KR100437550B1 - Lanthanide-chelated sappyrins with dendrons having light-harvesting effect and their synthetic methods - Google Patents

Abstract

The present invention relates to a complex salt type spirin dendrimer compound comprising a rare earth ion having a structure of the formula (1) and a method for producing the same.

[Formula 1]

Description

Complexed sapyrin dendrimer compounds containing rare earth ions and methods for preparing the same {Lanthanide-chelated sappyrins with dendrons having light-harvesting effect and their synthetic methods}

The present invention relates to a complex salt type spirin dendrimer compound comprising a rare earth ion having a structure of the formula (1) and a method for producing the same.

[Formula 1]

The present invention improves the solubility in the polymer medium through the design of the molecular structure to more efficiently dop into the polymer medium, absorb the photon energy (or light) to transfer energy to the composite central system to exhibit a light harvesting effect The present invention relates to the development of a new planar waveguide optical amplification material that maximizes the photophysical properties by collecting and transmitting artificial light using an arylether optical antenna using the principles of photosynthetic antenna complexes existing in nature.

In particular, it is related with the compound represented by the following formula, and its manufacturing method. These compounds are complex salt type spirin dendrimer compounds containing rare earth ions having a structure that encapsulates rare earth metal ions efficiently into a sapphire derivative to impart a condensing function by introducing a dendrimer, and to prevent interaction between rare earth metals, and It relates to a manufacturing method.

The present invention relates to a new planar waveguide optical amplification material with improved solubility and energy transfer capability. This is to compensate for the decrease in light intensity, which is a fundamental problem of the optical information polymer material.

The concentration of Er ⁺³ doped in the conventional optical silica is about 100-1000 ppm, and if it is higher than that, the non-luminescence process mainly occurs due to the interaction between the Er ⁺³ ions, thereby rapidly decreasing the optical amplification efficiency. For this reason, high gain optical amplification is not possible by doping Er ⁺³ to silica optical fiber, and thus it is difficult to expect about 30 dB of optical amplification in the form of a planar waveguide integrated circuit. As a new material for solving such a problem and implementing a planar waveguide optical amplification device, a material having a rare earth ion doped into a polymer has attracted attention. Optically amplified polymer materials are currently being studied in advanced countries such as Japan, the United States, and Europe to develop planar waveguide optical amplified materials in which a rare earth ion complex compound is doped into a polymer medium. The polymer amplification element is a fiber amplification element doped with organic dye at a concentration of about 1 ppm in PMMA-based polymer fiber core media, first released by Keio University in 1993, and the optical element length is 50 cm, which is relatively long and 30 dB. It showed very good amplification characteristics. However, since the light emission process is caused by spontaneous light emission, and the light amplification time is short, it cannot be used in the planar waveguide optical amplification device. To overcome this problem, the team presented a photo-amplified polymer device by doping rare earth metal with amplification effect to PMMA polymer fiber.

Recently, Kuzyk and colleagues at the University of Texas (Austin) in the United States announced the fabrication of a very short optical amplification device of 2.2 cm by spin coating method by doping Nd ⁺³ on a water-soluble polymer, photolime gel, with an amplification wavelength of 1.06 µm. The gain was relatively good at 8.5 dB. Philips, the Netherlands, filled a Teflon capillary with a MA-based lauryl methacrylate monomer, and then doped the rare earth metal Eu ⁺³ and polymerized it to develop an optical amplification device in the form of a very short polymer optical fiber of about 1.5 cm. The amplification gain was reported as 4.1 dB.

In recent years, NTT optoelectronic research teams in Japan, universities in the US (Colorado University, Arizona University) and corporate research institutes (Bellcore, Corning), and McGill University in Canada have used low-temperature sol-gel chemistry to uniformly distribute rare earth metals with inorganic polymer media. Research into the light-amplifying material of the guest-host system injected into (SiO ₂ ) is being actively conducted. In particular, in 1996, the development of a planar waveguide optical amplification device and WDM integrated optical amplification device was reported by this method. However, the problem of this system is that the rare earth metals have low solubility so that the doping concentration is limited, resulting in low optical amplification effect, and the rare earth ion-silica phase separation problem is very low optical amplification effect.

