenylporphyrin which is not complexed with tetraphenylporphyrin complexed with a metal atom, excited electrons can be used more efficiently.

On the other hand, metal elements used in the metal complex compound of tetraphenylporphyrin may be zinc, magnesium, copper, cobalt, iron, nickel, manganese, and the like, but zinc, magnesium, nickel, cobalt, and manganese may be used among these metals. The best is because the reaction of these metals proceeds most quantitatively.

The reaction process of the present invention as described above is shown as follows continuously according to the reaction formula.

Wherein, X is a 5- to 30 integer, Y is a poly a cyanamide was diazotized, and then the low temperature when combined with the tetraphenyl porphyrin N ₂ is present and a high temperature in the N ₂ is not present, TPP is tetra Phenylporphyrin, DMF represents N, N-dimethylformamide, M and M ⁺⁺ represent metal ions zinc, magnesium, copper, cobalt, iron, nickel or manganese, n is an integer from 500 to 3000 to be.

When the polycyanamide-tetraphenylporphyrin metal complex compound of the present invention prepared in this way receives visible light, the electrons of the tetraphenylporphyrin metal complex compound are excited from the II state to the II ^* state, and the excited electrons are conductive polycyanamide. Conjugation of the chain is carried through a double bond

Therefore, when the metal complex compound of polycyanamide-tetraphenylporphyrin is connected to a device that allows the excitation electrons generated by visible light to flow in one direction, the foreign material is expected to be widely used in the real industrial field as a photovoltaic cell. .

On the other hand, in the present invention, polycyanamide-tetraphenylporphyrin synthesized using tetraphenylporphyrin instead of the metal complex compound of tetraphenylporphyrin and a method for producing the same are also included in the scope of the present invention.

In addition, when the metal complex compound of polycyanamide-tetraphenylporphyrin is doped with Br ₂ , the conductivity of the polycyanamide chain is further increased, thereby further improving the effect of the present invention.

Hereinafter, the present invention will be described in more detail with reference to detailed examples of the present invention.

Example 1

Preparation of Polycyanamide-tetraphenylporphyrin.

In a 250 ml beaker, concentrated sulfuric acid (38 ml) was added, and polycyanamide (1.5 g, 35.7 mmol) was slowly added while stirring, followed by stirring for 42 hours to completely dissolve it, which was then poured into an iced water bath and cooled to 0 ° C. In this solution, sodium nitrite (3.45g, 50mmole) was dissolved in concentrated sulfuric acid (54ml), cooled to 0 ° C, and the solution was slowly added, while the temperature of the mixed solution was kept at 0-5 ° C during the addition. Next, phosphoric acid (85%, 18 ml) is added again. In this case, the temperature of the mixed solution is 5 ° C. or less, and the mixture is stirred for 1 hour at room temperature in order to completely diazotize. The mixed solution was added to the water bath again and cooled, and tetraphenylporphyrin (2.63 g, 4.3 mmol) was dissolved in concentrated sulfuric acid (60 ml), and the solution cooled to 0 ° C. was slowly added while stirring.

Subsequently, the mixed solution is stirred at 0 ° C. for 2 hours, stirred at room temperature again for 10 hours, and then water (1000 ml) is added to precipitate the product.

The precipitated product is filtered off, washed with water until the filtrate is neutral, and then vacuum dried at 70 ° C. for 24 hours. In addition to the desired polycyanamide-tetraphenylporphyrin, the product remains unreacted with polycyanamide and tetraphenylporphyrin, of which tetraphenylporphyrin is removed using a Soxlet apparatus (solvent is chloroform). And polycyanamide by removing only polycyanamide-tetraphenylporphyrin in dimethylformamide in the other two substances, i.e., polycyanamide and polycyanamide-tetraphenylporphyrin. Only tetraphenylporphyrin was separated and vacuum dried at 70 ° C for 24 hours.

The yield is 1.10 g (39.67%).

Experimental results of the atomic absorber shows that tetraphenylporphyrin is bound every 5-30th -C = N-binding node when tetraphenylporphyrin is bound to polycyanamide due to steric hindrance of tetraphenylporphyrin.

Example 2

Preparation of Zinc Complex Compound of Polycyanamide-Tetraphenyl Porphyrin.

