KR20040014020A - Synthetic method of Terpyridine―Ruthenium complex - Google Patents

Abstract

PURPOSE: A synthesis method of a terpyridine-ruthenium complex is provided. The terpyridine-ruthenium complex is diamagnetic material and useful as an electroluminescence. CONSTITUTION: A synthesis method of a terpyridine-ruthenium complex comprises the steps of: dissolving 2.0g(0.23 mmol) of dendrimer(Gn-mTpy) in 100ml of methanol; adding 1.0g(2.3 mmol) of RuCl3-3H2O into the solution; stirring the mixture for 6 hours until the spectrum by 1H NMR does not appeared; distilling the mixture under reduced pressure to remove the solvent; washing the resulting product with pentane and diethylether; and recrystallizing the dendrimer in methanol, wherein the dendrimer(Gn-mTpy) contains siloxanetetramer in its center; and the generation growth is accomplished by using arylalcohol.

Description

Synthetic method of Terpyridine-Ruthenium complex

The present invention relates to a method for synthesizing a ruthenium complex of terpyridine widely used as an electroluminescent device, and more particularly, in the process of synthesizing a carbosilane dendrimer using siloxane tetramer, terpyridine (2,2: 6, 2-terpyridine was added and as a trifunctional ligand, terpyridine reacted with ruthenium ions on the surface of the dendrimer to form a diamagnetic substance, a terpyridine-ruthenium complex. Another object of the present invention is to provide a method for synthesizing terpyridine-ruthenium complexes by adding a pyridine derivative to synthesize terpyridine-ruthenium-terpyridine.

Prior art in this field with respect to the present invention has not been identified.

Synthesis of general siloxane dendrimers is well known in the present inventors' report.

See: 1. Preparation And Termination Of Carbosilane Dendrimers Based On A Siloxane Tetramer As A Core Molecule, C. Kim, K. An, J. Organomet. Chem. 547 (1997) 55. 2. Silane Arborols; XV: Dendritic Carbosilane Based On Siloxane Tetramers, C. Kim, A. Kwon, Synthesis (1998) 105. 3. Preparation And Termination Of Carbosilane Dendrimer Based On Siloxane Tetramer, C. Kim, E. Park, J. Korean Chem. Soc. 42 (1998) 277. 4. End-Capped Carbosiloxane Dendrimers With Cholesterol And Pyridine Derivatives, C. Kim, J. Park, J. Organomet. Chem. 629 (2001) 194. 5.C. Kim, H. Kim, Synthesis And Characterization Of End-Functionalized Carbosiloxane Dendrimers, J. Polym. Sci. A: Polym. Chem., 40. (2002) 326-333.].

Terpyridine is generally used as an organic electronic device, DNA-support, RNA hydrolyzate, and the like, and complexes thereof are widely used as organic light emitting devices and biochemical indicators.

[Note: 1. Tears, D. K. C .; McMillin, D. R. Coord. Chem. Rev. 2001, 211, 195. 2. McGarrah, J. E .; Kim, Y.-J .; Hissler, M .; Eisenberg, R. Inorg. Chem. 2001, 40, 4510. 3. Hobert, S. E .; Carney, J. T .; Cummings, S. D. Inorg. Chim. Acta 2001, 318, 89.]

Dendrimers generally have a spherical symmetry and the planar terpyridine functional groups are all present on the surface of the compound so that the dendrimers only carry the functional groups.

Terpyridine is present on the surface of the dendrimer is a trifunctional ligand (tridental ligand) has a property that easily binds to the metal.

In recent years, these properties have been used to synthesize compounds that are expected to have excellent luminous effects.

[Note: 1. F .; Gestermann, S .; Hesse, R .; Schwierz, H .; Windisch, B. Prog. Polym. Sci. 2000, 25, 987. 2. Inoue, K. Prog. Polym. Sci. 2000, 25, 453. 3.Astruc, D .; Chardac, F. Chem. Rev. 2001, 101, 2991. 4. Bossman, AW; Janssen, HM; Meijer, EW Chem. Rew. 1999, 99, 1665.]

The present invention relates to the synthesis of terpyridine-ruthenium-terpyridine derivatives on the surface of the dendrimer and the synthesis of siloxane polymer and 4- (hydroxyhexa) 2,2: 6,2-terpyridine Catalysis (dehydrogenation) was combined to add ruthenium ions (RuCl ₃ ) to make a semi-magnetic compound, and then terpyridine was introduced into the reactor to synthesize a new compound.

The present inventors synthesized a compound in which terpyridine-ruthenium ion is coordinated by adding ruthenium ion (RuCl ₃ ) to the first to third generation compounds in which terpyridine is added to the outermost portion of a carbosilane dendrimer. By adding terpyridine derivatives to the compounds, we attempted to synthesize new compounds that significantly improved the performance of coordination compounds.