In order to solve the above problems, the present invention, unlike the existing technology of doping the rare earth ions in the polymer, exhibits the light collecting effect of the principle of photosynthesis using molecular engineering, has excellent solubility in the polymer medium, rare earth SUMMARY OF THE INVENTION It is a technical object of the present invention to provide a complex salt type spirin dendrimer compound containing rare earth ions having no agglomeration of metals and no ion-ion interaction, and a method for preparing the same.

In order to achieve the above object, the present invention relates to a complex salt type spirin dendrimer compound comprising a rare earth ion having a structure of the formula (1) and a method for producing the same.

[Formula 1]

A brief summary of the preparation process of the complex salt type spirin dendrimer compound containing the rare earth ion of the present invention is as follows.

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8

Scheme 9

Scheme 10

Scheme 11

Scheme 12

Scheme 13

Scheme 14

Scheme 15

Scheme 16

Scheme 17

Scheme 18

Scheme 19

Scheme 20

Scheme 21

Scheme 22

Scheme 23

Hereinafter, the present invention will be described in detail with reference to the following Examples.

EXAMPLE

reagent

Hexane, dichloromethane, methyl alcohol, ethyl alcohol, benzene, tetrahydrofuran, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, and amonium chloride were used by Dongyang Chemical. And pyrrole, benzaldehyde, 4-anisaldehyde, 3,5-dimethoxybenzaldehyde, 4-bromobenzaldehyde, trifluoroacetic acid (TFA), acetonitrile, boron trifluoride diethyl etherate (BF ₃ · OEt ₂ ), sodium borohydride, 4-anisoylchloride, 4-bromobenzoyl chloride , 3,5-dimethoxybenzoyl chloride, ethyl magnesium bromide, boron tribromide, carbon disulfide, 18-crown-6, n-butyl lithium, zinc chloride, tetrakis (triphenylphosphine) palladium (0), erbium acetate hexahydrate, palladium carbon is Aldrich's The product was purchased and used, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) used the product of Acros. The above reagents were used without any purification.

Common way

All new compounds were identified by ¹ H-NMR, ¹³ C-NMR and FT-IR. ¹ H-NMR was recorded using a Varian 300 spectrometer and all chemical mobility was reported in ppm relative to tetramethyl silane, an internal standard. IR spectra were measured on KBr pellets using a Perkin-Elmer Spectrometer.

Example 1:

Method for preparing 5- (4-Methoxyphenyl) dipyrromethane

In a round flask, pyrrole (5 equiv.) And 4-anisaldehyde (1 equiv.) Were added and stirred at room temperature for 5 minutes, trifluoroacetic acid (TFA; 0.1 equiv.) Was added, followed by stirring at room temperature for 5 minutes, and then reaction. 25 ml of 0.1N NaOH aqueous solution was added to the vessel to stop the reaction. Then, the mixture was extracted with dichloromethane, and then the organic solvent and pyrrole were evaporated. The mixture was vacuum distilled using Kugelrohr to obtain a yellow compound, followed by distillation. The compound was dissolved in ethanol, and recrystallized by adding a small amount of water to obtain white crystals.

¹ H-NMR: 3.79 (s, 3H, OCH 3), 5.42 (s, 1H, meso-H), 5.90 (m, 2H, pyrrole-H), 6.15 (q, 2H, pyrrole-H), 6.68 (q , 2H, pyrrole-H), 6.85 (d, 2H, Ar-H), 7.12 (d, 2H, Ar-H), 7.88 (br s, 2H, NH)

Scheme 1

Example 2:

Method for preparing 5- (3,5-Dimethoxyphenyl) dipyrromethane

Using 3,5-Dimethoxybenzaldehyde, it was synthesized under the same conditions as 5- (4-methoxyphenyl) dipyrromethane.

