KR20150126809A - Emitting polymer and organic emitting device the emitting polymer - Google Patents

Abstract

Disclosed are a compound including a phosphorescent unit, a light emitting polymer, and an organic light emitting device including an organic layer containing a light emitting polymer.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent (EL)

A compound including a phosphorescent unit, a light emitting polymer, and an organic light emitting device having an organic layer containing the light emitting polymer.

An organic light emitting device includes a pair of electrodes and an organic layer interposed between the electrodes. When an electric current is supplied to the electrodes, electrons and holes injected through the electrodes couple to each other in the organic layer, Emitting device. Such an organic light emitting device is light in weight, has a simple structure and has a simple manufacturing process, and has a high viewing angle and a wide viewing angle. In addition, it can realize high color purity and moving picture perfectly, and has electric characteristics suitable for portable electronic devices with low power consumption and low voltage driving.

A typical organic light emitting device has a structure in which an anode is formed on a substrate, a hole transport layer, a light emitting layer, an electron transport layer, and the like are formed as an organic layer on the anode, and a cathode is sequentially formed thereon.

When an electric current is applied to the anode and the cathode, holes injected from the anode move to the light emitting layer via the hole transporting layer, and electrons injected from the cathode move to the light emitting layer via the electron transporting layer. The holes and electrons thus moved recombine in the light emitting layer region to generate an exciton. As the excitons are radiatively decayed, light of a wavelength corresponding to the band gap of the material is emitted.

The light emitting layer forming material of the organic light emitting diode can be classified into a fluorescent material using a singlet state exciton and a phosphorescent material using a triplet state according to its light emitting mechanism. The luminescent layer can be formed only by using such a fluorescent substance or a phosphorescent material, or by doping these fluorescent substances or phosphors to a suitable host. When the light emitting layer is formed together with the host, singlet excitons and triplet excitons are formed in the host as a result of the electron excitation. At this time, the statistical production ratio of singlet excitons and triplet excitons is 1: 3.

In an organic light emitting device using a fluorescent material as a material for forming a light emitting layer, triplet generated in a host may be wasted. However, when a phosphorescent material is used as a material for forming a light emitting layer, singlet excitons and triplet excitons can be used. The quantum efficiency can reach 100%.

However, as a high-efficiency light-emitting material using such phosphorescence, development of a material satisfying the performance required for realizing a high-efficiency full-color display and a low power consumption white light emitting application is required.

One aspect of the present invention is to provide a compound comprising a phosphorescent unit with a novel structure.

Another aspect of the present invention is to provide a light emitting polymer having a novel structure.

Another aspect of the present invention is to provide an organic light emitting device having an organic layer including the light emitting polymer.

According to one embodiment of the present invention there is provided a compound having the formula:

≪ Formula 1 >

In Formula 1,

Ha ₁ and Ha ₂ are, independently of each other, a halogen atom;

X ₁ is O or S;

Y ₁ is - (CR ₁ R ₂ ) _n1 - or - (CR ₃ R ₄ ) _n2 -O-, and R ₁ to R ₄ independently represent hydrogen, hydroxyl, amino, cyano, , A C ₁ -C ₂₀ alkyl group or a C ₂ -C ₂₀ alkenyl group, and n1 and n2 are each independently an integer of 0 to 20;

M ₁ is a divalent to tetravalent metal atom;

L ₁ and L ₂ are, independently of each other, an organic ligand having any one of the following formulas 2, 3, 4 and 4a, provided that when L 2 is L ₁ , If one of the atoms are connected by a single bond and Y _1, formula (3) in this case L ₁ day, one of the atoms constituting the CY3 of formula (3) are connected by a single bond and Y _1, the formula 4 L ₁ il , One of the atoms constituting CY 4 of formula (4) is connected to Y ₁ through a single bond, and when the formula (4a) is L ₁ , one of the atoms constituting A ₁₀ is connected to Y ₁ through a single bond;

t is 1 or 2;

(2) (3) ≪ Formula 4 >

≪ Formula 4a &

Of the above formulas (2), (3), (4) and (4a)

X ₂ and X ₃ are independently of each other C, S, O or N;

CY1, CY3 and CY4 are, independently of each other, a substituted or unsubstituted heteroaromatic ring or a substituted or unsubstituted heteroaliphatic ring;

CY2 is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heteroaromatic ring, a substituted or unsubstituted aliphatic ring or a substituted or unsubstituted heteroaliphatic ring;

A ₁₀ is _{- (CR 20 R 21) n3} - , and wherein n3 is an integer from 1 to 10, wherein the n3 of -CR ₂₀ R ₂₁ - least one of -NR ₂₂ -, -PR ₂₃ - or -S- And R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ are independently of each other hydrogen, a hydroxyl group, an amino group, a cyano group, a carboxylic acid, a C ₁ -C ₂₀ alkyl group or C ₂ -C ₂₀ alkyl group, -C ₂₀ alkenyl group;

m is an integer from 0 to 10;

* Represents a binding site with M &_lt; ₁ >

According to another aspect of the present invention, there is provided a polymer represented by the following formula (7): < EMI ID =

≪ Formula 7 >

In Formula 7,

Ar ₁ and Ar ₂ are, independently of each other, a substituted or unsubstituted C ₆ -C ₃₀ arylene group or a substituted or unsubstituted C ₄ -C ₃₀ heteroarylene group;

X ₁ is O or S;

Y ₁ is - (CR ₁ R ₂ ) _n1 - or - (CR ₃ R ₄ ) _n2 -O-, and R ₁ to R ₄ independently represent hydrogen, hydroxyl, amino, cyano, , A C ₁ -C ₂₀ alkyl group or a C ₂ -C ₂₀ alkylene group, and n1 and n2 are independently of each other an integer of 0 to 20;

M ₁ is a divalent to tetravalent metal atom;

L ₁ and L ₂ are, independently of each other, an organic ligand having any one of the above formulas 2, 3, 4 and 4a, provided that when L 2 is L ₁ , it constitutes any one of CY 1 and CY 2 If one of the atoms are connected by a single bond and Y _1, formula (3) in this case L ₁ day, one of the atoms constituting the CY3 of formula (3) are connected by a single bond and Y _1, the formula 4 L ₁ il , One of the atoms constituting CY 4 of formula (4) is connected to Y ₁ through a single bond, and when the formula (4a) is L ₁ , one of the atoms constituting A ₁₀ is connected to Y ₁ through a single bond;

t is 1 or 2;

,

,

또는

이며, 상기 Q₁₁, Q₁₂, Q₁₃, Q₁₄, Q₁₅ 및 Q₁₆는 서로 독립적으로, 수소, C₁-C₂₀알킬기 또는 C₁-C₂₀알콕시기이고;X < ₄ > is O, S,

,

,

or

Q ₁₁ , Q ₁₂ , Q ₁₃ , Q ₁₄ , Q ₁₅ and Q ₁₆ are independently of each other hydrogen, a C ₁ -C ₂₀ alkyl group or a C ₁ -C ₂₀ alkoxy group;

Y ₂ is a substituted or unsubstituted C ₆ -C ₃₀ arylene group or a substituted or unsubstituted C ₄ -C ₃₀ heteroarylene group;

R is H, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₂₀ cycloalkyl group, A C ₃₀ aryl group or a substituted or unsubstituted C ₄ -C ₃₀ heteroaryl group;

b is a real number of 0? b? 0.99, c is a real number of 0 <c? 0.99, d is a real number of 0? d? 0.99, a + b + c + d = 1:

According to another aspect of the present invention, there is provided an organic light emitting device having an organic layer including the polymer.

According to an aspect of the present invention, a light emitting polymer capable of emitting both fluorescence and phosphorescence is provided, and a high-quality organic light emitting device can be realized using the same.

1 is a schematic cross-sectional view of an organic light emitting device according to an embodiment of the present invention.
2 is a color purity diagram of an organic light emitting device according to an embodiment of the present invention.
3 is CIE color coordinates of an organic light emitting device according to an embodiment of the present invention.
4 is a graph of current density-voltage-luminance of an organic light emitting device according to an embodiment of the present invention.

According to one aspect of the present invention there is provided a compound having the formula:

&Lt; Formula 1 >

The compound having the formula (1) can be used as a monomer for synthesizing a polymer having the formula (7) as described below. The compound having the formula ( ₁₎ Has a phosphorescence unit capable of emitting light in accordance with the phosphorescence mechanism represented by -M ₁ - (L ₂ ) _t -.

In the general formula (1), Ha ₁ and Ha ₂ are, independently of each other, a halogen atom. For example, Ha &lt; _{1 &gt;} and Ha &lt; ₂ &gt; may be independently of each other Cl, Br or I.

In Formula 1, X ₁ is O or S. For example, X ₁ may be O, but is not limited thereto.

In the general formula (1), Y ₁ is - (CR ₁ R ₂ ) _n1 - or - (CR ₃ R ₄ ) _n2 -O-. Here, R ₁ to R ₄ may independently be hydrogen, a hydroxyl group, an amino group, a cyano group, a carboxylic acid, a C ₁ -C ₂₀ alkyl group, or a C ₂ -C ₂₀ alkenyl group, but is not limited thereto . For example, R ₁ to R ₄ independently of each other may be hydrogen, a hydroxyl group, an amino group, a cyano group, a carboxylic acid, a C ₁ -C ₁₀ alkyl group or a C ₂ -C ₁₀ alkenyl group. N1 and n2 may be independently of each other an integer of 0 to 20, for example, an integer of 0 to 10.

In the above formula (1), M ₁ may be a metal capable of simultaneously forming a triplet state and a singlet state through spin-orbital coupling generated by a heavy atom effect. For example, M &_lt; ₁ &gt; may be a divalent to tetravalent metal atom. Examples of the M ₁ include Ir, Pt, Rh, Pd, Os, Ti, Zr, Hf, Eu, Tb or Tm.

In Formula 1, L ₁ and L ₂ may independently be an organic ligand having any one of the following Formulas 2, 3, 4, and 4a.

(2) (3) &Lt; Formula 4 >

&Lt; Formula 4a &

When the formula (2) is L ₁ , one of the atoms constituting any one of CY 1 and CY 2 in the formula (2) is connected to Y ₁ through a single bond, and when the formula (3) is L ₁ , the formula one of the atoms that are connected by a single bond and Y _1, the formula (4) is, if L ₁ day, one of the atoms constituting the CY4 of formula (4) is connected by a single bond and Y _1, the formula 4a L ₁ il , One of the atoms constituting A ₁₀ is connected to Y ₁ by a single bond. This is evident from the structure of the compound represented by the above formula (1), and can be clearly recognized by those skilled in the art with reference to the following formulas (5a) to (5z).

In the general formulas (2) to (4), X ₂ and X ₃ are independently of each other C, S, O or N.

Wherein CY1, CY3 and CY4 are, independently of each other, a substituted or unsubstituted heteroaromatic ring or a substituted or unsubstituted heteroaliphatic ring, CY2 is a substituted or unsubstituted aromatic ring, a substituted or unsubstituted ring A substituted or unsubstituted heteroaromatic ring, a substituted or unsubstituted aliphatic ring, or a substituted or unsubstituted heteroaliphatic ring.

For example, the substituted or unsubstituted heteroaromatic ring may be substituted or unsubstituted pyrrole, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted heteroaromatic ring, Substituted or unsubstituted pyridines, substituted or unsubstituted pyrazines, substituted or unsubstituted pyrimidines, substituted or unsubstituted pyridazines, substituted or unsubstituted isoindoles, substituted or unsubstituted isoindoles, Substituted or unsubstituted indole, substituted or unsubstituted indazole, substituted or unsubstituted purine, substituted or unsubstituted quinoline, substituted or unsubstituted benzoquinoline ), Substituted or unsubstituted phthalazine, substituted or unsubstituted naphthyridine, substituted or unsubstituted quinoxaline, substituted or unsubstituted quinazoline, substituted or unsubstituted naphthyridine, substituted or unsubstituted quinoxaline, Substituted cinnoline, substituted &lt; RTI ID = 0.0 &gt; Substituted or unsubstituted carbazole, substituted or unsubstituted phenanthridine, substituted or unsubstituted acridine, substituted or unsubstituted phenanthroline, substituted or unsubstituted &lt; RTI ID = 0.0 &gt; Phenazine, substituted or unsubstituted benzooxazole, substituted or unsubstituted benzoimidazole, substituted or unsubstituted furan, substituted or unsubstituted benzopuran, , Substituted or unsubstituted thiophene, substituted or unsubstituted benzothiophene, substituted or unsubstituted thiazole, substituted or unsubstituted isothiazole, substituted or unsubstituted thiophene, Substituted or unsubstituted benzoxazole, substituted benzothiazole, substituted or unsubstituted isoxazole, substituted or unsubstituted oxazole, and substituted or unsubstituted benzooxazole. However, it is not limited to this. The.

For example, the substituted or unsubstituted heteroaliphatic ring may be substituted or unsubstituted pyrrolidine, substituted or unsubstituted pyrazolidine, substituted or unsubstituted imidazolidine ), A substituted or unsubstituted piperidine, a substituted or unsubstituted piperazine, and a substituted or unsubstituted morpholine. However, the present invention is not limited thereto.

For example, the substituted or unsubstituted aromatic ring may be substituted or unsubstituted benzene, substituted or unsubstituted pentalene, substituted or unsubstituted indene, substituted or unsubstituted Naphthalene, substituted or unsubstituted azulene, substituted or unsubstituted heptalene, substituted or unsubstituted indacene, substituted or unsubstituted acenaphthylene, substituted or unsubstituted acenaphthylene, Substituted or unsubstituted fluorene, substituted or unsubstituted phenanthrene, substituted or unsubstituted phenanthrene, substituted or unsubstituted anthracene, substituted or unsubstituted fluoranthene, Substituted or unsubstituted naphthacene, fluoranthene, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrene, substituted or unsubstituted chrysene, substituted or unsubstituted naphthacene. Substituted or unsubstituted picene, substituted or unsubstituted perylene, substituted or unsubstituted pentaphene, and substituted or unsubstituted hexacene, , But is not limited thereto.

The substituted or unsubstituted heteroaromatic ring, the substituted or unsubstituted heteroaliphatic ring, the substituted or unsubstituted aromatic ring or the substituted or unsubstituted heteroaliphatic ring, the substituted heteroaromatic ring, the substituted heteroaromatic ring aliphatic ring, said substituted aromatic ring or substituted hetero ring is an aliphatic, _{halogen, -CF 3, -CN, -Si (} a 1) (a 2) (a 3), C 1 -C 20 alkyl, C ₂ - C ₂₀ alkenyl group may have one or more substituents selected from C ₆ -C ₂₀ aryl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryloxy group, and the group consisting of an amino group. Here, A ₁ , A ₂ and A ₃ each independently may be hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group or a C ₁ -C ₂₀ alkoxy group. Examples of the substituent, _{halogen, -CF 3, -CN, -Si (} A 1) (A 2) (A 3), C 1 -C 10 alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₁₄ An aryl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₁₄ aryloxy group or an amino group, but is not limited thereto.

In the general formulas (2) to (4), m is an integer of 0 to 10. For example, m may be an integer of 0 to 5.

In the general formulas (2) to (4), * represents a binding site with M ₁ in the general formula (1).

In formula (4a), A ₁₀ may be represented by - (CR ₂₀ R ₂₁ ) _n3 -. Here, n3 is an integer of 1 to 10. For example, n3 is an integer of 1 to 5, but is not limited thereto. Wherein n3 of -CR ₂₀ R ₂₁ - least one of, -NR ₂₂ -, -PR ₂₃ - or may optionally be substituted with -S-. R ₂₀ , R ₂₁ , R ₂₂ and R ₂₃ independently of one another are each independently selected from the group consisting of hydrogen, hydroxyl, amino, cyano, carboxylic acid, C ₁ -C ₂₀ alkyl groups (for example, Propyl group, butyl group, etc.) or a C ₂ -C ₂₀ alkenyl group, but is not limited thereto.

In the above formula (4a), * represents a binding site with M ₁ in formula (1).

In the above formulas, non-limiting examples of the L ₁ may be represented by any one of the following formulas (5a) to (5z), but are not limited thereto:

In the above general formulas (5a) to (5z), Z ₁ is S, O or N.

Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ and Q ₇ are each independently selected from the group consisting of hydrogen, halogen, -CF ₃ , -CN, -Si (A ₁ ) (A ₂ ) (A ₃ ), a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ aryloxy group or an amino group. For example, the _{Q 1, Q 2, Q 3} , Q 4, Q 5, Q 6 and Q ₇ are each independently hydrogen, _{halogen, -CF 3, -CN, -Si (} A 1) (A 2) (A ₃ ), a C ₁ -C ₁₀ alkyl group, a C ₂ -C ₁₀ alkenyl group, a C ₆ -C ₁₄ aryl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₁₄ aryloxy group or an amino group, But is not limited thereto.

Q ₁ , Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ , and Q ₇ Two or more of which may be fused to each other to form a 5- or 7-membered aliphatic or aromatic ring. A ₁ , A ₂ and A ₃ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group or a C ₁ -C ₂₀ alkoxy group, for example, hydrogen, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl or C ₁ -C ₁₀ alkoxy date can be, but is not limited to this.

In the above formulas (5a) to (5z), * 'represents a binding site with Y ₁ in formula (1).

In the formula 5a to 5z, * shows a bonding site with the M ₁ of formula (I).

Non-limiting examples of L _{2 in} the above formula (1) may be represented by any one of the following formulas (6a) to (6z), but are not limited thereto:

In the above formulas (6a) to (6z), Z ₂ is S, O or N.

In the formula 6a to _{6z, T 1, T 2,} T 3, T 4, T 5, T 6, T 7 and T ₈ each independently represent hydrogen, _{halogen, -CF 3, -CN, -Si (} A 4) (A ₅ ) (A ₆ ), a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₆ -C ₂₀ aryl group, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ aryloxy group or an amino group to be. For _{example, T 2, T 3, T} 4, T 5, T 6, T 7 and T ₈ each independently represent hydrogen, _{halogen, -CF 3, -CN, -Si (} A 4) (A 5) (A ₆ ), a C ₁ -C ₁₀ alkyl group, a C ₂ -C ₁₀ alkenyl group, a C ₆ -C ₁₀ aryl group, a C ₁ -C ₁₀ alkoxy group, a C ₆ -C ₁₀ aryloxy group or an amino group.

_Two or more of T ₁ , T ₂ , T ₃ , T ₄ , T ₅ , T ₆ , T ₇ and T ₈ may be fused together to form a 5- or 7-membered aliphatic or aromatic ring . A ₄ , A ₅ and A ₆ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group or a C ₁ -C ₂₀ alkoxy group, for example, hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl group or may be C ₁ -C ₁₂ alkoxy group.

In the formula 6a to 6z, * shows a bonding site with the M ₁ of formula (I).

The compound having the formula (1) can be, for example, the following compounds 1, 2, or 3, but is not limited thereto;

&Lt; Compound 1 > <Compound 2>

<Compound 3>

According to another embodiment of the present invention there is provided a polymer having the following formula:

&Lt; Formula 7 >

The polymer having formula (7) can emit light in two or more colors according to a phosphorescent mechanism and / or a fluorescence mechanism. When such a polymer is used, a high quality organic light emitting device can be realized.

로 표시되는 반복 단위에서, 인광 메커니즘에 따라 발광이 일어날 수 있고, -(Ar₁)-, -(Ar₂)-, 및/또는

로 표시되는 반복 단위에서, 형광 메커니즘에 따라 발광이 일어날 수 있다. 따라서, 높은 내부양자 효율을 달성할 수 있다. 또한, 화학식 7을 갖는 화합물은, 인광 단위인 -(L₁)-M₁-(L₂)_t-가 페녹사진 모이어티 또는 페노티아진 모이어티와 결합되어 있는 바, 화학식 7을 갖는 고분자의 주쇄(backbone)와 인광 단위에서 동시에 EL 특성을 관찰할 수 있다. 또한, 분자내 에너지 이동(intermolecular energy transfer)이 일어날 수 있어, 우수한 효율 특성을 얻을 수 있다. The polymer having the formula (7)

(Ar ₁ ) -, - (Ar ₂ ) -, and / or a repeating unit represented by -

In the repeating unit represented by the formula (I), luminescence may occur depending on the fluorescence mechanism. Therefore, a high internal quantum efficiency can be achieved. In addition, the compound having the general formula (7) has a structure in which the phosphorescent unit - (L ₁ ) -M ₁ - (L ₂ ) _t - is bonded to the phenoxazine moiety or the phenothiazine moiety, EL characteristics can be observed simultaneously in the backbone and the phosphorescence unit. In addition, intermolecular energy transfer can occur, and excellent efficiency characteristics can be obtained.

로 표시되는 반복 단위에서, 적색 발광 및/또는 녹색 발광이 이루어질 수 있고, -(Ar₁)-, -(Ar₂)-, 및/또는

로 표시되는 반복 단위에서, 청색 발광이 이루어질 수 있는 등, 상기 반복 단위들의 구조 및 몰비에 따라 다양한 컬러 조합이 가능하다. 이로써, 상기 화학식 7을 갖는 고분자는 백색 발광도 가능하다. The polymer having formula (7) can simultaneously realize two or more colors. For example,

(Ar ₁ ) -, - (Ar ₂ ) -, and / or a repeating unit represented by -

, Blue light emission can be achieved, and various combinations of colors are possible depending on the structure and molar ratio of the repeating units. As a result, the polymer having formula (7) can also emit white light.

In the formula 7, Ar ₁ and Ar ₂ is Ar ₁ and Ar ₂ are each independently of each other, substituted or unsubstituted C ₆ -C ₃₀ aryl group or a substituted or unsubstituted C ₄ -C ₃₀ heteroaryl group.

Non-limiting examples of Ar &lt; _{1 &gt;} and Ar &lt; ₂ &gt; may be represented by any one of the following formulas (8a) to (8s)

In the above formulas (8a) to (8c), R ₅ to R ₈ are, independently of each other, hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group or a C ₆ -C ₂₀ aryl group. For example, R ₅ to R ₈ independently of each other may be hydrogen, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, or a C ₆ -C ₁₀ aryl group.

In the above formulas (8a) to (8s), * represents a binding site with adjacent repeating units.

For a detailed description of X ₁ , Y ₁ , M ₁ , L ₁ , L ₂ and t in Formula 7, refer to the detailed description of the compound having Formula 1 above.

,

,

또는

이다. 예를 들여, 상기 X₄는 O 또는 S일 수 있다. 상기 Q₁₁, Q₁₂, Q₁₃, Q₁₄, Q₁₅ 및 Q₁₆는 서로 독립적으로, 수소, C₁-C₂₀알킬기 또는 C₁-C₂₀알콕시기이다. 예를 들어, 상기 Q₁₁, Q₁₂, Q₁₃, Q₁₄, Q₁₅ 및 Q₁₆는 서로 독립적으로, 수소, C₁-C₁₀알킬기 또는 C₁-C₁₀알콕시기일 수 있다.In Formula 7, X ₄ represents O, S,

,

,

or

to be. For example, X &lt; ₄ &gt; may be O or S. Q ₁₁ , Q ₁₂ , Q ₁₃ , Q ₁₄ , Q ₁₅ and Q ₁₆ are, independently of each other, hydrogen, a C ₁ -C ₂₀ alkyl group or a C ₁ -C ₂₀ alkoxy group. For example, Q ₁₁ , Q ₁₂ , Q ₁₃ , Q ₁₄ , Q ₁₅ and Q ₁₆ may be, independently of each other, hydrogen, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ alkoxy group.

In Formula 7, Y ₂ is a substituted or unsubstituted C ₆ -C ₃₀ arylene group or a substituted or unsubstituted C ₄ -C ₃₀ heteroarylene group. For example, Y ₂ may be a substituted or unsubstituted C ₆ -C ₁₄ arylene group. Non-limiting examples of Y ₂ include a phenylene group, a naphthalene group and an anthrylene group. The substituent of the substituted arylene group and the heteroarylene group may be a cyano group, a hydroxyl group, a thiol group, a nitro group, a halogen atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₂ -C ₁₀ alkenyl group , C ₆ -C ₁₄ aryl group, but is not limited thereto.

In Formula 7, R is H, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group (for example, a C ₁ -C ₁₂ alkyl group), a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group (for example, (E.g., a C ₁ -C ₁₂ alkoxy group), a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group (for example, a C ₃ -C ₁₂ cycloalkyl group), a substituted or unsubstituted C ₆ -C ₃₀ aryl group A C ₆ -C ₁₄ aryl group) or a substituted or unsubstituted C ₆ -C ₃₀ heteroaryl group (for example, a C ₆ -C ₁₄ heteroaryl group). Here, the aryl group or heteroaryl group at least one hydrogen of which is unsubstituted, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy group, or _{-N (Z 1) (Z 2} ) ( of which, Z ₁ And Z ₂ are, independently of each other, hydrogen or a C ₁ -C ₁₂ alkyl group.

Wherein a is a real number of 0 < a < = 0.99, b is a real number of 0 b 0.99, c is a real number of 0 < c < = 0.99, d is a real number of 0 & + b + c + d = 1. That is, b and / or d may be 0, but 0 in a and c are excluded. For example, a is a real number of 0.5 <a ≦ 0.95, b is a real number of 0 ≦ b ≦ 0.95, c is a real number of 0.5 <c ≦ 0.95, d is a real number of 0 ≦ d ≦ 0.95, b + c + d = 1.

The weight average molecular weight of the polymer having formula (7) may be from 10,000 to 500,000, for example, from 200,000 to 40,000. When the weight average molecular weight range as described above is satisfied, it can be used in an organic layer of an organic light emitting device to provide excellent lifetime, luminance characteristics, and the like.

The molecular weight distribution of the polymer having the formula (7) may be 1.5 to 5, for example, 2 to 3. When the molecular weight distribution as described above is satisfied, it can be used in an organic layer of an organic light emitting device to provide excellent lifetime, luminance characteristics, and the like.

The polymer having the formula (7) may be represented by any one of the following formulas (7a) to (7d), but is not limited thereto:

<Formula 7a>

&Lt; Formula 7b >

&Lt; Formula 7c >

<Formula 7d>

In the above formulas (7a) to (7d), R ₅ to R ₉ independently represent hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group, or a C ₆ -C ₃₀ aryl group, B is a real number of 0? B? 0.99, c is a real number of 0 <c? 0.99, d is a real number of 0? D? 0.99, and a + b + c + d = 1.

In the above formulas (7c) and (7d), Y ₂ and R are described in detail above.

Specific examples of the unsubstituted C ₁ -C ₂₀ alkyl group include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl. atom is a halogen atom, C ₁ -C ₃₀ alkyl group of the alkoxy group, C ₁ -C _30, the lower alkylamino group, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, hydrazine, hydrazone, a carboxyl group, a sulfonic acid group, Phosphoric acid group and the like.

In the above formulas, specific examples of the unsubstituted C ₂ -C ₁₂ alkenyl group include an ethenyl group, and at least one hydrogen atom in the alkenyl group is substituted with the same substituent as the substituent of the above-mentioned C ₁ -C ₂₀ alkyl group It is possible.

Specific examples of the unsubstituted C ₁ -C ₂₀ alkoxy group include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, And at least one hydrogen atom of the alkoxy group may be substituted with the same substituent as the substituent of the above-mentioned C ₁ -C ₂₀ alkyl group.

In the above formulas, a C ₆ -C ₃₀ aryl group means a carbocyclic aromatic system comprising at least one ring, which rings may be attached together or fused together by a pendant method. The term aryl includes aromatic systems such as phenyl, naphthyl, tetrahydronaphthyl. At least one hydrogen atom of the aryl group may be substituted with the same substituent as the substituent of the above-mentioned C ₁ -C ₂₀ alkyl group.

In the above formulas, the C ₄ -C ₃₀ heteroaryl group comprises monovalent monosaccharides having from 2 to 30 ring atoms having 1, 2 or 3 heteroatoms selected from N, O, P or S and the remaining ring atoms C The click-ring compound or said rings may be attached together or fused together by a pendant method. Examples of the heteroaryl group include pyridyl, thienyl, furyl, and the like. At least one hydrogen atom of said heteroaryl group is as described above. May be substituted with the same substituent as the substituent of the C ₁ -C ₂₀ alkyl group

In the above formulas, the C ₅ -C ₃₀ cycloalkyl group is a cyclic alkyl group, for example, a cyclohexyl group. At least one hydrogen atom of the cycloalkyl group may be substituted with the same substituent as the substituent of the above-mentioned C ₁ -C ₂₀ alkyl group

In the above formulas, the C ₅ -C ₃₀ heterocycloalkyl group is one in which at least one carbon of the cycloalkyl group is replaced by at least one heteroatom selected from N, O, P or S, for example, a pyrrolidinyl group, And a zolydinyl group. At least one hydrogen atom of the above-mentioned heterocycloalkyl group may be substituted with the same substituent as the substituent of the above-mentioned C ₁ -C ₂₀ alkyl group

The polymer having formula (7) can be synthesized by a conventional polymer synthesis method such as Suzuki coupling or Yamamoto coupling.

For example, a polymer having formula (7) can be prepared by first synthesizing a polymer having the following formula (9) and then bonding -M ₁ - (L ₂ ) _t to the end of L ₁ :

&Lt; Formula 9 >

Details of Ar ₁ , Ar ₂ , X ₁ , Y ₁ , L ₁ , X ₄ , Y ₂ , R and a to d in the above formula (9) are described above.

반복 단위를 제공할 수 있는 모노머와 함께 스즈키 커플링을 수행함으로써, 합성될 수 있다. 상기 화학식 1을 갖는 화합물을 이용하여 상기 화학식 7을 갖는 고분자를 합성할 경우, 화학식 7 중 인광 단위인 -L₁-M₁-(L₂)_t의 결합 사이트 및 결합 몰비를 용이하게 조절할 수 있다.Alternatively, the polymer having the formula (7) can be prepared by using a compound having the formula (1) as a comonomer, a - (Ar ₁ ) - repeating unit, - (Ar ₂ )

Can be synthesized by performing Suzuki coupling with monomers capable of providing repeating units. When the polymer having formula (7) is synthesized using the compound having formula (1), the bonding site and the bonding molar ratio of -L ₁ -M ₁ - (L ₂ ) _t , which is a phosphorescent unit in formula .

According to another embodiment of the present invention, there is provided an organic light emitting device having an organic layer containing a polymer having the above-described formula (7). The organic light emitting device includes a pair of electrodes and an organic layer interposed between the electrodes, wherein the organic layer may include a polymer having the formula (7). The organic layer including the light emitting polymer may be a light emitting layer.

The polymer having formula (7) may be used alone or in combination with a known host. Examples of the host include Alq ₃ , CBP (4,4'-N, N'-dicarbazole-biphenyl), PVK (poly (n-vinylcarbazole) (N, N-phenylbenzimidazole-2-yl) benzene), anthracene (ADN), TCTA, TPBI (1,3,5-tris ), TBADN (3-tert-butyl-9,10-di (naphth-2-yl) anthracene), and the like.

When the polymer having the formula (7) is used together with the host, the concentration of the host is not particularly limited, but may be about 10 to 30 parts by weight based on 100 parts by weight of the polymer.

The organic light emitting device having the organic layer including the light emitting polymer as described above may have excellent lifetime, brightness, efficiency, color purity characteristics, and the like. Further, since light can be emitted in two or more colors, it is possible to emit white light through appropriate combination of the colors.

FIG. 1 schematically shows an embodiment of the organic light emitting device, wherein the organic light emitting device includes a substrate, a first electrode, and a light emitting layer including a polymer having the formula (7) as an organic layer and a second electrode. Hereinafter, an organic light emitting device according to an embodiment of the present invention and a method of manufacturing the same will be described.

First, a first electrode material having a high work function is formed on a substrate by a vapor deposition method, a sputtering method, or the like to form a first electrode. The first electrode may be an anode. As the substrate, a substrate used in a conventional organic light emitting device is used, and a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness can be used. As the material for the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) or the like which is transparent and excellent in conductivity is used.

Next, although not shown in FIG. 1, at least one layer of a hole injection layer (HIL) and a hole transport layer (HTL) may be formed first on the first electrode, if necessary.

The hole injection layer (HIL) may be formed by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method.

When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal characteristics of the desired hole injection layer, and the like. In general, A degree of vacuum of 10 ^-8 to 10 ^-3 torr, and a deposition rate of 0.01 to 100 Å / sec.

When the hole injection layer is formed by the spin coating method, the coating conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal properties of the desired hole injection layer, and the coating speed is about 2000 rpm to 5000 rpm, The heat treatment temperature for removing the solvent after coating may be suitably selected in the temperature range of about 80 캜 to 200 캜.

As the hole injection layer material, known hole injection materials can be used. For example, a phthalocyanine compound such as copper phthalocyanine, m-MTDATA [4,4 ', 4 "-tris (3-methylphenylphenylamino) NPB (N, N'-di (1-naphthyl) -N, N'-di (1-naphthyl) -N, N'- diphenylbenzidine)), TDATA, 2T-NATA , Poly (3,4-ethylenedioxythiophene) / poly (4-ethylenedioxythiophene) / PEDOT / PSS (polyaniline / dodecylbenzenesulfonic acid) (4-styrenesulfonate), poly (4-styrenesulfonate), PANi / CSA (polyaniline / camphor sulfonicacid) or PANI / PSS (polyaniline) ), But the present invention is not limited thereto.

The thickness of the hole injection layer may be about 100 Å to 10000 Å, for example, 100 Å to 1000 Å. When the thickness of the hole injection layer is less than 100 angstroms, the hole injection characteristics may be deteriorated. When the thickness of the hole injection layer exceeds 10000 angstroms, the driving voltage may increase.

A hole transport layer (HTL) can be formed on the hole injection layer by various methods such as vacuum evaporation, spin coating, casting, LB and the like. In the case of forming the hole transporting layer by the vacuum deposition method and the spin coating method, the deposition conditions and the coating conditions vary depending on the compound used, but they can be generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The hole transport layer material may be formed using a known hole transport material. Examples of the hole transport layer material include carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N, N'-bis (3-methylphenyl) N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD), N, N'-di (naphthalen- (4,4 ', 4 "-tris (N-carbazolyl) triphenylamine (4,4', 4" )), And the like can be used as the hole transporting material. Among them, for example, in the case of TCTA, besides the hole transporting role, it can also prevent the exciton from diffusing from the light emitting layer.

The thickness of the hole transporting layer may be about 50 Å to 1000 Å, for example, 100 Å to 600 Å. When the thickness of the hole transporting layer is less than 50 Å, the hole transporting property may be deteriorated. When the thickness of the hole transporting layer is more than 1000 Å, the driving voltage may increase.

Next, the light emitting layer (EML) may be formed by a method such as spin coating, casting, LB method, or the like. In the case of forming the light emitting layer by the spin coating method, the film forming conditions vary depending on the compound used, but are generally selected from the substantially same condition range as the formation of the hole injection layer.

The light emitting layer includes a polymer having the formula (7), and may further include a host as described above.

The thickness of the light emitting layer may be about 100 Å to 1000 Å, for example, 200 Å to 600 Å. When the thickness of the light emitting layer is less than 100 Å, the light emitting characteristics may be degraded. If the thickness of the light emitting layer is more than 1000 Å, the driving voltage may increase.

Although not shown in FIG. 1, at least one layer of a hole blocking layer, an electron transport layer, and an electron injection layer may be further provided between the light emitting layer and the second electrode, if necessary.

The hole blocking layer (HBL) can prevent diffusion of triplet excitons or holes from the light emitting layer into the second electrode or the like. The hole blocking layer may be formed by a vacuum deposition method, a spin coating method, a casting method, an LB method, or the like. In the case of forming the hole blocking layer by the vacuum deposition method and the spin coating method, the conditions vary depending on the compound used, but generally, the conditions can be selected from almost the same range as the formation of the hole injection layer. Known hole blocking materials which can be used, for example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, and the like.

The thickness of the hole blocking layer may be about 50 Å to 1000 Å, for example, 100 Å to 300 Å. When the thickness of the hole blocking layer is less than 50 angstroms, the hole blocking characteristics may be deteriorated. When the thickness of the hole blocking layer exceeds 1000 angstroms, the driving voltage may be increased.

Next, the electron transport layer (ETL) can be formed by various methods such as a vacuum evaporation method, a spin coating method, and a casting method. When an electron transporting layer is formed by a vacuum deposition method and a spin coating method, the conditions vary depending on the compound used, but generally, the conditions can be selected from substantially the same range as the formation of the hole injection layer. The electron transport layer material serves to stably transport electrons injected from an electron injection electrode, and has a quinoline derivative, Bphen (4,7-diphenyl-1,10-phenanthroline, 1,10-phenanthroline) and the like may be used.

The thickness of the electron transporting layer may be about 100 ANGSTROM to 1000 ANGSTROM, for example, 200 ANGSTROM to 500 ANGSTROM. When the thickness of the electron transporting layer is less than 100 angstroms, the electron transporting characteristics may be lowered. When the thickness of the electron transporting layer exceeds 1000 angstroms, the driving voltage may increase.

Further, an electron injection layer (EIL), which is a material having a function of facilitating the injection of electrons from the cathode, may be laminated on the electron transporting layer, which is not particularly limited.

As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li ₂ O, BaO, or the like can be used. The deposition conditions of the electron injection layer may vary depending on the compound used, but may generally be selected from the same range of conditions as the formation of the hole injection layer.

The thickness of the electron injection layer may be about 1 to about 100, for example, about 5 to about 50. When the thickness of the electron injection layer is less than 1 angstrom, the electron injection characteristics may be deteriorated. When the thickness of the electron injection layer exceeds 100 angstroms, the driving voltage may increase.

Finally, the second electrode can be formed on the electron injection layer by a vacuum evaporation method, a sputtering method, or the like. The second electrode may be used as a cathode. As the metal for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, or a mixture thereof may be used. Specific examples thereof include Ba, Li, Mg, Al, Al-Li, Ca, Mg-In, Mg- -Ag). It is also possible to use two or more of these materials to form a multilayer of two or more layers. Also, a transmissive cathode using ITO or IZO may be used to obtain a front light emitting element.

[Example]

Synthetic example  1: Synthesis of compound 1

Compound 1 was synthesized according to Scheme 1 below:

<Reaction Scheme 1>

Synthesis of substance A

Two drops of phenoxazine (2.43 g, 12.9 mmoL), 1,4-dibromobutane (31 mL, 257 mmoL), NaOH (14.4 g, 360 mmoL) and Aliquat The mixture containing 44 mL of water is boiled in an oil bath. When the reaction is complete, the organic layer is extracted with MC, treated with MgSO ₄ , and the solvent is removed from the rotary. The excess 1,4-dibromobutane is distilled off using Kugel Rohr under vacuum. Thereafter, the A material can be obtained in a yield of 98% through column purification.

^One&Lt; 1 &gt; H-NMR (300 MHz, CDCl3₃2H), 6.53-6.50 (d, 2H), 3.57-3.47 (m, 4H), 2.04-1.98 (m, 2H) 1.91-1.84 (m, 2H)

^{13 C-NMR (75 MHz,} CDCl 3) δ (ppm) 162.33, 145.04, 133.20, 123.72, 120.97, 115.50, 111.32, 43.13, 33.07, 29.99, 23.78

B synthesis

A material (2.23 g, 7.01 mmol) is dissolved in 100 mL of MC and NBS (3.2 g, 17.5 mmol) is added in portions at 0 &lt; 0 &gt; C. When the addition is complete, the reaction temperature is raised to room temperature. Once the reaction is complete, work up and column purification yields material B in 76% yield.

^One&Lt; 1 &gt; H-NMR (300 MHz, CDCl3₃) [delta] (ppm) 6.88-6.84 (dd, 2H), 6.72-6.69 (d, 2H), 6.28-6.25 (d, 2H), 3.45-3.37 1.79-1.71 (m, 2 H)

^{13 C-NMR (75 MHz,} CDCl 3) δ (ppm) 145.06, 131.81, 126.52, 118.61, 112.39, 112.32, 43.22, 32.76, 30.27, 29.60, 23.32

Synthesis of C material

Acetylacetone (1.2 mL, 11.4 mmol) was added to the reaction flask containing NaH (720 mg, 28.5 mmol) and 60 mL of THF at 0 ° C, stirred for 10 minutes, and n-BuLi Hexane, 14.4 mL, 22.7 mmol) and stirred for 30 min. The dianion thus synthesized is added in small portions to a flask in which B material (1.81 g, 3.80 mmol) is dissolved in 60 mL of THF. Once the reaction is complete, the reaction can be completed by adding HCl (aq.), Work-up followed by column purification to yield the C material in 52% yield.

^One&Lt; 1 &gt; H-NMR (300 MHz, CDCl3₃) [delta] (ppm) 6.89-6.85 (dd, 2H), 6.70 (d, 2H), 6.27-6. 25 (d, 2H), 5.49 (m, 2H), 3.06 (s, 3H), 1.70-1.60 (m, 4H), 1.43-1.41

¹³C-NMR (75 MHz, CDCl3₃) [delta] (ppm) 193.87, 191.16, 145.13, 132.03, 126.54, 118.57, 112.40, 112.25, 99.93, 43.97, 38.07, 26.35, 25.25, 24.88, 24.64, 24.53

Synthesis of Compound 1

C The material (127 mg, 0.257 mmoL), [Ir (ppy)₂(μ-Cl)]₂(138 mg, 0.128 mmoL), Na₂CO₃ (54 mg, 0.514 mmol) and CH₃The reaction mixture containing 15 mL of CN was boiled for 24 hours to form a complexCompound 1Is synthesized in 65% yield.

^One&Lt; 1 &gt; H-NMR (300 MHz, CDCl3₃) (ppm) 8.55-8.50 (t, 2H), 7.88-7.66 (m, 4H), 7.58-7.49 (dd, 2H), 7.14-7.10 (M, 2H), 2.82 (s, 3H), 2.28 (m, 2H) 1.43-1.26 (m, 4H), 1.14-1.02 (m, 2H)

Synthetic example  2: Synthesis of Compound 2

Compound 2 was synthesized according to Scheme 2 below;

<Reaction Scheme 2>

Synthesis of D material

4-bromoanisole (28.9 g, 155 mmol) was reacted with n-BuLi and trimethylborate at -78 ° C, acid-treated, and extracted with methyl chloride (MC) , And the D compound is obtained in a yield of 60% through column purification.

Synthesis of E material

D The material (14.1 g, 92.7 mmol) was dissolved in THF and Na₂CO₃Solution, Pd (PPh₃)₄(4.7 g, 4.7 mmol) and 2-bromopyridine (14.7 g, 93.3 mmol), and the aqueous layer was extracted with MC. The organic layer was dried, E The material was obtained in 70% yield.

Synthesis of G-material

65.3 g of BBr ₃ was added dropwise to the E material (12.1 g, 65.3 mmol) at -10 ° C and the mixture was stirred at room temperature for 2 hours. Water was added to the resulting mixture, and the aqueous layer was extracted with MC to obtain an F compound . Thereafter, F material (7.8 g, 46 mmoL) in DMF after the reaction for 1,4-dibromobutane (1,4-dibromobutane) and two hours of 14.8g at 80 ℃ in the presence of K ₂ CO ₃ The filtrate was concentrated to separate the G material 40% yield.

Synthesis of H Substance

G The material (10.4 g, 18.4 mmoL) was reacted with 2,6-dibromophenoxazine (6.85 g, 20.1 mmol)HThe material was obtained in 30% yield.

^One&Lt; 1 &gt; H-NMR (300 MHz, CDCl3₃), 8.69 (d, 1H), 7.99-7.96 (d, 2H), 7.78-7.69 (m, 2H) 2H), 3.63 (t, 2H), 1.96-1.76 (m, 4H)

Synthesis of Compound 2

H (13 mg, 0.20 mmol), [Ir (piq) ₂ (μ-Cl)] ₂ (127 mg, 0.10 mmol) and AgCF ₃ SO ₃ (35 mg, 0.127 mmol) were dissolved in 3 mL of ethoxyethanol. After substitution, boil in an oil bath for 24 hours. When the reaction was completed, the reaction temperature was lowered to room temperature, the solvent was removed, and Compound 2 was obtained in a yield of 30% through column purification.

^{1 H-NMR (300 MHz,} CDCl 3) δ 8.56-8.40 (m, 3H), 8.12 (d, 2H), 7.98 (d, 3H), 7.7 (d, 2H), 7.54-7.50 (m, 6H) 2H), 3.93 (t, 4H), 1.71-1.52 (m, 4H), 7.32-7.28 (m, 6H)

Synthetic example  3: Synthesis of Compound 3

Compound 3 was synthesized according to Scheme 3 below:

<Reaction Scheme 3>

Synthesis of I material

PdCl ₂ (dppf) ₂ (245 mg, 0.30 mmoL) and KOAc (3 g, 30 mmoL) were placed in a flask and the air was removed from the reaction vessel by replacing N ₂ (g) with 1-bromo-4-iodobenzene 2.9 g, 10 mmoL) and 60 mL of DMSO were added. The reaction vessel was placed in an oil bath and heated to 100 ° C. to conduct the reaction. When the reaction was completed, the reaction mixture was extracted with MC and washed with H ₂ O. This was purified through column to give I material in 78% yield.

Synthesis of J material

Pd (PPh ₃ ) ₄ (18 mg, 0.159 mmol) was dissolved in 15 mL of DME and N _{2 (g) was} replaced with 2-bromopyridine (522 μL, 5.30 mmol) and Pd To this mixture was added I material (1.5 g, 5.3 mmol) and 15 mL EtOH, bubbling Na ₂ CO ₃ (2.0 M in H ₂ O, 8.0 mL) into N _{2 (g} ) For 20 minutes, the needle was removed and the temperature was raised. After completion of the reaction, work-up was carried out and the product was purified through a column to obtain J material 78% yield.

Synthesis of K material

J substance (967 mg, 4.10 mmoL), phenoxazine (phonoxazine) (759 mg, 4.14 mmoL), Pd (OAc) 2 (28 mg, 0.123 mmoL), P (t Bu) 3 (99 mg, 0.492 mmoL) and NaOtBu (569 mg, 5.92 mmol) was dissolved in toluene (40 mL) and heated at 110 ° C until the reaction was complete. When the reaction was complete, work-up was carried out and the K material was obtained in a yield of 80% by separation through a column.

^{1 H-NMR (300 MHz,} CDCl 3) δ (ppm) 8.78-8.75 (m, 1H), 8.27-8.24 (d, 2H), 7.81-7.79 (m, 2H), 7.48-7.45 (d, 2H) , 7.32-7.27 (m, 1 H), 6.77-6.60 (m, 7H), 6.07-6.04 (dd, 2H)

^{13 C-NMR (75 MHz,} CDCl 3) δ (ppm) 156.41, 149.88, 143.99, 139.65, 139.60, 137.02, 134.28, 131.16, 129.66, 123.35, 122.77, 122.60, 121.47, 120.72, 115.84, 115.53, 113.40

Synthesis of L material

K material (772 mg, 2.29 mmol) was dissolved in 20 mL of DMF and cooled to 0 ° C. NBS (823 mg, 4.58 mmol) was added thereto and the reaction was allowed to proceed at room temperature. When the reaction was completed, L- material was obtained in 79% yield after work-up and column purification.

H-NMR ¹ (300 MHz, CDCl ₃₎ δ (ppm) 8.75-8.73 (dd, 1H), 8.25-8.20 (d, 2H), 7.83-7.80 (m, 2H), 7.42-7.38 (d, 2H) , 7.33-7.28 (m, IH), 6.83 (d, 2H), 6.73-6.70 (dd, 2H), 5.88-5.85

^{13 C-NMR (75 MHz,} CDCl 3) δ (ppm) 156.09, 149.86, 144.04, 140.04, 138.60, 136.95, 133.02, 130.61, 129.81, 126.23, 122.65, 120.65, 118.61, 114.41, 112.90

Synthesis of Compound 3

L material (108.7 mg, 0.22 mmoL), [Ir (ppy) 2 (μ-Cl)] 2 (118 mg, 0.11mmoL) and _{AgCF 3 SO 3 (38 mg,} 0.148 mmoL) the melt, the nitrogen in 3 mL ethoxyethanol After substitution, boil in an oil bath for 24 hours. When the reaction was completed, the reaction temperature was lowered to room temperature, the solvent was removed, and Compound 3 was obtained in a yield of 27% through column purification.

^{1 H-NMR (300 MHz,} CDCl 3) δ 8.56 (d, 3H), 8.0-7.9 (d, 2H), 7.54-7.47 (m, 6H), 7.40-7.37 (m, 6H), 6.98-6.90 ( m, 7H), 6.6 (t, 2H), 6.31 (d, 2H)

Synthetic example  4: Synthesis of Polymer 1

Synthesis of Polymer A

240 mg of Ni (cod) ₂ , 134 mg of 2,2-bipyridyl, and 106 μl of 1,5-cyclooctadiene were dissolved in 20 mL of THF and replaced with nitrogen. The mixture was heated for 30 minutes to form an activated catalyst complex. To this reaction was added 2,7-dibromo- (2 ', 3', 6 ', 7'-tetraoctyl) spirofluorene (540 mg, 0.5 mmoL), 2,7-dibromo-9,9 -Dioctyloxyphenylfluorene (293 mg, 0.4 mmol) and H material (56 mg, 0.1 mmol) were dissolved in THF (10 mL) and the mixture was reacted at 60 ° C. for 3 days. After completion of the reaction, the polymer A is obtained by reprecipitation in toluene. The obtained polymer is removed from the impurities through a Soxhelt apparatus and dried in a vacuum oven for 24 hours.

¹ H-NMR (300 MHz, CDCl ₃ )? 7.87-7.82 (t, 1H), 7.79-7.62 (d, 1H). (Br, 2H), 6.73-6.23 (d, 2H), 6.23-6.19 (m, 2H), 7.51-7.48 2H), 1.91 (m, 2H), 1.86-1.71 (m, 2H), 1.70-1.63 (m, , 6H), 1.31-1.21 (m, 30H), 0.90-0.89 (m, 9H);

GPC analysis; Mn = 7929, PDI; 2.33

<Polymer A>

Synthesis of Polymer 1

In a 250 mL two-necked flask equipped with a thermometer, a mechanical stirrer and a reflux condenser, 200 mg of Polymer A synthesized in the above Synthesis Example was dissolved in 30 mL of toluene under a nitrogen atmosphere, and AgCF ₃ SO ₃ 19 mg were added. 30 ml of a slurry of 2-methoxyethanol containing the synthesized compound [Ir (piq) ₂ (μ-Cl)] ₂ (50 mg) was added to the reaction product obtained, And reacted for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and then the reaction solvent was removed by distillation under reduced pressure. The product was dissolved in toluene to form a precipitate in methanol. This procedure was repeated twice to obtain the following polymer 1 (160 mg)

^{1 H-NMR (300 MHz,} CDCl 3) δ 7.65-7.62 (m, 1H), 7.57-7.51 (d, 1H), 7.48 (br, 2H), 7.28 (d, 1H), 7.23 (d, 1H) 2H), 7.18-7.13 (d, 2H), 7.06-6.85 (m, 2H), 6.78-6.73 (d, 2H), 6.37 (br, 2H), 1.73 (m, 2H), 1.74 (m, 2H), 1.70 (m, 2H)

GPC analysis; Mn = 8565, PDI; 1.88

<Polymer 1>

Synthetic example  5: Synthesis of Polymer 2

Yamamoto Polymerization;

240 mg of Ni (cod) ₂ , 134 mg of 2,2-bipyridyl and 106 μl of 1,5-cyclooctadiene were dissolved in 20 mL of THF, and the mixture was heated for 30 minutes to form an activated catalyst complex. To this reaction was added 2,7-dibromo- (2 ', 3', 6 ', 7'-tetraoctyl) spirofluorene (278 mg, 0.28 mmoL), 2,7-dibromo-9,9 -Deoctyloxyphenylfluorene (167 mg, 0.224 mmol) and Compound 1 (55 mg, 0.05 mmol) were dissolved in THF (10 mL) and the reaction was allowed to proceed at 60 ° C. for 3 days. After completion of the reaction, the polymer 2 is recovered by re-precipitation in toluene. The obtained polymer is removed from the impurities through a Soxhelt apparatus and dried in a vacuum oven for 24 hours.