Dimethylformamide (120 ml) and polycyanamide-tetraphenylporphyrin (5.4 g, 3.64 mmol) were added to a 500 ml reactor, and the mixture was refluxed for 30 minutes with stirring, followed by addition of zinc chloride (0.52 g, 3.87 mmol). After continuing to reflux for 30 minutes, the reaction was cooled in an ice-water bath and ice-water (300 ml) was added to precipitate and filter the resulting material.

The filtered material was washed several times with water to remove dimethylformamide and excess zinc chloride and then vacuum dried at 70 ° C. for 24 hours.

The yield is 5.60 (99.30%).

Experimental results of the atomic absorber shows that tetraphenylporphyrin is bound to every 20th -C = N-binding node due to steric hindrance of tetraphenylporphyrin when tetraphenylporphyrin is bound to polycyanamide.

IR spectrum and UV spectrum of the prepared target compound are shown in FIGS. 1 and 2, respectively.

Example 3

Preparation of Magnesium Complex Compound of Polycyanamide-Tetraphenyl Porphyrin.

Dimethylformamide (120 ml) and polycyanamide-tetraphenylporphyrin (5.4 g, 3.82 mmol) were added to a 500 ml reactor, and the mixture was refluxed for 30 minutes with stirring. Then, magnesium chloride (0.37 g, 3.90 mmol) was added to the reaction solution. do.

Subsequently, the reaction was refluxed for 1 hour, and then the reaction product was cooled in an ice water bath, and then ice water (300 ml) was added thereto to precipitate and filter the product. The filtered material was washed several times with water to remove dimethylformamide and excess magnesium chloride, followed by vacuum drying at 70 ° C. for 24 hours.

The yield is 5.23 g (95.44%).

According to the experimental results of the atomic absorber, tetraphenylporphyrin is bound to every 18th -C = N- binding node due to steric hindrance of tetraphenylporphyrin when tetraphenylporphyrin is bound to polycyanamide.

Example 4

Preparation of Copper Complex Compound of Polycyanamide-Tetraphenyl Porphyrin.

Dimethylformamide (120 ml) and polycyanamide-tetraphenylporphyrin (5.4 g, 3.64 mmol) were added to a 500 ml reactor, and the mixture was refluxed for 30 minutes with stirring. Then, two molecules of water-hydrated copper chloride (II) (0.66 g, 3.90 mmol) is added to the reaction solution.

After refluxing for 1 hour, the reaction was cooled in an ice-water bath and ice-water (300 ml) was added to precipitate and filter the resulting material. The filtered material was washed several times with water to remove dimethylformamide and excess copper chloride and vacuum dried at 70 ° C. for 24 hours.

The yield is 5.30 g (94.30%).

Experimental results of the atomic absorber shows that tetraphenylporphyrin is bound to every 20th -C = N-binding node due to steric hindrance of tetraphenylporphyrin when tetraphenylporphyrin is bound to polycyanamide.

Example 5

Preparation of Cobalt Complex of Polycyanamide-tetraphenylporphyrin.

Dimethylformamide (120 ml) and polycyanamide-tetraphenylporphyrin (5.4 g, 4.07 mmol) were added to a 500 ml reactor, and the mixture was refluxed for 30 minutes with stirring, followed by 6 minutes of water-hydrated cobalt chloride (II) (0.93). g, 3.90 mmol) is added to the reaction solution.

After refluxing for 1 hour, the reaction was cooled in an ice-water bath, and then ice-water (300 ml) was added to precipitate and filter the product. The filtered material was washed several times with water to remove dimethylformamide and excess cobalt chloride (II) and vacuum dried at 70 ° C. for 24 hours.

The yield is 5.61 g (94.64%).

Experimental results of the atomic absorber shows that tetraphenylporphyrin is bound to every 16th -C = N-binding node due to steric hindrance of tetraphenylporphyrin when tetraphenylporphyrin is bound to polycyanamide.

Example 6

Preparation of Iron Complex Compound of Polycyanamide-Tetraphenyl Porphyrin.

Dimethylformamide (120 ml) and polycyanamide-tetraphenylporphyrin (5.4 g, 3.64 mmol) were added to a 500 ml reactor, and the mixture was refluxed for 30 minutes with stirring. Then, ferric chloride (0.78 g and 3.90 mmol) was hydrated in four molecules of water. ) Is added to the reaction solution.