Scheme 2

Example 3:

Method for preparing 5- (4-Bromophenyl) dipyrromethane

It was prepared by synthesizing under the same conditions as 5- (4-methoxyphenyl) dipyrromethane using 4-Bromobenzaldehyde.

¹ H-NMR: 5.43 (s, 1H, meso-H), 5.89 (m, 2H, pyrrole-H), 6.17 (q, 2H, pyrrole-H), 6.71 (q, 2H, pyrrole-H), 7.09 (d, 2H, Ar-H), 7.44 (d, 2H, Ar-H), 7.90 (br s, 2H, NH)

Scheme 3

Example 4:

Method for preparing 1- (4-Methoxybenzoyl) -5- (4-methoxyphenyl) dipyrromethane

After dissolving 5- (4-Methoxyphenyl) dipyrromethane in THF, EtMgBr (5.5 equiv.) Was added, stirred at room temperature under nitrogen for 1 hour, and then 4-anisoylchloride (1.2 equiv.) Was added to the reaction vessel for 12 hours at room temperature. After stirring for a while, a saturated NH ₄ Cl aqueous solution was added to the reaction vessel to stop the reaction, and extracted with dichloromethane, and then all organic solvents were evaporated and separated by column chromatography.

Scheme 4

Example 5:

{5-[{5 '-[{5- [Hydroxy- (4-methoxyphenyl) methyl] -1H-pyrrol-2-yl}-(4-methoxyphenyl) methyl] -1H, 1'H- [2,2 Method for preparing '] bipyrrolyl-5-yl}-(4-metho-xyphenyl) methyl] -1H-pyrrol-2-yl}-(4-methoxyphenyl) methanol

Dissolve 1- (4-Methoxybenzoyl) -5- (4-methoxyphenyl) dipyrromethane in acetonitrile (5 x 10 ^-3 M), add NH ₄ Cl (10 equiv.), And stir for 5 minutes at room temperature. After adding DDQ (3 eq.) And stirring at room temperature for 1 hour, water was added to the reaction vessel to stop the reaction, extracted with dichloromethane, all solvents were evaporated, dissolved in methanol and transferred to a hydrogenation vessel. Pd / C was added and hydrogenated. After the reaction, the remaining catalyst was filtered off, THF was added, NaBH ₄ (100 eq.) Was added thereto, stirred at room temperature for 1 hour, and water was added to the reaction vessel. NaBH ₄ was decomposed, extracted with dichloromethane, and evaporated, followed by vacuum drying for 30 minutes.

Scheme 5

Scheme 6

Example 6:

Method for preparing 5,10,15,20-Tetra (4-methoxyphenyl) sapphyrin

{5-[{5 '-[{5- [hydroxy- (4-methoxyphenyl) methyl] -1H-pyrrol-2-yl}-(4-met-hoxyphenyl) methyl] -1H, 1'H- [2 , 2 '] bipyrrolyl-5-yl}-(4-methoxyphenyl) met-hyl] -1H-pyrrol-2-yl}-(4-methoxyphenyl) methanol (1equiv.) Was dissolved in acetonitrile and then NH ₄ Cl (10 equiv.) and pyrrole (1 equiv.), add BF ₃ · OEt ₂ (0.1 equiv.) in an ice bath, stir for 30 minutes, add DDQ (3 equiv.), and stir at room temperature for 1 hour. , Solvents were all evaporated and prepared by column chromatography.

Scheme 7

Example 7:

Method for preparing 5,10,15,20-Tetra (4-hydroxyphenyl) sapphyrin

5,10,15,20-tetra (4-methoxyphenyl) sapphyrin was added to a round bottom flask and CS ₂ was dissolved. BBr ₃ was added and stirred at room temperature, and then the solvents were all evaporated, followed by CH ₂ Cl ₂ / Hexane. Prepared by recrystallization.

Scheme 8

Example 8:

Method for preparing 4-Phnoxy bridged sapphyrin dendrimer

Put 5,10,15,20-tetra (4-hydroxyphenyl) sapphyrin and K ₂ CO ₃ , 18-crown-6 in a round bottom flask, add THF to dissolve, add dendron to the reaction vessel, and stir at room temperature. All organic solvents were evaporated and the remaining material was dissolved in THF / EtOH mixed solvent, KOH aqueous solution was added and refluxed. The mixture was extracted with CH ₂ Cl ₂ , all solvents were evaporated and separated by column chromatography.

Scheme 9

Example 9:

Method for preparing 4-phenoxy bridged sapphyrin dendrimer Er (III) complex

4-Phenoxy bridged sapphyrin dendrimer, erbium acetate hexahydrate, and triethylamine were added together in methanol / chloroform and refluxed in air.The reaction was terminated after about 12 hours, cooled to room temperature, and then the solvent and triethylamine were removed under reduced pressure. After separation, the resulting complex was prepared by drying under vacuum and recrystallization.

Scheme 10

Example 10

Method for preparing 1- (4-Methoxybenzoyl) -5- (4-methoxyphenyl) dipyrromethane

Dissolve 5- (3,5-Dimethoxyphenyl) dipyrromethane in THF, add EtMgBr (5.5 equiv.), Stir at room temperature under nitrogen for 1 hour, and then add 3,5-dimethoxybenzoyl chloride (1.2 equiv.) To the reaction vessel. After stirring for 12 hours at room temperature, a saturated NH ₄ Cl aqueous solution was added to the reaction vessel to stop the reaction, extracted with dichloromethane, and all organic solvents were evaporated and separated by column chromatography.

Scheme 11

Example 11:

{5-[{5 '-[{5- [Hydroxy- (3,5-dimethoxyphenyl) methyl] -1H-pyrrol-2-yl}-(3,5-dimethoxyphenyl) methyl] -1H, 1'H- Preparation of [2,2 '] bipyrrolyl-5-yl}-(3,5-dimethoxyphenyl) methyl] -1H-pyrrol-2-yl}-(3,5-dimethoxy-phenyl) methanol

Dissolve 1- (3,5-Dimethoxybenzoyl) -5- (3,5-dimethoxyphenyl) dipyrromethane in acetonitrile (5 x 10 ^-3 M), add NH ₄ Cl (10 equiv.), And stir at room temperature for 5 minutes. After adding DDQ (3 eq.) To the reaction vessel and stirring at room temperature for 1 hour, water was added to the reaction vessel to stop the reaction, extracted with dichloromethane, and evaporated all the solvents, dissolved in methanol, and placed in a hydrogenation vessel. After transfer, Pd / C was added and hydrogenated. After the reaction, the remaining catalyst was filtered out, THF was added, NaBH ₄ (100 eq.) Was added thereto, stirred at room temperature for 1 hour, and water was added to the reaction vessel. The NaBH ₄ remaining after the reaction was decomposed and extracted with dichloromethane, and all solvents were evaporated, followed by vacuum drying for 30 minutes.

Scheme 12

Scheme 13

Example 12:

Method for preparing 5,10,15,20-Tetra (3,5-dimethoxyphenyl) sapphyrin

{5-[{5 '-[{5- [hydroxy- (3,5-dimethoxyphenyl) methyl] -1H-pyrrol-2-yl}-(3,5-dimehoxyphenyl) methyl] -1H, 1'H- Dissolved [2,2 '] bipyrrolyl-5-yl}-(3,5-dimethoxyphe-nyl) methyl] -1H-pyrrol-2-yl}-(3,5-dimethoxyphenyl) methanol (1equiv.) In acetonitrile After NH ₄ Cl (10 equiv.) And pyrrole (1 equiv.) Were added, BF ₃ · OEt ₂ (0.1 equiv.) Was added to an ice bath, stirred for 30 minutes, and then DDQ (3 equiv.) Was added thereto at room temperature. After stirring for 1 hour, the solvents were all evaporated and prepared by separation by column chromatography.