^{1 H-NMR (300 MHz,} CDCl 3) δ 7.72 (m, 2H), 7.57 (br, 2H), 7.41 (m, 3H), 7.24-7.19 (m, 3H), 7.27 (d, 2H), 6.79 (m, 3H), 4.06 (t, 4H), 3.94 (br, 7H), 1.74-1.71

&Lt; Polymer 2 >

Synthetic example  5; Synthesis of Polymer 3

240 mg of Ni (cod) ₂ , 134 mg of 2,2-bipyridyl, and 106 μl of 1,5-cyclooctadiene were dissolved in 20 mL of THF and replaced with nitrogen. The mixture was heated for 30 minutes to form an activated catalyst complex. To this reaction was added 2,7-dibromo- (2 ', 3', 6 ', 7'-tetraoctyl) spirofluorene (278 mg, 0.28 mmoL), 2,7-dibromo-9,9 (66 mg, 0.112 mmoL) and Compound 1 (55 mg, 0.112 mmol) were added to a solution of 4-heptyloxyphenylfluorene (84 mg, 0.112 mmoL) and 3,7-dibromo-10- , 0.05 mmol) is dissolved in 10 mL of THF, and the reaction is carried out at 60 ° C for 3 days. After completion of the reaction, the polymer 3 is obtained by re-precipitation in toluene. The obtained polymer is removed from the impurities through a Soxhelt apparatus and dried in a vacuum oven for 24 hours.

<Polymer 3>

Example

First, the transparent electrode substrate coated with ITO (indium-tin oxide) on a glass substrate was thoroughly cleaned, and ITO was patterned into a desired shape using a photosensitive resin and an etchant, and cleaned again. PEDOT (Batron P 4083, manufactured by Bayer Co.) was coated on the ITO to a thickness of about 800 Å and baked at 180 ° C for about 1 hour to form a hole injection layer. A composition for forming a light emitting layer containing toluene (99 parts by weight) and the polymer 1 (1 part by weight) synthesized in Synthesis Example was spin-coated on the hole injection layer, the solvent was completely removed in a vacuum oven after baking treatment Thereby forming a light emitting layer. At this time, the composition for forming the light emitting layer was filtered with a 0.2 mm filter before spin coating. The thickness of the light emitting layer was adjusted to about 80 nm by controlling the concentration of the light emitting layer forming composition and the spin coating speed.

Then, a second electrode was formed by sequentially depositing Ba and Al as a second electrode while maintaining the degree of vacuum below 4 x 10 &lt; ^-6 &gt; torr using a vacuum evaporator on the light emitting layer. The film thickness and film growth rate during deposition were controlled by using a crystal sensor.

Evaluation example

The color purity of the organic light emitting device of the above example was evaluated using PR650 (Spectroscan) Source Measurement Unit. As a result, it was confirmed that the organic light emitting element of the example emits white light. More specific color purity graphs, CIE color coordinates, and current density-voltage-luminance curves are shown in Figures 2, 3 and 4.

Claims (8)

A polymer represented by the following general formula (7)
&Lt; Formula 7 >

In Formula 7,
Ar ₁ and Ar ₂ are, independently of each other, represented by any one of the following formulas (8c), (8q), (8r) and (8s);
X ₁ is O or S;
Y ₁ is - (CR ₁ R ₂ ) _n1 - or - (CR ₃ R ₄ ) _n2 -O-, and R ₁ to R ₄ independently represent hydrogen, hydroxyl, amino, cyano, , A C ₁ -C ₂₀ alkyl group or a C ₂ -C ₂₀ alkylene group, and n1 and n2 are independently of each other an integer of 0 to 20;
M ₁ is Ir or Pt;
L ₁ is selected from the ligands represented by the following formulas (5a) and (5z), L ₂ is selected from the ligands represented by the following formulas (6a) and (6h);
t is 1 or 2;
X ₄ is O or S;
Y ₂ is a substituted or unsubstituted phenylene group, a naphthylene group or an anthrylene group, and the substituent of the substituted phenylene group, naphthylene group and anthrylene group is a cyano group, a hydroxyl group, a thiol group, a nitro group, a halogen An atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₂ -C ₁₀ alkenyl group and a C ₆ -C ₁₄ aryl group;
R is a substituted or unsubstituted C ₆ -C ₁₄ aryl group, and the substituent of the substituted C ₆ -C ₁₄ aryl group is a C ₁ -C ₁₂ alkyl group or a C ₁ -C ₁₂ alkoxy group;
a is a real number of 0 <a? 0.99, b is a real number of 0? a? 0.99, c is a real number of 0 <c? 0.99, d is a real number of 0? d? 0.99, a + b + c + d = 1:

Of the above formulas (8c), (8r), (8q) and (8s)
R ₅ to R ₈ independently of one another are hydrogen, a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ alkoxy group or a C ₆ -C ₂₀ aryl group;
* Represents a binding site with adjacent repeating units.

Of the above chemistry 5a and 5z,
Q _1, Q _2, Q ₃ and Q ₄ are each independently hydrogen, _{halogen, -CF 3, -CN, -Si (} A 1) (A 2) (A 3), C 1 -C 20 alkyl, C ₆ A C ₂ -C ₂₀ aryl group or a C ₁ -C ₂₀ alkoxy group;
* Represents a binding site with Y ₁ in formula (1);
* Shows a bonding site with the M ₁ of formula (I).

Among the above-mentioned formulas (6a) and (6h)
_{T 1, T 2, T 3} , T 4 and T ₅ are each independently hydrogen, _{halogen, -CF 3, -CN, -Si (} A 4) (A 5) (A 6), C 1 -C 20 alkyl group , A C ₆ -C ₂₀ aryl group or a C ₁ -C ₂₀ alkoxy group;
* Shows a bonding site with the M ₁ of formula (I). The method according to claim 1,
d is 0. The method according to claim 1,
The polymer represented by any one of formulas (7a) to (7d)
<Formula 7a>

&Lt; Formula 7b >

&Lt; Formula 7c >

<Formula 7d>

Among the above formulas,
Y ₂ is a substituted or unsubstituted phenylene group, a naphthylene group or an anthrylene group, and the substituent of the substituted phenylene group, naphthylene group and anthrylene group is a cyano group, a hydroxyl group, a thiol group, a nitro group, a halogen An atom, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₂ -C ₁₀ alkenyl group and a C ₆ -C ₁₄ aryl group;
R is a substituted or unsubstituted C ₆ -C ₁₄ aryl group, and the substituent of the substituted C ₆ -C ₁₄ aryl group is a C ₁ -C ₁₂ alkyl group or a C ₁ -C ₁₂ alkoxy group;
In the above formulas, R ₅ to R ₈ independently represent hydrogen, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group or a C ₆ -C ₁₀ aryl group,
a is a real number of 0 <a? 0.99, b is a real number of 0? a? 0.99, c is a real number of 0 <c? 0.99, d is a real number of 0? d? 0.99, a + b + d = 1. The method according to claim 1,

In the repeating unit, a red light or a green light is emitted, or a red light and a green light are simultaneously emitted. The method according to claim 1,

In the repeating unit, the polymer emitting blue light. The method according to claim 1,
White light emitting polymer. The polymer according to claim 1, which has a weight average molecular weight of 10,000 to 500,000. An organic light emitting device comprising an organic layer containing a polymer according to any one of claims 1 to 7 between a pair of electrodes.

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