Subsequently, the reaction was refluxed for 1 hour, the reaction was cooled in an ice water bath, and ice water (300 ml) was added to precipitate and filter the resulting material. The filtered material was washed several times with water to remove dimethylformamide and excess ferric chloride, followed by vacuum drying at 70 ° C. for 24 hours.

The yield is 5.29 g (94.80%).

Experimental results of the atomic absorber shows that tetraphenylporphyrin is bound to every 20th -C = N-binding node due to steric hindrance of tetraphenylporphyrin when tetraphenylporphyrin is bound to polycyanamide.

Example 7

Preparation of Nickel Complex Compound of Polycyanamide-tetraphenylporphyrin.

Dimethylformamide (120 ml) and polycyanamide-tetraphenylporphyrin (5.4 g, 5.05 mmol) were added to a 500 ml reactor, and the mixture was refluxed for 30 minutes with stirring, followed by 6 minutes of water-hydrated nickel chloride (II) (0.80 g). , 3.90mmole) is added to the reaction solution.

After refluxing for 1 hour, the reaction was cooled in an ice-water bath and ice-water (300 ml) was added to precipitate and filter the resulting material. The filtered material was washed several times with water to remove dimethylformamide and excess nickel (II) chloride, followed by vacuum drying at 70 ° C. for 24 hours.

The yield is 5.33 g (93.84%).

According to the experimental results of the atomic absorber, tetraphenylporphyrin is bound every 10th -C = N- binding node due to steric hindrance of tetraphenylporphyrin when tetraphenylporphyrin is combined with polycyanamide.

Example 8

Preparation of Manganese Complex Compounds of Polycyanamide-tetraphenylporphyrin.

Dimethylformamide (120 ml) and polycyanamide-tetraphenylporphyrin (5.4 g, 3.82 mmole) were added to a 500 ml reactor, and the mixture was refluxed for 30 minutes with stirring, followed by 4 minutes of water-hydrated manganese chloride (II) (0.77 g). , 3.90mmole) is added to the reaction solution.

Subsequently, the mixture was refluxed for 1 hour, the reaction was cooled in an ice-water bath, and then ice-water (300 ml) was added to precipitate and filter the product. The filtered material was washed several times with water to remove dimethylformamide and excess manganese chloride (II), followed by vacuum drying at 70 ° C. for 24 hours.

The yield is 5.42 g (96.79%).

According to the experimental results of the atomic absorber, tetraphenylporphyrin is bound to every 18th -C = N- binding node due to steric hindrance of tetraphenylporphyrin when tetraphenylporphyrin is bound to polycyanamide.

Claims (5)

A metal complex compound of polycyanamide-tetraphenylporphyrin represented by the following structural formula (I).

Wherein M is zinc, magnesium, copper, cobalt, iron, nickel or manganese, X is an integer from 5 to 30, Y is N ₂ at low temperature when diazolated polycyanamide and then combined with tetraphenylporphyrin Is present and N ₂ is not present at high temperatures. The polycyanamide represented by the following structural formula (II) is diazotized in concentrated sulfuric acid, which is then coupled with tetraphenylporphyrin represented by the following structural formula (III) to form the polycyanamide-tetraphenylporphyrin of the following structural formula (IV). A method for producing a polycyanamide-tetraphenylporphyrin metal complex represented by Structural Formula (I), which is prepared and formed into a complex with a metal ion.

Wherein, X is an integer from 5 to 30, Y is in the low temperature when combined with the next-tetraphenyl porphyrin was conditioner dia poly cyanamide N ₂ is present and a high temperature, N ₂ is not present, n is from 500 to 3000 Is an integer. The method according to claim 2, wherein the metal compound is one selected from zinc, magnesium, copper, cobalt, iron, nickel or manganese. A method of doping the metal complex compound of polycyanamide-tetraphenylporphyrin represented by Structural Formula (I) with Br ₂ to further improve the conductivity of the polycyanamide-tetraphenylporphyrin metal complex. Polycyanamide-tetraphenyl porphyrin represented by the following structural formula (IV).

Wherein, X is an integer from 5 to 30, Y is in a low temperature when combined with the next-tetraphenyl porphyrin was conditioner dia poly cyanamide N ₂ is present and is not present in the N ₂ temperature.

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