Scheme 14

Example 13:

Method for preparing 5,10,15,20-Tetra (3,5-dihydroxyphenyl) sapphyrin

Add 5,10,15,20-tetra (3,5-dimethoxyphenyl) sapphyrin to a round bottom flask, add CS ₂ to dissolve, add BBr ₃ , stir at room temperature, evaporate all solvents, and remove CH ₂ Cl ₂ / Prepared by recrystallization with Hexane.

Scheme 15

Example 14

Synthesis of 3,5-Phnoxy bridged sapphyrin dendrimer

In a round bottom flask, add 5,10,15,20-tetra (3,5-dihydroxyphenyl) sapphyrin and K ₂ CO ₃ , 18-crown-6 and dissolve in THF. Add dendron to the reaction vessel and stir at room temperature. The organic solvent is evaporated and the remaining material is dissolved in a THF / EtOH mixed solvent, and then KOH aqueous solution is added and refluxed. Extract with CH ₂ Cl ₂ , evaporate all solvents and separate by column chromatography

Scheme 16

Example 15:

Method for preparing 3,5-Phenoxy bridged sapphyrin dendrimer Er (III) complex

3,5-Phenoxy bridged sapphyrin dendrimer, erbium acetate hexahydrate, and triethylamine were added together in methanol, refluxed in air, and after about 12 hours, the reaction was completed and cooled to room temperature. Then, the solvent and triethylamine were removed under reduced pressure. After separation, the resulting complex was prepared by drying under vacuum and recrystallization.

Scheme 17

Example 16:

Method for preparing 1- (4-Bromobenzoyl) -5-bromophenyldipyrromethane

After dissolving 4-Bromophenyldipyrromethane in THF, EtMgBr (5.5 equiv.) Was added, stirred at room temperature under nitrogen for 1 hour, and then 4-bromobenzoyl chloride (1.2 equiv.) Was added to the reaction vessel and stirred at room temperature for 12 hours. In the reaction vessel, saturated NH ₄ Cl aqueous solution was added to stop the reaction. The mixture was extracted with dichloromethane, and all organic solvents were evaporated and separated by column chromatography.

Scheme 18

Example 17:

{5-[{5 '-[[5- (4-Bromobenzoyl) -pyrrol-2-ylidene]-(4-bromophenyl) -methyl]-(1'H- [2,2'] bipyrrolyl] -5- Method for preparing ylidene}-(4-bromophenyl) -methyl] -1H-pyrrol-2-yl}-(4-bromophenyl) methanone

Dissolve 1- (4-Bromobenzoyl) -5-bromophenyldipyrromethane in acetonitrile (5 x 10 ^-3 M), add NH ₄ Cl (10 equiv.), Stir at room temperature for 5 minutes, and then add DDQ (3 eq. After stirring for 1 hour at room temperature, water was added to the reaction vessel to stop the reaction, extracted with dichloromethane, and evaporated all the solvents, dissolved in methanol, transferred to a hydrogenation vessel, and then added with Pd / C and hydrogenated. After the reaction, the remaining catalyst was filtered off, THF was added, NaBH ₄ (100 eq.) Was added thereto, and stirred at room temperature for 1 hour. Water was added to the reaction vessel to decompose the remaining NaBH ₄ after the reaction and dichloromethane. Extraction was carried out, followed by evaporation of the solvent, followed by vacuum drying for 30 minutes.

Scheme 19

Scheme 20

Example 18:

Method for preparing 5,10,15,20-Tetra (3,5-dihydroxyphenyl) sapphyrin

{5-[{5 '-[[5- (4-Bromobenzoyl) -pyrrol-2-ylidene]-(4-bromophenyl) methyl]-(1'H- [2,2'] bipyrrolyl] -5-ylidene }-(4-bromophenyl) methyl] -1H-pyrrol-2-yl}-(4-bromophenyl) methanone (1equiv.) Was dissolved in acetonitrile and NH ₄ Cl (10 equiv.) And pyrrole (1 equiv.) Were dissolved. After adding BF ₃ · OEt ₂ (0.1 equiv.) In an ice bath and stirring for 30 minutes, DDQ (3 equiv.) Was added and stirred at room temperature for 1 hour, and then the solvents were all evaporated and separated by column chromatography. It was prepared by.

Scheme 21

Example 19:

Process for preparing phenyl-phenyl direct linked sapphyrin dendrimer

Put bromophenyl sappyrin in a round bottom flask, dissolve in THF, add n- BuLi under nitrogen, stir at -78 ° C, add ZnCl ₂ to the reaction vessel, stir at room temperature, and add another dendron and Pd (PPh _{3 4} ) dissolved in THF and stirred at room temperature, mixed in a flask with porphyrin, evaporated all organic solvents, dissolved in THF / EtOH mixed solvent, added KOH aqueous solution and refluxed, followed by CH ₂ Cl ₂ After extraction, the solvents were all evaporated and prepared by separation by column chromatography.

Scheme 22

Example 20:

Process for the preparation of phenyl-phenyl direct linked sapphyrin dendrimer Er (III) complex

Sapphyrin dendrimer, erbium acetate hexahydrate and triethylamine were added, dissolved in methanol and refluxed in air. After about 12 hours, the reaction was completed and cooled to room temperature. After removal of the solvent and triethylamine under reduced pressure, separation was carried out by column chromatography. The resulting complex was prepared by drying under vacuum and recrystallization.

Scheme 23

By the present invention, the effect of simultaneously solving the problems of the recently developed optically amplified material is expected.

(a) The concentration of Er ³⁺ doped into the conventional optical fiber silica is limited to about 100-1000 ppm, and if it is higher than that, the non-luminescence process mainly occurs due to the interaction between the Er ⁺³ ions, and the optical amplification efficiency drops sharply. For this reason, high gain optical amplification is not possible with Er ³⁺ doping in silica optical fibers, and therefore it is difficult to expect about 30 dB of optical amplification in the form of a planar waveguide optical integrated circuit.

(b) Until recently, many researches have been conducted on the development of optical amplification materials by doping Er ³⁺ rare earth ions or chelate complexes to inorganic or polymeric media. However, in the conventional master-guest system, the doping concentration is limited due to the low solubility of rare earth metals in the medium. Therefore, high photoamplification effect cannot be expected. When introduced at high concentration, the phase between rare earth ion and silica as well as agglomeration of ion-ion There is a problem in that separation occurs rather lowering the optical amplification effect.

Claims (4)

A complex salt type porphyrin dendrimer compound comprising rare earth ions having the following chemical formula 1 having excellent solubility in a polymer medium and having no agglomeration of rare earth metals and thus having no ion-ion interaction. [Chemical Structural Formula 1] The complex salt polypyrrole dendrimer compound of claim 1, wherein the complex salt polypyrrole dendrimer compound including the rare earth ion is a 4-Phenoxy bridged sapphyrin dendrimer Er (III) complex having the following Chemical Formula 2: . [Chemical Structural Formula 2] The complex salt polypyrrole dendrimer compound of claim 1, wherein the complex salt pyrroline dendrimer compound including rare earth ions is a 4-Phenoxy bridged sapphyrin dendrimer Er (III) complex having the following Chemical Formula 3: . [Chemical Structural Formula 3] The complex salt polypyrrole dendrimer compound of claim 1, wherein the complex salt polypyrrole dendrimer compound including the rare earth ion is a 4-Phenoxy bridged sapphyrin dendrimer Er (III) complex having the following Chemical Formula 4. . [Chemical Structural Formula 4]