KR102188522B1 - 4h-imidazo[1,2-a]imidazoles for electronic applications - Google Patents

Abstract

The present invention relates to the following compounds of formula (I), to methods for their preparation and to their use in electronic devices, in particular electroluminescent devices. The compounds of formula (I) can provide improved efficiency, stability, manufacturability or spectral properties of an electroluminescent device when used as an electron transport and/or host material for phosphorescent emitters in an electroluminescent device.
<Formula I>

Description

4H-imidazo[1,2-A]imidazole {4H-IMIDAZO[1,2-A]IMIDAZOLES FOR ELECTRONIC APPLICATIONS}

The present invention relates to compounds of formula (I), to methods for their preparation and to their use in electronic devices, in particular electroluminescent devices. The compounds of formula (I) can provide improved efficiency, stability, manufacturability or spectral properties of an electroluminescent device when used as an electron transport and/or host material for phosphorescent emitters in an electroluminescent device.

Literature [B. A. Priimenko et al., Chemistry of Heterocyclic Compounds 17 (1981) 937-40 (D1) investigate the formylation, acetylation, nitration and bromination of 1,2-diphenyl-imidazo[1,2a]benzimidazole. V. S. Ponomar et al., Chemistry of Heterocyclic Compounds 8 (1972) 229-231 (D2)] discloses the synthesis of 1H-imidazo[1,2a]benzimidazole derivatives. Literature [M. V. Povstyanol et al., Chemistry of Heterocyclic Compounds 8 (1972) 738-741 (D3)] discloses the synthesis of naphth[1,2-d]imidazo[3,2-b]imidazole derivatives. .

(R = H, Me, Et)의 합성이 기재되어 있다.See Khan, Misbahul Ain; Ribeiro, Vera Lucia Teixeira, Pakistan Journal of Scientific and Industrial Research 43 (2000) 168-170] include 1-(o-nitrophenyl)- and 1-(o-azidophenyl) trialkyl phosphites of benzimidazole- Benzimidazole[1,2-a]benzimidazole by induced deoxygenation and pyrolysis

The synthesis of (R = H, Me, Et) is described.

See Pedro Molina et al. In Tetrahedron (1994) 10029-10036], the aza Wittig-type reaction between bis(iminophosphoran) derived from bis(2-aminophenyl)amine and 2 equivalents of isocyanate was benzimidazo [1, It is reported to directly provide 2,a] benzimidazole derivatives.

See Kolesnikova, I. V.; Zhurnal Organicheskoi Khimii 25 (1989) 1689-95] includes 5H-benzimidazo[1,2-a]benzimidazole 1,2,3,4,7,8,9,10-octafluoro-5-( The synthesis of 2,3,4,5,6-pentafluorophenyl) is described.

(R = H, -CH(CH₃)₂)의 합성이 기재되어 있다.Achour, Reddouane; Zniber, Rachid, Bulletin des Societes Chimiques Belges 96 (1987) 787-92] includes benzimidazobenzimidazole prepared from benzimidazolinone derivatives.

The synthesis of (R = H, -CH(CH ₃ ) ₂ ) is described.

의 합성이 기재되어 있다.See Hubert, Andre J.; Reimlinger, Hans, Chemische Berichte 103 (1970) 2828-35] includes benzimidazobenzimidazole

The synthesis of is described.

에 의해 나타내어지는 1종 이상의 화합물을 함유하는 것인 전계발광 소자가 기재되어 있다. 하기 화합물이 명시적으로 개시되어 있다:JP2001160488 has a light emitting layer having a single or multilayer organic compound film between the opposite anode and cathode, wherein at least one layer of the organic compound film has a formula

An electroluminescent device containing at least one compound represented by is described. The following compounds are explicitly disclosed:

(I)에 의해 나타내어지는 화합물은 하나 이상의 유기 층에 함유되며, 여기서 n은 2 이상의 정수를 나타내고, L은 n-가 연결기를 나타내고, R¹, R², R³ 및 R⁴는 각각 독립적으로 수소 원자 또는 치환기를 나타낸다.US20100244006, a cathode; Anode; And at least one organic layer between a cathode and an anode. The at least one organic layer comprises a light emitting layer containing at least one light emitting material. The following formula

The compound represented by (I) is contained in at least one organic layer, wherein n represents an integer of 2 or more, L represents an n-valent linking group, and R ¹ , R ² , R ³ and R ⁴ are each independently It represents a hydrogen atom or a substituent.

는 US20100244006에 개시된 화합물의 예를 나타낸다.The compounds described in US20100244006 are preferably used as hosts in the light emitting layer.

Shows examples of compounds disclosed in US20100244006.

의 신규 유기 발광 화합물 및 그를 포함하는 유기 전계발광 장치에 관한 것이다.KR1020110008784 (WO2011010842) is the chemical formula

It relates to a novel organic light emitting compound and an organic electroluminescent device comprising the same.

US2005079387 relates to an imidazole ring-containing compound of the formula Ar ₁ -Ar ₂ -Ar ₄ (blue light emitting host compound) and an organic electroluminescence (EL) display device using the same.

로 이루어진 군으로부터 선택되고,Ar ₂ is

Is selected from the group consisting of,

로부터 선택되고, 여기서 X'는 O 또는 S이다.Each of Ar ₂ and Ar ₃ is independently

Is selected from, wherein X'is O or S.

의 이미다졸 고리 함유 화합물 및 그를 사용하는 유기 전계발광 (EL) 표시 장치에 관한 것이다. 특히, 이미다졸 고리-함유 화합물은 단독으로, 또는 전계발광 층과 같은 유기 필름용 재료로서 도펀트와 조합하여 사용될 수 있다. US2005074632 is the chemical formula

It relates to an imidazole ring-containing compound of and an organic electroluminescence (EL) display device using the same. In particular, the imidazole ring-containing compound may be used alone or in combination with a dopant as a material for an organic film such as an electroluminescent layer.

, -N(R₁₃R₁₄) 및

로 이루어진 군으로부터 선택되고, B는

및

로 이루어진 군으로부터 선택된다. X는 -O-, -S-, -Se- 및 -NH-로 이루어진 군으로부터 선택된다.A is

, -N(R ₁₃ R ₁₄ ) and

Is selected from the group consisting of, B is

And

It is selected from the group consisting of. X is selected from the group consisting of -O-, -S-, -Se- and -NH-.

JP2007180147 relates to an organic electroluminescent device comprising at least a light emitting layer containing a compound represented by Formula 1, 2, 3 or 4, with an anode and a cathode interposed therebetween:

Ar ₁ -Ar ₄ = aromatic group or aromatic heterocyclic group; R ₁ -R ₅ = H or a substituent; Z ₁ = residue required to form a 5 or 6 membered heterocyclic ring; L ₁ , L ₂ = bonding or coupling group; And X ₁ -X ₁₆ = carbon or nitrogen. A new ring may be formed in Ar ₁ and Ar ₂ , and at one of Ar ₃ and Ar ₄ .

The following compounds are explicitly disclosed:

.

.

(I)의 시클릭 화합물의 개환 중합을 수행함으로써 수득된 1종 이상의 중합체, 및 삼중항 여기자로부터 발광하는 1종 이상의 발광 재료를 함유한다.JP2004158327 relates to an organic electroluminescent device comprising at least one organic compound-containing layer provided between an anode and a cathode facing each other. The organic compound content layer has the formula

It contains at least one polymer obtained by carrying out ring-opening polymerization of the cyclic compound of (I) and at least one light-emitting material emitting light from triplet excitons.

,

.The following compounds are explicitly disclosed:

,

.

US6551723 relates to an organic electroluminescent device comprising a light-emitting layer or a plurality of thin organic compound layers containing a light-emitting layer between a pair of electrodes, wherein at least one layer in the organic electroluminescent device is represented by the following formulas I to VII. And one or more heterocyclic compounds represented by:

R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ , R ₅₁ , R ₆₁ and R ₇₁ are each independently a hydrogen atom or a substituent; Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ and Z ₇ are atomic groups necessary to form a 5- or 6-membered ring. The compounds represented by formulas I to VII are especially added to the light emitting layer and/or the electron injection/transport layer. The following compounds are explicitly disclosed:

WO2011099718 relates to a novel organic electroluminescent compound of the following formula (1) and an organic electroluminescent device using the same:

(1)

(One)

In the above formula,

A ₁ to A ₄ independently represent CR ₃ or N;

X represents -N(R ₁₀ )-, -S-, -O- or -Si(R ₁₁ )(R ₁₂ )-;

Y represents CR ₄ or N;

Ar ₁ and Ar ₂ independently represent (C6-C30)arylene with or without substituent(s) or (C3-C30)heteroarylene with or without substituent(s), and Ar3 is substituent(s) ) With or without (C6-C30) aryl or (C3-C30) heteroaryl with or without substituent(s). The compound of the above formula functions as a host in the electroluminescent layer. Among them, the following compounds are explicitly mentioned:

의 화합물 (여기서, X는 단일 결합일 수 있고, L은 2가 기일 수 있음)을 함유하는 하나 이상의 유기 층을 포함하는 전자 장치에 관한 것이다. 하기 4H-이미다조[1,2-a]이미다졸 화합물이 명시적으로 개시되어 있다:WO2011160757 is an anode, a cathode, and a chemical formula

To an electronic device comprising at least one organic layer containing a compound of (wherein X may be a single bond and L may be a divalent group). The following 4H-imidazo[1,2-a]imidazole compounds are explicitly disclosed:

In spite of these developments, there is still a need for organic light emitting devices that include novel electron transport materials that provide improved efficiency, stability, manufacturability and/or spectral properties of electroluminescent devices.

Accordingly, it is an object of the present invention to provide additional materials suitable for use in OLEDs and further applications in organic electronics, in connection with the above-mentioned prior art. More particularly, it should be possible to provide electron transport materials, hole/excitation blocker materials and matrix materials for use in OLEDs. The material should be particularly suitable for OLEDs comprising at least one phosphorescent emitter, in particular at least one green emitter or at least one blue emitter. In addition, the material must be suitable to provide an OLED that ensures good efficiency, good operating life and high stability against thermal stress of the OLED, and low usage and operating voltage.

This object was solved by the following compounds of formula I.

<Formula I>

In the above formula,

X ⁶ is -N= and X ⁷ is -NR ⁶ -, or

X ⁷ is =N- and X ⁶ is -NR ⁶ -,

의 기이고;R ⁶ is the formula

Is a group of;

A ¹ is a "branching unit" having 3 linking sites,

A ² and A ³ are independently of each other a C ₆ -C ₂₄ arylene group optionally substituted by G, or a C ₂ -C ₃₀ heteroarylene group optionally substituted by G; Wherein at least one group -(SiR ⁷ R ⁸ )- may be interposed in the groups A ¹ , A ² and A ³ ;

R ⁷ and R ⁸ are independently of each other a C ₁ -C ₂₅ alkyl group, or a C ₆ -C ₂₄ aryl group optionally substituted by G;

의 기이고;R ¹ and R ^1′ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interposed; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G, e.g. the formula

Is a group of;

R ² , R ³ , R ⁴ and R ⁵ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interposed; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G;

X ⁸ is -N=, and X ⁹ is >NL-, or

X ⁹ is =N- and X ⁸ is >NL-;

L is a single bond or a linking group;

X ¹ is N or CR ⁹ ,

X ² is N or CR ¹⁰ ,

X ³ is N or CR ⁴⁸ ,

X ⁴ is N or CR ⁴⁹ ,

X ⁵ is N or CR ⁵⁰ , provided that at least one of X ³ , X ⁴ and X ⁵ is N,

R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁹ , R ¹⁰ , R ^9'and R ^10' are independently of each other H, optionally C ₁ -C ₂₅ alkyl which may be substituted by E and/or D may be interposed group; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G; or

R ⁹ and R ¹⁰ and/or R ^9'and R ^10' together form a ring, which may be optionally substituted,

p is 0, or an integer of 1 or 2; q is 0 or an integer of 1 or 2;

D is -CO-, -COO-, -S-, -SO-, -SO ₂ -, -O-, -NR ⁶⁵ -, -SiR ⁷⁰ R ⁷¹ -, -POR ⁷² -, -CR ⁶³ =CR ⁶⁴ -Or -C≡C-,

E is -OR ⁶⁹ , -SR ⁶⁹ , -NR ⁶⁵ R ⁶⁶ , -COR ⁶⁸ , -COOR ⁶⁷ , -CONR ⁶⁵ R ⁶⁶ , -CN or halogen,

G is E, or a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₂₄ aryl group, a C ₆ -C ₂₄ aryl group substituted by C ₁ -C ₁₈ alkyl; A C ₂ -C ₃₀ heteroaryl group, or a C ₂ -C ₃₀ heteroaryl group substituted by C ₁ -C ₁₈ alkyl;

R ⁶³ and R ⁶⁴ are each independently H, C ₆ -C ₁₈ aryl; C ₁ -C ₁₈ alkyl, C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl; Or C ₁ -C ₁₈ alkyl interrupted by -O-;

R ⁶⁵ and R ⁶⁶ are each independently a C ₆ -C ₁₈ aryl group; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; A C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-; or

R ⁶⁵ and R ⁶⁶ together form a 5 or 6 membered ring,

R ⁶⁷ is a C ₆ -C ₁₈ aryl group; C ₁ -C ₁₈ alkyl group or C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkoxy; A C ₁ -C ₁₈ alkyl group; Or -O- is a C ₁ -C ₁₈ alkyl group interrupted,

R ⁶⁸ is H; A C ₆ -C ₁₈ aryl group; A C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; A C ₁ -C ₁₈ alkyl group; Or -O- is a C ₁ -C ₁₈ alkyl group interrupted,

R ⁶⁹ is C ₆ -C ₁₈ aryl; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; A C ₁ -C ₁₈ alkyl group; Or -O- is a C ₁ -C ₁₈ alkyl group interrupted,

R ⁷⁰ and R ⁷¹ are each independently a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl,

R ⁷² is a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl, provided that the following compounds:

Is excluded.

The compounds of the present invention are electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaic power), switching elements such as organic transistors, such as organic FETs and organic TFTs, organic light emitting field effect transistors (OLEFETs), image sensors, It can be used in dye lasers and electroluminescent devices (=organic light emitting diodes (OLEDs)).

Accordingly, a further subject of the invention relates to an electronic device comprising the compound according to the invention. The electronic device is preferably an electroluminescent device.

The compound of formula I can in principle be used in any layer of the EL device, but is preferably used as a host, electron transport and/or hole blocking material. In particular, the compounds of formula I are used as host and/or electron transport materials for green or blue luminescent phosphorescent emitters with good efficiency and durability.

Accordingly, a further subject of the invention relates to an electron transport layer comprising a compound of formula I according to the invention.

A further object of the invention relates to a light-emitting layer comprising a compound of formula I according to the invention. In this embodiment, the compound of compound I is preferably used in combination with a phosphorescent emitter as a host material.

A further object of the invention relates to a hole blocking layer comprising a compound of formula I according to the invention.

The compound of formula I is preferably a compound of formula I'

<Formula I'>

Wherein X ¹ , X ² , X ⁶ and X ⁷ are as defined above; R ² , R ³ , R ⁴ and R ⁵ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interposed; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G; Where E, D and G are as defined above.

의 화합물일 수 있고, X⁶은 -N=이고 X⁷은 -NR⁶-이거나, 또는 X⁷은 =N-이고 X⁶은 -NR⁶-이다. 화학식 Id의 화합물이 특히 바람직하고, 여기서 R⁹ 및 R¹⁰은 함께 고리

을 형성하고, 여기서 R¹¹, R¹², R¹³ 및 R¹⁴는 하기 정의된 바와 같다. R¹¹, R¹², R¹³ 및 R¹⁴는 바람직하게는 H이다.The compound of formula I'is the formula

May be a compound of, X ⁶ is -N= and X ⁷ is -NR ⁶ -, or X ⁷ is =N- and X ⁶ is -NR ⁶ -. Particularly preferred are compounds of formula Id, wherein R ⁹ and R ¹⁰ together are a ring

Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are as defined below. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably H.

R ² , R ³ , R ⁴ and R ⁵ are preferably H.

Compounds of formula I that are not axially symmetric, such as, for example, compounds of formula Id, wherein R ⁹ and R ¹⁰ are H, may exist in two isomeric forms:

See Example 5, which describes the synthesis of a mixture of the following compounds:

및

And

R ⁹ and R ¹⁰ are preferably H, C ₆ -C ₁₄ aryl, such as for example phenyl, naphthyl, or biphenylyl, which may optionally be substituted by one or more C ₁ -C ₈ alkyl groups ; Or C ₂ -C ₃₀ heteroaryl, such as for example dibenzofuranyl, which may optionally be substituted by one or more C ₁ -C ₈ alkyl groups.

In a preferred embodiment, the invention relates to compounds of formula II

<Formula II>

In the above formula, X ⁶ and X ⁷ are as defined above.

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interrupted; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G, and E, D, G, L, X ³ , X ⁴ , X ⁵ , R ¹ , R ^1' , R ² , R ³ , R ⁴ and R ⁵ are as defined above. Preferably, R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are H.

Preferably, X ⁶ is -N= and X ⁷ is -NR ⁶ -, or X ⁷ is =N- and X ⁶ is -NR ⁶ -; here

, 특히

의 기이고, 여기서 A¹은 화학식

의 기이고, A² 및 A³은 화학식

의 기이다.R ⁶ is the formula

, Especially

Is a group of, wherein A ¹ is the formula

And A ² and A ³ are the formula

It's a flag.

의 기는 바람직하게는 화학식

의 기, 보다 바람직하게는 화학식

의 기, 가장 바람직하게는 화합식

의 기이다. R¹은 바람직하게는 수소 원자 이외의 것이다. X⁴가 N인 경우에, R^1'는 바람직하게는 수소 원자와 상이하다. L은 바람직하게는 단일 결합 또는 화학식 -(A⁴)_r-(A⁵)_s-A⁶-의 기이다.Chemical formula

The group of is preferably the formula

Group, more preferably the formula

Group, most preferably a compounded formula

It's a flag. R ¹ is preferably anything other than a hydrogen atom. In the case where X ⁴ is N, R ^{1 'it} is preferably different from hydrogen atoms. L is preferably a single bond or a group of the formula -(A ⁴ ) _r -(A ⁵ ) _s -A ⁶ -.

및

의 화합물이 보다 바람직하고, 여기서 R¹, R^1' 및 L은 상기 정의된 바와 같다.In the above embodiment, the formula

And

More preferred are compounds of, wherein R ¹ , R ^1′ and L are as defined above.

Even more preferred are compounds of formulas IIa, IIb and IIc.

R ¹ and R ^1′ may be H, optionally a C ₁ -C ₂₅ alkyl group which may be substituted by E and/or may be interrupted by D. Preference is given to a C ₆ -C ₂₄ aryl group which may be optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group which may be optionally substituted by G.

C ₆ -C ₂₄ aryl groups R ¹ or R ^1′, which may be optionally substituted by G, are typically phenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrene Nyl, 2-, 4- or 9-fluorenyl, phenanthryl, or anthryl, which may be unsubstituted or may be substituted, for example by one or more C ₁ -C ₈ alkyl groups.

C ₂ -C ₃₀ heteroaryl group R ¹ or R ^1′, which may be optionally substituted by G, represents a ring having 5 to 7 ring atoms, or a condensed ring system, wherein nitrogen, oxygen or sulfur are possible heteroatoms , A heterocyclic group having 5 to 30 atoms, typically having at least 6 conjugated pi-electrons, such as thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl , Benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxyenyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl , Indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolinyl, kinolyl, isokinolyl, phthalazinyl, naphthyridinyl, kinoxalinyl, kinazolinyl, cinnolinyl, p Teridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, Furazanyl, 4-imidazo[1,2-a]benzimidazoyl, 5-benzimidazo[1,2-a]benzimidazoyl, carbazolyl or phenoxazinyl, which may be unsubstituted Or can be substituted.

Preferred C ₂ -C ₃₀ heteroaryl groups are pyridyl, triazinyl, pyrimidinyl, 4-imidazo[1,2-a]benzimidazoyl, 5-benzimidazo[1,2-a]benzimida Zoyl, carbazolyl (e.g. 3-(9-phenyl-carbazolyl) or 9-carbazolyl) or dibenzofuranyl (e.g. dibenzofuran-2-yl or dibenzo Furan-4-yl), which may be unsubstituted or in particular C ₆ -C ₁₀ aryl, or C ₆ -C ₁₀ aryl substituted by C ₁ -C ₈ alkyl; Or it may be substituted by C ₂ -C ₅ heteroaryl.

C ₆ -C ₂₄ aryl and C ₂ -C ₃₀ heteroaryl groups may be substituted by G, preferably by one or more C ₁ -C ₈ alkyl groups.

L is a linking group or a single bond. In a preferred embodiment of the invention, L is a single bond. In another preferred embodiment, L is a group of the formula -(A ