KR100704655B1 - Light emitting polymer or derivative thereof and electroluminescent device using same - Google Patents

Abstract

The present invention relates to a light emitting polymer represented by Formula 1:

[Formula 1]

Where R ₁ and R ₂ are C _1-20 linear or branched alkyl group,

, R₄-HTL(정공수송층) 또는 R₅-ETL(전자수송층)이고;

, R ₄ -HTL (hole transport layer) or R ₅ -ETL (electron transport layer);

Where R ₃ is C _1-20 linear or branched alkyl group;

R ₄ and R ₅ C _1-20 linear or branched alkyl group.

Electroluminescent, PCPP, poly [4,4-bis (2-ethylhexyl) -4H-cyclopenta [def] phenanthrene-2,6-diyl], blue light emitting polymer, LED, energy device

Description

Light emitting polymers or derivatives thereof and electroluminescent devices using the same             

1 is a cross-sectional view of an electroluminescent device using a light emitting polymer according to the present invention.

2 is a graph showing an electroluminescence (EL) spectrum of a single layer light emitting device using PCPP.

3 is a graph showing the EL spectrum of a single layer light emitting device using PDHCPP.

4 is a graph illustrating current-voltage characteristics of a single layer device using PCPP.

5 is a graph showing the current-voltage characteristics of a single layer device using PDHCPP.

6 is a graph showing the light emission efficiency characteristics according to the current of a single layer device using PCPP.

7 is a graph illustrating the light emission efficiency characteristics according to the current of a single layer device using PDHCPP.

<Description of the symbols for the main parts of the drawings>

1 substrate 2 translucent electrode

3: hole transport layer 4: polymer light emitting layer

5: metal electrode

The present invention relates to a light emitting polymer represented by Formula 1:

[Formula 1]

Where R ₁ and R ₂ are C _1-20 linear or branched alkyl group,

, R₄-HTL(정공수송층) 또는 R₅-ETL(전자수송층)이고;

, R ₄ -HTL (hole transport layer) or R ₅ -ETL (electron transport layer);

Where R ₃ is C _1-20 linear or branched alkyl group;

R ₄ and R ₅ C _1-20 linear or branched alkyl group.

Over the years, efforts have been made in the design and synthesis of new light emitting polymers for the use of light emitting polymers in light-emitting diodes (LEDs). Among them, the development of blue light-emitting polymers is the main challenge, poly-para-phenylene (PPP) s, polythiophene (PT) s, polyfullerenes (PF) s, polyindenofullerenes (PIF) s, leather-poly- Para-phenylene (LPPP) s and the like were used as blue light emitting polymers, and various functional groups were applied to the side chains of polymers in order to improve processability and other electronic properties of light emitting polymers. Polyfullene and its derivatives have been most widely developed with relatively high blue luminous efficiency. One of the problems associated with blue light emitting devices using these polymers is that they exhibit low luminous efficiency and efforts are being made to solve this problem.

Accordingly, the present inventors have studied a material having excellent luminous efficiency by dissolving in an organic solvent while emitting blue fluorescent light such as polyfullerene and smoothing electron transport. As a result, it was found that PCPP and its derivatives using substituted cyclopentaphenanthrene as monomers exhibited the above characteristics and completed the present invention.

Accordingly, an object of the present invention is to provide a light emitting polymer using pentaphenanthrene substituted as a monomer, which can be dissolved in an organic solvent while emitting fluorescent light, facilitates transport of electrons, and has good luminous efficiency.

It is also an object of the present invention to provide an electroluminescent device and an optical energy conversion device using the light emitting polymer.

In order to achieve the above object, the present invention provides a light emitting polymer represented by the following Chemical Formula 1:

Where R ₁ and R ₂ are C _1-20 linear or branched alkyl group,

, R₄-HTL(정공수송층) 또는 R₅-ETL(전자수송층)이고;

, R ₄ -HTL (hole transport layer) or R ₅ -ETL (electron transport layer);

Where R ₃ is C _1-20 linear or branched alkyl group;

R ₄ and R ₅ C _1-20 linear or branched alkyl group.

In addition, the HTL (hole transport layer)

Is;

The ETL (electron transport layer)

이고,

ego,

Where R ₆ is OR ₇ , or R ₈ , and R ₇ , R ₈ are C _1-20 linear or branched alkyl group.

Examples of the light emitting polymer compound of Formula 1 synthesized in the present invention,

Poly [4,4-bis (2-ethylhexyl) - 4H - cyclopenta [def] phenanthrene-2,6-Dail] (PCPP), poly [(4,4-dimethyl-hexyl) - 4H - cyclopenta [ def] phenanthrene-2,6-Dail] (poly [4,4-bis ( 2-ethylhexyl) - 4H -cyclopenta [def] and phenanthrene-2,6-diyl], hereinafter referred to "PDHCPP"), poly [ 4,4-bis (4'-n- octyloxy-phenyl) cyclopenta [def] phenanthrene-2,6-Dail] (poly [4,4-bis ( 4'-n-octyloxyphenyl) - 4H -cyclopenta [ def] phenanthrene-2,6-diyl] , hereinafter "PBOPCPP" referred to), poly [4,4-bis (6- (9H - carbazole-9-yl) hexyl) - 4H - cyclopenta [def] phenanthrene Transistor Dail 2,6)] (poly [4,4-bis (6- (9 H -carbazole-9-yl) hexyl) - 4H -cyclopenta [def] phenanthrene-2,6-diyl], hereinafter referred to as " Cz-PCPP "), poly [4- (6- (4- (5- (5-phenyl-1,3,4-oxadiazol-2-yl) phenoxy) hexyl) -4- (6- ( 9H -Carbazol-9-yl) hexyl) -4H -cyclopenta [ def ] phenanthrene-2,6-diyl] (poly [4- (6- (4- (5-phenyl-1,3,4-oxadiazole -2-yl) phenoxy) hexyl) -4- (6- (9 H -carbazole-9-yl) hexyl) - 4H - cyclopenta [def] phenanthre ne-2,6-diyl], hereinafter referred to as "Oxd-Cz-PCPP", and these polymers are well soluble in general organic solvents and have high luminous efficiency, and thus may be useful as materials for electroluminescent devices. Can be.