By modeling the compound, terpyridine functional groups were added to the siloxane polymer which is easier to synthesize than the dendrimer to realize the convenience of synthesis that the spherical dendrimer cannot have.

The technical problem to be achieved by the present invention is;

1. Synthesis of terpyridine-ruthenium ion complex dendrimers (first to third generation)

2. Synthesis of dendrimers with terpyridine-ruthenium-terpyridine complexes (first to third generations)

3. Synthesis of terpyridine-ruthenium ion complex on siloxane polymer to solve the technical problems of paragraphs 1 and 2 more easily and to form terpyridine-ruthenium-terpyridine complex on siloxane polymer will be.

1 is a method for preparing a terpyridine-ruthenium-terpyridine complex which is the subject of the present invention.

A synthesis process

Figure 2 of the first to third generation compounds of terpyridine-ruthenium-terpyridine synthesized in the present invention

¹³ C NMR Spectrum with Top View

3 is synthesized by introducing terpyridine-ruthenium-terpyridine into the stem of the siloxane polymer

Synthesis of Compounds and Floor Plans of Unit Cells

In the present invention, a terpyridine derivative in the chemical formula shown in FIG. Synthesis method for coordinating to form terpyridine-ruthenium-terpyridine complex, terpyridine derivative on the product and siloxane polymer to synthesize terpyridine-ruthenium complex on the surface, and then It is characterized by obtaining a series of processes and products for adding pyridine.

In Formula 1 (Scheme), Gn-mTPY means m (m = 4, 8, 16) terpyridine (TPY) of the n-generation (n = 1 to 3) dendrimers (Gn-Ru- mTPY is a model in which ruthenium ions (RuCl ₃ ) are added to each generation of dendrimers (1 to 3) and means that n generations have m terpyridine-ruthenium complexes and Gn-m [TPY-Ru -TPY] means a model in which a terminal ruthenium ion is substituted with a terpyridine derivative.

In the present invention, by using RdCl ₂ (COD) as a catalyst using the synthesis method of the formula 1, 4-hydroxyhexa-2,2; 6,2-terpyridine ether is added to the siloxane polymer chain to have terpyridine. A polymer was synthesized, and as shown in Chemical Formula 1, platinum ions were added and a chemical process of changing a ligand was expressed.

The reaction products of Formulas 1 and 2 have been identified by nuclear magnetic resonance spectra and UV spectra and various embodiments of the invention are described below.

The present invention is a compound formed by adding terpyridine back to the ruthenium complex using the synthesis method of the materials shown in Chemical Formulas 1 and 2 and has 16 functional groups on the surface. The first and second generation compounds have the same shape and have four or eight functional groups on the surface.

Formula 4 represents a chemical process of synthesizing a ruthenium complex by reacting a siloxane polymer with terpyridine with RuCl ₃ and adding pyridine again to the synthesis of a complex consisting of terpyridine-ruthenium-terpyridine. .

This chemical process is an invention of a method that can more easily achieve the chemical process that can be achieved on the carbosilane dendrimer can be formed by the formula (1).

Formula 5 is a schematic diagram of the compound synthesized by Formula 4 can be expected to be applied to a material that does not require accurate molecular properties.

(Example 1)

Molecular formula (see Formula 2 above)

In the synthesis of the molecule, the siloxane tetramer is present as a nuclear molecule in the center of the dendrimer having 16 terpyridine functional groups of the third generation, and the growth up to the third generation is achieved by using aryl alcohol to grow functional groups and dichloromethylsilane (HMeSiCl). ₂ ) and hydrolylation of allyloxy (CH ₂ = CHCH ₂ O-) groups, and for the introduction of terpyridine end groups, dimethyl crorosilane (HMe ₂ SiCl) is added to the hydrosyl group in the allyloxy functional group. The synthesis method was synthesized by the inventor as a model in which 4-hydroxyhexa-2,2; 6,2-terpyridine ether was added in the presence of TMEDA (tetrametnyethylenediamine) in the presence of TMEDA.

Here, the method of adding ruthenium ion is as follows, and the introduction of four functional groups of the first generation and the introduction of eight functional groups of the second generation are performed by the same method.

2.0 g (0.23 mmol) of the third generation 16 terpyridine-added dendrimer (G3-16Tpy) was dissolved in 100 ml of methanol, and then stirred under reflux for 6 hours by adding 1.0 g (2.3 mmol) of RuCl ₃ H ₂ O. The solvent is then removed by distillation under reduced pressure distillation (reflux until no spectra is shown by ¹ H NMR), the reaction product is washed with pentane and diethyl ether and recrystallized from methanol.

(Example 2)

* Molecular formula (see formula 3)

2.4 g of G3-16Tpy was sesspanned in 125 ml of methanol and stirred at reflux for 2 hours by adding 0.9 g (3.8 mmol) terpyridine and 0.4 g (4.1 mmol) methylmorpholine (red clear solution Formed) Confirm that the reaction is terminated by ¹ H NMR, and then add an excess of NH ₄ PF ₆ to exchange the anion.

The product was removed in vacuo, washed with H ₂ O, pentane, diethyl ether and dried in vacuo to yield 2.4 g (0.54 mmol, 75%) of a red solid.

(Example 3)

Molecular formula

2.0 g (4.9 mmol) of terpyridine-added compound was dissolved in 250 ml of methanol, and 1.4 g (6.7 mmol) of RuCl ₃ H ₂ O was added thereto, followed by stirring under reflux for 6 hours ( ¹ H NMR Reflux is removed by distillation under reduced pressure, the reaction product is washed with pentane and diethyl ether and recrystallized from methanol.

(Example 4)

Molecular formula

A compound (Poly-Tpy-Ru) having terpyridine added to 2.1 g (3.4 mmol) siloxane polymer (separated in 125 ml of methanol), 1.0 g (4.3 mmol) terpyridine and 0.4 g (3.9 mmol) methylmo The mixture was refluxed for 2 hours with the addition of porin (red clear solution was formed), and then confirmed that the reaction was terminated by ¹ H NMR, and an excess of NH ₄ PF ₆ was added to exchange anions.

The product was removed in vacuo, washed with H ₂ O, pentane, diethyl ether and dried in vacuo to give 2.4 g (0.54 mmol, 75%) of a red solid.

As described in detail above, the compounds synthesized by the present invention are all functional groups oriented on the surface of the carbosilane dendrimer as a compound based on a terpyridine derivative and a ruthenium complex of the polymer as a functional functional group.

The compounds in particular have a feature that can be widely used as an electronic device, a light emitting device.

The compound is divided into three sizes and is classified into three types from the first generation to the third generation. In the case of a compound formed of a siloxane polymer, which is a model for improving the applicability of the compound, various applications are possible when accurate molecularity is not required.

Claims (4)

Siloxane tetramer is present as a nuclear molecule in the center of dendrimer (Gn-mTpy) having m tertidine functional groups (n = 1 to 3) m (m = 4,8,16) Growth to grow functional group using aryl alcohol, dichloromethylsilane (HMeSiCl ₂ ) and allyloxy (CH ₂ = CHCH ₂ O-) groups grow by hydrosilylation and introduction of terpyridine end group For this purpose, dimethyl crorosilane (HMe ₂ SiCl) was added to the allyloxy functional group by hydrosilylation, and 4-hydroxyhexa-2,2; 6,2-terpyridine ether was added to the dendrimer in the presence of tetramethnyethylenediamine (TMEDA). In (Gn-mTpy); 2.0 g (0.23 mmol) of the dendrimer (Gn-mTpy) was dissolved in 100 ml of methanol, and then 1.0 g (2.3 mmol) of RuCl ₃ H ₂ O was added thereto for 6 hours until no spectrum was observed by ¹ H NMR. A method for synthesizing terpyridine-ruthenium complex, which is obtained by stirring under reflux, removing the solvent by distillation under reduced pressure, washing the reaction product with pentane and diethyl ether, and recrystallization from methanol. The method of claim 1; The 2.4 g of Gn-mTpy was separated in 125 ml of methanol, and 0.9 g (3.8 mmol) of terpyridine and 0.4 g (4.1 mmol) of methylmorpholine were refluxed for 2 hours, followed by reaction by ¹ H NMR. After confirming termination, an excess of NH ₄ PF ₆ is added to exchange the anion, The product is a method of synthesizing terpyridine-ruthenium complex, characterized in that the product is obtained by removing the solvent in vacuo, washing with H ₂ O, pentane, diethyl ether and drying in vacuo. Of the terpyridine it was added to the siloxane polymer compound (Polysiloxane-Tpy-Ru) 2.0g (4.9 mmol) of was dissolved in 250ml of methanol and then added to the RuCl ₃ .3H ₂ O in 1.4g (6.7 mmol) for 6 hours ^per Terpyridine-ruthenium complex, which was obtained by stirring under reflux until the spectrum was absent by H NMR, removing the solvent by distillation under reduced pressure, washing the reaction product with pentane and diethyl ether, and recrystallization from methanol. Method of synthesis. The method of claim 3; 2.1 g (3.4 mmol) of the compound in which terpyridine was added to the siloxane polymer (separation) in 125 ml of methanol, 1.0 g (4.3 mmol) of terpyridine and 0.4 g (3.9 mmol) of methyl After adding the morpholine and refluxing for 2 hours to terminate the reaction by ¹ H NMR, an excess of NH ₄ PF ₆ was added to exchange anions. The product was removed from the solvent in vacuo, washed with H ₂ O, pentane, diethyl ether and dried in vacuo to give 2.4 g (0.54 mmol, 75%) of a red solid. Synthesis Method of Ruthenium Complex