A polymer compound represented by the formula (1) of said compound is poly [4,4-bis (2-ethylhexyl) - 4H - cyclopenta [def] phenanthrene-2,6-Dail] (PCPP), poly [ (4,4-dimethyl-hexyl) - 4H - cyclopenta [def] phenanthrene-2,6-Dail] a, and a compound represented by the general formula (2) is poly [4,4-bis (4'-n- octyl Oxyphenyl) cyclopenta [ def ] phenanthrene-2,6-diyl], the compound represented by the formula (3) is a poly [4,4-bis (6- ( 9H -carbazol-9-yl) hexyl)- 4H -cyclopenta [ def ] phenanthrene-2,6-diyl) and poly [4- (6- (4- (5- (5-phenyl-1,3,4-oxadiazol-2-yl) phenoxy) Hexyl) -4- (6- ( 9H -carbazol-9-yl) hexyl) -4H -cyclopenta [ def ] phenanthrene-2,6-diyl].

In the method for synthesizing the compound, a substituent is introduced into cyclopentaphenanthrene, then hydrogenated using palladium, a bromo group is introduced using copper bromide (CuBr ₂ ), and carbon disulfide (CS ₂ ) is further introduced. Oxidation reaction with and bromine (Br ₂ ) to obtain a cyclo penta phenanthrene monomer, and through the Yamamoto coupling reaction to obtain a cyclo penta phenanthrene polymer substituted with various substituents.

In the method of manufacturing an electroluminescent device of the present invention, as shown in the accompanying FIG. It is characterized by forming with PCPP and Oxd-Cz-PCPP.

The present invention synthesizes a PCPP derivative using a substituted cyclopentaphenanthrene as a monomer, which emits blue fluorescent light, such as polyfullerene, thereby facilitating the transport of electrons, so that the luminous efficiency is good and can be dissolved in an organic solvent. The manufacturing process is easy. In addition, there is an advantage that the polymer light emitting device can be used in the bendable electroluminescent device.

 First, the synthesis method of PCPP and its derivatives PDHCPP, PBOPCPP, Cz-PCPP and Oxd-Cz-PCPP using cyclopentaphenanthrene as a monomer as the light emitting material of the present invention will be described.

Synthesis of (PCPP) poly [cyclopenta [def] phenanthrene-2,6-Dail 4,4-bis (2-ethylhexyl) - - 4H]

As shown in the above scheme, the compound cyclopenta-phenanthrene (formula 1a) and ethylhexyl bromide (formula 1b) are reacted with sodium hydroxide to give 4,4-bis- (2-ethylhexyl) -4H -cyclopenta [ def ] Phenanthrene (Formula 1c) and the 4,4-bis- (2-ethylhexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 1c) by hydrogenation with palladium to give 4,4-bis- (2-ethylhexyl) -8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1d) was obtained, and the 4,4-bis- (2-ethylhexyl) -8,9-di Hydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1d) was reacted with an aluminum dibromide complex to give 2,6-dibromo-4,4-bis- (2-ethylhexyl) -8,9-di Hydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1e) was obtained, and 2,6-Dibromo-4,4-bis- (2-ethylhexyl) -8,9-dihydro- 4H- was obtained . cyclopenta [def] phenanthrene (formula 1e) Through the oxidation of 2,6-dibromo-4,4-bis (2-ethylhexyl) - 4H-cyclopenta [def] phenanthrene (Formula 1f) of the 2,6-dibromo-4, to give , 4-bis (2-ethylhexyl) - 4H-cyclopenta [def] phenanthrene (formula 1f) a polyester through the Yamamoto coupling reaction, [4,4-bis (2-ethylhexyl) - 4H-cyclopenta [ def ] phenanthrene-2,6-diyl (PCPP) (Formula 1 g) is obtained.

Synthesis of (PDHCPP) poly [cyclopenta [def] phenanthrene-2,6-Dail (4,4-dimethyl-hexyl) - - 4H]

As shown in the above scheme, the compound cyclopenta-phenanthrene (Formula 2a) and hexyl bromide (Formula 2b) are reacted with sodium hydroxide to give (4,4-dihexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 2). 2c), and the (4,4-dihexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 2c) was hydrogenated with palladium to give (4,4-dihexyl) -8,9-dihydro Obtain 4H -cyclopenta [ def ] phenanthrene (Formula 2d), and (4,4-dihexyl) -8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 2d). Reaction with the aluminum bromide bromide complex yields 2,6-dibromo- (4,4-dihexyl) -8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 2e), wherein , 6-Dibromo- (4,4-dihexyl) -8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 2e) was subjected to oxidation through 2,6-dibromo- (4, 4-die Hexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 2f) was obtained, and the 2,6-dibromo- (4,4-dihexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 2f) was obtained. Was subjected to Yamamoto polymer reaction using a nickel catalyst and end-capped with 9-bromoanthracene to obtain poly [(4,4-dihexyl) -4H -cyclopenta [ def ] phenanthrene-2,6-diyl]. (PDHCPP) (Formula 2 g) is obtained.

Synthesis of Poly [4,4-bis (4'-n-octyloxyphenyl) cyclopenta [ def ] phenanthrene-2,6-diyl] (PBOP-CPP)

As shown in the above scheme, compound 4H -cyclopenta [ def ] phenanthrene (Formula 3a) was subjected to hydrogenation to obtain 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 3b), The 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 3b) was subjected to bromination for 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene To obtain 2,6-dibromo by reacting the 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (formula 3c) with bromine (Formula 3c) 4H -cyclopenta [ def ] phenanthrene (Formula 3d), and 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 3d) were subjected to oxidation through 2,6- Dibromo-cyclopenta [ def ] phenanthren-4-one (Formula 3e) was obtained, and the 2,6-dibromo-cyclopentta [ def ] phenanthren-4-one (Formula 3e) was mixed with phenol. Zinc claw Id and hydrogen chloride gas was reacted with 2,6-dibromo-4,4-bis (4-hydroxyphenyl) cyclopenta [def] phenanthrene (Formula 3f) to obtain, and the 2,6-di-bromo Mo-4,4-bis (4-hydroxyphenyl) -cyclopenta [ def ] phenanthrene (Formula 3f) was subjected to alkylation reaction to give 2,6-dibromo-4,4-bis (4-octyloxy phenyl) cyclopenta [def] phenanthrene (yield the formula 3g), and the 2,6-dibromo-4,4-bis (4-octyloxy-phenyl) cyclopenta [def] phenanthrene (formula 3g ) To a Yamamoto polymer reaction using a nickel catalyst and end-capped with 9-bromoanthracene to poly [4,4-bis (4'-n-octyloxyphenyl) cyclopenta [ def ] phenanthrene-2, 6-dyl] (Formula 3h).

Poly [4,4-bis (6- (9H - carbazole-9-yl) hexyl) - 4H - cyclopenta [def] phenanthrene-2,6-Dail) Synthesis of (Cz-PCPP)

As shown in the above scheme, compound 9H -carbazole (Formula 4a) and 1,6-dibromohexane (Formula 4b) were mono-coupled with sodium hydride to give 9- (6-bromohexyl) -9H -carbazole Obtained (Formula 4c), the 9- (6-bromohexyl) -9H -carbazole (Formula 4c) and 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 4d) Reacted with sodium 9- (6- (2,6-dibromo-4- (6- ( 9H -carbazol-9-yl) hexyl) -4H -cyclopenta [ def ] phenanthren-4-yl) hexyl ) -9H -carbazole (Formula 4e), wherein 9- (6- (2,6-dibromo-4- (6- ( 9H -carbazol-9-yl) hexyl) -4H -cyclopenta [ def ] Phenanthren-4-yl) hexyl) -9H -carbazole (Formula 4e) was subjected to Yamamoto polymer reaction using a nickel catalyst, followed by end-capping with 9-bromoanthracene to give poly [4,4- Bis (6- ( 9H -carbazol-9-yl) hexyl) -4H -cyclopenta [ def ] phenanthrene-2,6-diyl)] (Cz-P CPP) (Formula 4f).

Poly [4- (6- (4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenoxy) hexyl) -4- (6- ( 9H -carbazol-9-yl) synthesis of the cyclopenta [def] phenanthrene-2,6-Dail] (Oxd-Cz-PCPP) - cyclohexyl) - 4H

As shown in the above scheme, compound 4-hydroxybenzohydrazide (Formula 5a) is coupled with compound benzoylchloride (Formula 5b) to form N-benzoyl-4-hydroxybenzohydrazide (Formula 5c). Obtained, and the N-benzoyl-4-hydroxybenzohydrazide (Formula 5c) was subjected to cyclization reaction using a cyonyl chloride (4- (5-phenyl-1,3,4-oxadiazole-2). -Yl) phenol (Formula 5d), and the (4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenol (Formula 5d) is prepared as 1,6-dibromohexane (Formula 5d). Coupling with 5e) yields 2- (4-((6-bromohexyl) oxy) phenyl) -5-phenyl-1,3,4-oxadiazole (Formula 5f) to give compound 2,6 -Dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 5g) and compound 9- (6-bromohexyl) -9H -carbazole (Formula 5h) and 2- (4-((6-bromo Hexyl) oxy) phenyl) -5-phenyl-1,3,4-oxadiazole (chemical Equation 5f) was reacted with sodium hydroxide to give 9- (6- (2,6-dibromo-4- (6- (4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenoxy C) hexyl) -4H -cyclopenta [ def ] phenanthren-4-yl) hexyl) -9H -carbazole (Formula 5i) to give 9- (6- (2,6-dibromo-4-) (6- (4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenoxy) hexyl) -4H -cyclopenta [ def ] phenanthren-4-yl) hexyl) -9H- Carbazole (Formula 5i) was subjected to Yamamoto polymer reaction using a nickel catalyst and end-capped with 9-bromoanthracene to give poly [4- (6- (4- (5-phenyl-1,3,4-oxa). diamond-2-yl) phenoxy) hexyl) -4- (6- (9H - carbazole-9-yl) hexyl) - 4H - cyclopenta [def] phenanthrene-2,6-Dail] (Oxd- Cz-PCPP) (Formula 5j) is obtained.

The present invention also relates to an electroluminescent device and an optical energy conversion device manufactured using the light emitting polymer.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are intended to illustrate the present invention in detail, and the scope of the present invention is not limited by the following examples.

<Example 1> poly [4,4-bis (2-ethylhexyl) cyclopenta [def] phenanthrene-2,6-Dail-4H] Preparation of (PCPP)

1) Synthesis of 4,4-bis- (2-ethylhexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 1c)

1H (5.3 mmol) of 4H -cyclopenta [ def ] para-xylene (Formula 1a) and a catalytic amount of trideethylammonium chloride were dissolved in 20 ml of dimethyl sulfoxide, followed by stirring at 60 ° C for 1 hour, followed by 2-ethylhexyl bromide (Formula 1b). 2.25 ml (12.61 mmol) were added. After stirring for 1 hour, 5 ml of 50% sodium hydroxide was added, followed by stirring at room temperature for 5 hours. An excess of ethyl acetate was added to form a sodium hydroxide precipitate, which was filtered off and the organic layer was neutralized with 100 ml of 1.0 M hydrochloric acid and extracted with 150 ml of water. The product was separated through a column chromatograph of the liquid residue resulting from vacuum distillation of the solvent of the remaining organic solution. 2 g (91%) of a colorless liquid were obtained.

Rf 0.64 (SiO ₂ , hexane 100%)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 0.46-0.92 (m, 30H), 2.19 (d, 2H, J = 4.2 Hz), 2.17 (d, 2H, J = 4.6 Hz), 7.52-7.63 (m, 4 H), 7.77-7. 81 (m, 4 H).

¹³ C-NMR (50 MHz, CDCl ₃ ): δ (ppm) 10.14, 13.82, 22.50, 27.09, 28.05, 33.89, 34.97, 44.02, 58.77, 120.34, 122.56, 125.12, 126.83, 127.60, 137.34, 149.06.

FAB-MS m / z 414.36 ([M + H] &lt; + &gt;, calcd 414.67).

2) Synthesis of 4,4-bis- (2-ethylhexyl) -8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1d)

2 g (4.82 mmol) of the compound of Formula 1c and 1 g of 10% palladium were dissolved in 100 ml of ethanol, followed by stirring at room temperature for 20 hours under hydrogen gas. After filtering off the catalyst, the residue was vacuum distilled to separate the product through a column chromatograph. 1.8 g (90%) of a colorless oil was obtained.

Rf 0.64 (SiO ₂ , hexane 100%)

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) 0.45-0.94 (m, 30H), 1.95 (d, 2H, J = 4.7 Hz), 1.94 (d, 2H, J = 5.1 Hz), 3.11 (s, 4H), 7.05-7.07 (m, 2H), 7.09-7.16 (m, 4H).

¹³ C-NMR (75 MHz, CDCl ₃ ): δ (ppm) 10.31, 13.97, 22.66, 26.15, 27.05, 28.27, 33.85, 34.88, 43.95, 58.09, 121.87, 124.52, 126.79, 129.98, 138.45, 147.69.

FAB-MS m / z 416.35 ([M + H] &lt; + &gt;, calcd 416.68).

3) Synthesis of 2,6-Dibromo-4,4-bis- (2-ethylhexyl) -8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 1e)

1.5 g (3.59 mmol) of the compound of Chemical Formula 1d obtained in 2) were dissolved in 80 ml of carbon tetrachloride, and 11.67 g of aluminum bromide complex was added thereto, followed by reaction at 80 ° C. for 5 hours. After the reaction, the by-products were removed using a filter paper, and the liquid residue generated after vacuum distillation of the solvent of the remaining solution was separated through a tube chromatograph. 1.88 g (91%) of pale yellow liquid were obtained.

Rf 0.58 (SiO ₂ , hexane 100%)

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) 0.57-0.95 (m, 30H), 1.92 (d, 2H, J = 4.9 Hz), 1.91 (d, 2H, J = 5.4 Hz), 3.07 ( s, 4H), 7.23 (s, 2H), 7.29 (s, 2H).

¹³ C-NMR (125 MHz, CDCl ₃ ) δ (ppm) 10.59, 14.25, 22.94, 25.88, 27.45, 28.45, 34.03, 35.29, 43.94, 58.97, 121.25, 125.64, 128.37, 131.66, 136.55, 149.48.

FAB-MS m / z 574.14 ([M + H] &lt; + &gt;, calcd 574.47).

4) Synthesis of 2,6-Dibromo-4,4-bis- (2-ethylhexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 1f)

1.5 g (2.61 mmol) of the compound of Formula 1e obtained in 3) was dissolved in 30 ml of carbon disulfide, and 0.5 g (3.13 mmol) of bromine was slowly added for 3 hours. After further stirring for 1 hour, the product was separated through a column chromatograph of the liquid residue generated after vacuum distillation of the solvent. 1.2 g (80%) of a white solid were obtained.

Rf 0.44 (SiO ₂ , hexane 100%)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 0.47-0.87 (m, 30H), 2.12 (d, 2H, J = 5.4 Hz), 7.64 (s, 2H), 7.74 (s, 2H), 7.95 (s, 2 H).

¹³ C-NMR (50 MHz, CDCl ₃ ) δ (ppm) 10.53, 14.20, 22.86, 27.55, 28.28, 34.06, 35.45, 44.03, 59.72, 121.84, 124.68, 125.63, 125.89, 128.64, 135.44, 150.97.

FAB-MS m / z 572.28 ([M + H] &lt; + &gt;, calcd 572.46).

5) Poly [4,4-bis (2-ethylhexyl) cyclopenta [def] phenanthrene-2,6-Dail-4H] Synthesis of (PCPP) (Formula 1g)

349 mg (1.27 mmol) of nickel catalyst (biscyclooctadiene nickel, Ni (COD) ₂ ), 198 mg (1.27 mmol) of 2,2-dipyridyl and 0.16 ml (1.27 mmol) of cyclooctadiene were added to 5 ml of dimethylformamide. After heating to 80 ℃ in anhydrous to form a purple complex. 300 mg (0.52 mmol) of the monomer of Formula 1f obtained in 4) was added to 5 ml of toluene, and then reacted at 80 ° C. for 3 days. After addition of 9-bromoanthracene used as a terminal, the reaction was further performed for 24 hours. After stirring for 3 hours in 100 ml of hydrochloric acid, 100 ml of acetone, and 200 ml of distilled water, the solid was filtered, re-dissolved in tetrahydrofuran, and recrystallized with methanol for 2 hours to obtain the desired product poly [4,4-bis (2-ethylhexyl) -4H -cyclo. 0.2 g of penta [ def ] phenanthrene-2,6-diyl] (PCPP) was obtained.

<Example 2> poly [(4,4-dimethyl-hexyl) cyclopenta [def] phenanthrene-2,6-Dail-4H] Preparation of (PDHCPP)

1) Synthesis of (4,4-dihexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 2c)

In Example 1 1, using 1 g (5.3 mmol) of 4H -cyclopenta [ def ] para-xylene (Formula 2a) and 2.21 ml (15.75 mmol) of catalytic amount of trideethylammonium chloride and hexylbromide (Formula 2b) 1.8 g (96%) of a white solid were obtained in the same manner as.

Rf 0.43 (SiO ₂ , Hexane 100%)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 0.71-0.15 (m, 22H) 2.07-2.15 (m, 4H) 7.50 (d, 2H J = 6.96 Hz) 7.618 (t, 2H J = 6.96 Hz ) 7.79 (d, 2H J = 7.69 Hz) 7.82 (s, 2H).

¹³ C-NMR (125 MHz, CDCl ₃ ) δ (ppm) 14.24 22.82 24.53 30.00 31.74 39.54 59.24 119.79 122.97 125.56 127.58 127.93 137.23 149.85.

FAB-MS m / z 359.27 ([M + H] &lt; + &gt;, calcd 358.56).

2) Synthesis of (4,4-dihexyl) -8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 2d)

1.8 g (5.02 mmol) of the compound of formula 2c prepared in 1) and 1.5 g of the palladium catalyst were used to obtain 1.61 g (89%) of a white solid in the same manner as in Example 2).

Rf 0.79 (SiO ₂ , Hexane 100%)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 0.74-1.15 (m, 22H) 1.94-2.00 (m, 4H) 7.05-7.20 (m, 6H).

¹³ C-NMR (125 MHz, CDCl ₃ ) δ (ppm) 14.28 22.88 24.63 26.31 30.07 31.81 39.37 58.49 121.25 124.95 127.50 130.40 138.37 148.46.

FAB-MS m / z 361.34 ([M + H] &lt; + &gt;, calcd 360.57).

3) Synthesis of 2,6-dibromo- (4,4-dihexyl) -8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 2e)

2.02 g (94%) of a pale yellow solid was obtained in the same manner as in Example 1, 3 using 1.5 g (4.16 mmol) of the compound of formula 2d and 13.53 g of an aluminum copper bromide complex obtained in 2).

Rf 0.46 (SiO ₂ , hexane 100%)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 0.77-1.13 (m, 22H) 2.04-2.12 (m, 4H) 7.60 (s, 2H) 7.76 (s, 2H) 7.96 (s, 2H).

¹³ C-NMR (125 MHz, acetone) δ (ppm) 14.31 22.91 24.53 25.83 29.96 31.79 39.26 59.27 121.66 124.74 128.55 131.77 136.35 149.77.

FAB-MS m / z 518.31 ([M + H] &lt; + &gt;, calcd 518.37).

4) Synthesis of 2,6-dibromo- (4,4-dihexyl) -4H -cyclopenta [ def ] phenanthrene (Formula 2f)

1.5 g (2.89 mmol) and 0.5 g (3.13 mmol) of bromine of the compound of Formula 2e obtained in 3) were used to obtain 1.26 g (85%) of a white solid in the same manner as in Example 4).

Rf 0.50 (SiO ₂ , Hexane 100%)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 0.73-1.13 (m, 22H) 2.04-2.12 (m, 4H) 7.60 (s, 2H) 7.76 (s, 2H) 7.96 (s, 2H).

¹³ C-NMR (125 MHz, CDCl ₃ ) δ (ppm) 13.56 22.52 24.38 29.57 31.50 38.92 60.23 122.07 123.94 125.97 126.13 128.90 135.16 151.43.

FAB-MS m / z 516.10 ([M + H] &lt; + &gt;, calcd 516.35).

5) Poly [(4,4-dimethyl-hexyl) cyclopenta [def] phenanthrene-2,6-Dail-4H] Preparation of (PDHCPP) (Formula 1g)

200 mg (0.2 mmol) of clean monomer of formula 2f obtained in 4), 230 mg (0.84 mmol) of Ni (COD) ₂ , 130 mg (0.84 mmol) of 2,2-dipyridyl, 0.1 ml (0.84 mmol) of cyclo 0.2 g of a polymer was obtained in the same manner as in Example 1, 5) using octadiene.

Example 3 Preparation of Poly [4,4-bis (4'-n-octyloxyphenyl) cyclopenta [ def ] phenanthrene-2,6-diyl] (PBOPCPP)

1) Synthesis of 8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 3b)

1 g (5.25 mmol) of 4H -cyclopenta [ def ] phenanthrene (Formula 3a) and 1 g of palladium catalyst were used to obtain 0.9 g (46%) of a white solid in the same manner as in Example 2).

Rf 0.45 (SiO ₂ , Hexane 100%)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 7.36 (d, 2H, J = 6.8 Hz), 7.21 (t, 2H, J = 7.4 Hz), 7.13 (d, 2H, J = 7.4 Hz), 3.91 (s, 2 H), 3.17 (s, 4 H).

2) Synthesis of 2,6-dibromo-8,9-dihydro- 4H -cyclopenta [ def ] phenanthrene (Formula 3c)

1.6 g (59%) of a white solid was obtained in the same manner as in Example 1, 3) using 0.9 g (2.6 mmol) of the compound of formula 3b and 8 g of an aluminum copper bromide complex.

Rf 0.28 (SiO ₂ , Hexane 100%)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 7.50 (s, 2H), 7.30 (s, 2H), 3.87 (s, 2H), 3.12 (s, 4H).

3) Synthesis of 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 3d)

Using 1.6g (4.6mmol) of the compound of formula 3c and 0.28ml (5.5mmol) of bromine of 2), 0.86g (54%) of a white solid was obtained in the same manner as in Example 4).

Rf 0.49 (SiO ₂ , methylene chloride: hexane = 1: 1)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 8.03 (s, 2H), 7.84 (s, 2H), 7.79 (s, 2H), 4.35 (s, 2H).

4) Synthesis of 2,6-dibromo-cyclopenta [ def ] phenanthren-4-one (Formula 3e)

0.86 g (2.5 mmol) and 10 g (115 mmol) of manganese dioxide were dissolved in 100 ml of benzene. After 1 hour of reaction at 80 ° C, the filter paper was filtered. The remaining solution was collected and vacuum solids distilled to separate the product through a column chromatograph. 0.64 g (70%) of a yellow solid was obtained.

Rf 0.4 (SiO ₂ , methylene chloride: hexane = 1: 1)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 8.09 (s, 2H), 7.72 (s, 2H), 7.25 (s, 2H).

5) Synthesis of 2,6-dibromo-4,4-bis (4-hydroxyphenyl) -cyclopenta [ def ] phenanthrene (Formula 3f)

0.64 g (1.8 mmol) and 0.68 g (5.2 mmol) of zinc dichloride were dissolved in 5 ml of phenol. Gas hydrochloric acid was injected at room temperature for 1 hour. The product was separated through a column chromatograph of the liquid residue generated after the reaction at 60 ° C. for 3 hours. 0.44 g (47%) of a yellow solid was obtained.

Rf 0.3 (SiO ₂ , ethyl acetate: hexane = 1: 3)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 8.02 (s, 2H), 7.83 (s, 2H), 7.68 (s, 2H), 7.11 (d, 4H, J = 8.4 Hz), 6.74 (d , 4H, J = 8.4 Hz).

6) Synthesis of 2,6-dibromo-4,4-bis (4-octyloxyphenyl) -cyclopenta [ def ] phenanthrene (Formula 3g)

0.44 g of the compound of formula 3f obtained in 5) was dissolved in 0.12 g (0.83 mmol) of sodium iodide and 0.69 g (5 mmol) of potassium carbonate in 30 ml of acetone. 0.86 ml (0.83 mmol) of 1-bromooctane was added. After reacting at 70 DEG C for 24 hours, the solution was vacuum distilled and the resulting solid residue was separated through a column chromatograph. Extraction with ethyl acetate and the liquid residue resulting from vacuum distillation of the solvent separated the product through a column chromatograph. 0.34 g (54%) of yellow liquid was obtained.

Rf 0.49 (SiO ₂ , Ethyl Acetate: Hexane = 1: 3)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 8.01 (s, 2H), 7.81 (s, 2H), 7.68 (s, 2H), 7.13 (d, 2H, J = 8.2 Hz), 7.09 (d , 2H, J = 6.2Hz), 6.78 (d, 2H, J = 8.8Hz), 6.73 (d, 2H, J = 8.8Hz), 6.73 (t, 4H, J = 6.5Hz), 1.77 (m, 2H ), 1.28 (m, 10H), 0.89 (t, 3H, J = 3.2 Hz).

7) Preparation of poly [4,4-bis (4'-n-octyloxyphenyl) cyclopenta [ def ] phenanthrene-2,6-diyl] (PBOPCPP) (Formula 3h)

340 mg (0.45 mmol) of clean monomer (3 g) obtained in 6) and 270 mg (1 mmol) of Ni (COD) ₂ , 160 mg (1 mmol) of 2,2-dipyridyl, 0.13 ml (1 mmol) of cyclooctata 0.2 g of a polymer was obtained by the same method as 5) of Example 1 using 1.28 g (5 mmol) 9-bromoanthracene.

In the (Cz-PCPP) <Example 4> poly [cyclopenta [def] phenanthrene-2,6-Dail 4,4-bis (6- (9H - carbazole-9-yl) hexyl) - - 4H] Produce

1) Synthesis of 9- (6-bromohexyl) -9H -carbazole (Formula 4c)

10 g (59.8 mmol) of 9H -carbazole (4a) was added to a 100 ml solution of 2.9 g (71.8 mmol) of tetrahydrofuran sodium hydride, stirred for 10 minutes, and 19 ml of 1,6-dibromohexane (4b). (119.6 mmol) was added. After refluxing for 24 hours, the mixture was extracted with methylene chloride and distilled water, the solvent was distilled under vacuum, and the resulting liquid residue was separated by column chromatography. 12.68 g (64.2%) of a white solid were obtained.

Rf 0.30 (SiO ₂ , CH ₂ Cl ₂ : Hexane = 1: 4)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 1.39-1.55 (m, 4H), 1.74-1.96 (m, 4H), 3.36 (t, 2H, J = 7.33 Hz), 4.31 (t, 2H, J = 7.51 Hz), 7.21 (t, 2H, J = 6.04 Hz), 7.27-7.52 (m, 4H), 8.10 (d, 2H, J = 7.69 Hz).

¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm) 26.30, 27.77, 28.67, 32.44, 33.63, 42.66, 108.51, 118.70, 120.25, 122.73, 125.52, 140.28.

2) 9- (6- (2,6-dibromo-4- (6- ( 9H -carbazol-9-yl) hexyl) -4H -cyclopenta [ def ] phenanthrene-4-yl) hexyl)- Preparation of 9H -carbazole (Formula 4e)

1.40g (4.24 mmol) of the compound of formula 4c obtained in 1) and 0.67g (1.92 mmol) of 2,6-dibromo- 4H -cyclopenta [ def ] phenanthrene (Formula 4d) were used. 1.02 g (64%) of a white solid was obtained in the same manner as in 1).

Rf 0.3 (SiO ₂ , methylene chloride: hexane = 1: 3)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 0.56-0.61 (m, 4H) 1.05-1.15 (m, 8H) 1.66-1.73 (m, 4H) 1.99 (t, 4H, J = 4.2 Hz) 4.18 (t, 4H, J = 7 Hz) 7.20-7.35 (m, 8H) 7.45 (d, 4H J = 8 Hz) 7.591 (s, 2H) 7.765 (s, 2H) 7.996 (s, 2H) 8.12 (d, 4H , J = 8 Hz).

3) Poly [4,4-bis (6- (9H - carbazole-9-yl) hexyl) - 4H - cyclopenta [def] phenanthrene-2,6-Dail] (Cz-PCPP) (Formula 4f) Synthesis of

260 mg (0.31 mmol) of clean monomer of formula 4e obtained in 2) and 187 mg (0.68 mmol) of Ni (COD) ₂ , 106 mg (0.68 mmol) of 2,2-dipyridyl, 0.08 ml (0.68 mmol) of cyclo 150 mg of polymer was obtained in the same manner as in Example 1, 5) using octadiene, 1.28 g (5 mmol) 9-bromoanthracene.

Example 5 Poly [4- (6- (4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenoxy) hexyl) -4- (6- ( 9H -carbazole 9-yl) hexyl) - 4H - preparation of cyclopenta [def] phenanthrene-2,6-Dail] (Oxd-Cz-PCPP)

1) Synthesis of N-benzoyl-4-hydroxybenzohydrazide (Formula 5c)

10 g (64.4 mmol) of 4-hydroxy benzohydrazide (Formula 5a) and 9.16 ml (77.3 mmol) of benzoyl chloride (Formula 5b) were dissolved in 200 ml of pyridine and refluxed at 120 ° C. for 6 hours. At room temperature, 1M hydrochloric acid was added, acidified to pH 4-5, precipitated using 500 ml of ethanol, and filtered to obtain 13.58 g (82.3%) of a white solid product.

¹ H-NMR (200 MHz, DMSO): δ (ppm) 6.82 (d, 2H, J = 8.42 Hz), 7.47-7.89 (m, 7H), 10.21 (s, 1H), 10.37 (s, 1H).

¹³ C-NMR (75 MHz, DMSO) δ (ppm) 122.85, 128.15, 129.20, 129.72, 129.76, 130.57, 132.55, 134.91, 165.81, 166.53.

2) Synthesis of 4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenol (Formula 5d)

13.5 g (58.0 mmol) of the compound of Chemical Formula 5c obtained in 1) and 200 ml of cionyl chloride were refluxed at 80 ° C. for 5 hours for cyclization. An excess of cionyl chloride was vacuum distilled and then recrystallized in 500 ml of distilled water to obtain 10.3 g (74.7%) of a white solid product.

¹ H-NMR (200 MHz, DMSO): δ (ppm) 6.94 (d, 2H, J = 8.4 Hz), 7.71-7.86 (m, 3H), 7.93 (d, 2H, J = 8.06 Hz), 8.03-8.11 (m, 2 H).

¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm) 122.65, 126.98, 128.41, 128.71, 129.11, 130.28, 131.80, 133.95.

3) Synthesis of 2- (4-((6-bromohexyl) oxy) phenyl) -5-phenyl-1,3,4-oxadiazole (Formula 5f)

4.4 g (43.0) in the same manner as in Example 4 1), using 6.1 g (25.6 mmol) of the compound of Formula 5d and 8.1 ml (51.2 mmol) of 1,6-dibromohexane (Formula 5e) obtained in 2). %) White solid.

Rf 0.40 (SiO ₂ , ethyl acetate: hexane = 1: 4)

¹ H-NMR (200 MHz, CDCl ₃ ): δ (ppm) 1.51-1.61 (m, 4H), 1.84-1.91 (m, 4H), 3.43 (t, 2H, J = 6.78 Hz), 4.04 (t, 2H , J = 6.23 Hz), 7.01 (d, 2H, J = 8.43 Hz), 7.51-7.55 (m, 3H), 8.06 (d, 2H, J = 9.16 Hz), 8.10-8.15 (m, 2H).

¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm) 25.25, 27.88, 28.95, 32.63, 33.69, 67.99, 114.98, 116.32, 126.82, 128.33, 128.69, 129.02, 129.52, 131.49, 161.86.

4) 9- (6- (2,6-dibromo-4- (6- (4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenoxy) hexyl) -4H- Synthesis of cyclopenta [ def ] phenanthren-4-yl) hexyl) -9H -carbazole (Formula 5i)

The 3) 1.70g (4.20mmol) of the compound obtained in Formula 5f, 9 (6-Bromo-hexyl) - 9H - carbazole (formula 4c) 1.40g (4.24mmol) and 2,6-dibromo - 4H 850 mg (24%) of a white solid was obtained in the same manner as in Example 1-1 using 1.34 g (3.85 mmol) of -cyclopenta [ def ] phenanthrene (Formula 5 g).

Rf 0.4 (SiO ₂ , Ethyl Acetate: Hexane = 1: 3)

¹ H-NMR (200 MHz, CDCl ₃ ) δ (ppm) 0.56-0.61 (m, 4H) 1.05-1.15 (m, 8H) 1.66-1.73 (m, 4H) 2.07-2.16 (m, 4H) 3.91 (t , 2H, J = 6.35 Hz) 4.19 (t, 2H, J = 7 Hz) 6.96 (d, 2H J = 8.8 Hz) 7.18-7.34 (m, 2H) 7.43 (d, 2H J = 7 Hz) 7.54-7.57 (m , 3H) 7.56 (s, 2H) 7.77 (s, 2H) 7.98 (s, 2H) 8.05 (d, 4H, J = 8 Hz) 8.11-8.15 (m, 6H).

5) Poly [4- (6- (4- (5-phenyl-1,3,4-oxadiazol-2-yl) phenoxy) hexyl) -4- (6- ( 9H -carbazole-9- 1) hexyl) -4 H -cyclopenta [ def ] phenanthrene-2,6-diyl] (Oxd-Cz-PCPP)

267 mg (0.97 mmol) of Ni (COD) ₂ , 152 mg (0.97 mmol) of 2,2-dipyridyl, 0.10 ml (0.97 mmol) together with 400 mg (0.44 mmol) of the clean monomer of Formula 5i obtained in 4). 200 mg of the polymer was obtained by the same method as in Example 1, 5) using cyclooctadiene and 1.28 g (5 mmol) 9-bromoanthracene.

PCPP, PDHCPP, PBOPCPP, Cz-PCPP and Oxd-Cz-PCPP prepared by synthesis in Examples 1 to 5 had good solubility in organic solvents and completely dissolved in general organic solvents. The molecular weight is measured using GPC, and the measured molecular weight is 15,000-37,000 with a number average molecular weight, 50,000-144,000 with a mass average molecular weight, and a dispersity of 3.3-6.0.

They exhibit maximum absorption at 360-370 nm, and PL exhibit maximum emission at about 410 nm and emit in the blue region.

1 is a cross-sectional view of an electroluminescent device using PCPP, PDHCPP, PBOPCPP, Cz-PCPP, and Oxd-Cz-PCPP as light emitting layers, wherein the light emitting device is made of ITO and aluminum (Al) coated on glass as a cathode and an anode, respectively It is produced.

Example 6 Fabrication of Light-Emitting Element Using PCPP

 A semitransparant electrode 2 of indium tin oxide (ITO) is formed on the glass or plastic substrate 1, and a hole transport layer made of a polymer or an organic material is formed on the semitransparant electrode 2. transporting layer) 3 was formed.

The PCPP prepared in Example 1 was coated on the hole transport layer 3 to form a polymer light emitting layer 4 using PCPP, and an aluminum (Al) metal electrode 5 was formed on the polymer light emitting layer 4. . Luminescence occurs in PCPP.

The measurement of the element produced as mentioned above was performed in air. The EL (electroluminescence) spectrum showed an emission spectrum in a region similar to PL, and emitted fluorescent light at about 410-430 nm.

<Example 7 to 10> Preparation of light emitting device using PDHCPP, PBOPCPP, Cz-PCPP and Oxd-Cz-PCPP

In the same manner as in Example 6, a semitransparant electrode 2 of indium tin oxide (ITO) is formed on the glass or plastic substrate 1, and on the semitransparant electrode 2 A hole transporting layer 3 made of a polymer or organic material was formed.

PDHCPP, PBOPCPP, Cz-PCPP and Oxd-Cz-PCPP prepared in Examples 2 to 5 were applied on the hole transport layer 3 to form a polymer light emitting layer 4, and the polymer light emitting layer 4 An aluminum (Al) metal electrode 5 was formed thereon. Luminescence occurs at PDHCPP, PBOPCPP, Cz-PCPP and Oxd-Cz-PCPP, respectively.

The measurement of the device fabricated as above was carried out in air. The EL spectrum showed an emission spectrum in a region similar to that of PL, and emitted fluorescent light at about 410-430 nm.

2 and 3 show the EL spectrum of the light emitting device using PCPP and PDHCPP, and FIGS. 4, 5 and 6 show the current-voltage characteristics and the light emission efficiency of the manufactured light emitting device. The current-voltage curve shows typical device characteristics in which the current increases in proportion to the voltage increase, and emits visible bright fluorescent light from about 5-10V.

As described above, PCPP and its derivatives PDHCPP, PBOPCPP, Cz-PCPP and Oxd-Cz-PCPP using cyclopentaphenanthrene as monomers according to the present invention have good luminous efficiency, and the final synthesized polymer is used in a general organic solvent. Melted well. Since the polymer synthesized in the present invention can be used in a device in a dissolvable form, it does not require a high temperature heat treatment process and thus has excellent workability, and has an excellent advantage of manufacturing an electroluminescent device on a bendable plastic substrate.

Claims (7)

A light emitting polymer having a number average molecular weight of 15,000-37,000, a mass average molecular weight of 50,000-144,000, and represented by the following Chemical Formula 1: [Formula 1]

Where R ₁ and R ₂ are C _1-20 linear or branched alkyl group,

, R ₄ -HTL (hole transport layer) or R ₅ -ETL (electron transport layer); Where R ₃ is C _1-20 linear or branched alkyl group; R ₄ and R ₅ C _1-20 linear or branched alkyl group. The method of claim 1, wherein the HTL (hole transport layer)

Light emitting polymer, characterized in that. The method of claim 1, wherein the ETL (electron transport layer) is

Is, Where R ₆ is OR ₇ , or R ₈ , and R ₇ , R ₈ are Light-emitting polymer, characterized in that a linear or branched alkyl group of C _1-20 . The method of claim 1, wherein the light emitting polymer is represented by the formula (1) is poly-cyclopenta phenanthrene (PCPP), poly [(4,4-dimethyl-hexyl) - 4H - cyclopenta [def] phenanthrene-2,6-Dail ] (PDHCPP), poly [4,4-bis (4'-n-octyloxyphenyl) cyclopenta [ def ] phenanthrene-2,6-diyl] (PBOPCPP), poly [4,4-bis (6- ( 9H -carbazol-9-yl) hexyl) -4 H -cyclopenta [ def ] phenanthrene-2,6-diyl) (Cz-PCPP) and poly [4- (6- (4- (5- phenyl-1,3,4-oxadiazol-2-yl) phenoxy) hexyl) -4- (6- (9H - carbazole-9-yl) hexyl) -4 H - cyclopenta [def] phenanthrene -2,6-diyl] (Oxd-Cz-PCPP) light-emitting polymer, characterized in that selected from the group consisting of. A semi-transparent electrode, a hole transport layer, a polymer light emitting layer and a metal electrode are sequentially formed on the substrate, wherein the polymer light emitting layer is formed of the light emitting polymer according to any one of claims 1 to 4. The electroluminescent device according to claim 5, wherein the substrate is glass or plastic. An optical energy conversion element using the light emitting polymer according to any one of claims 1 to 4.

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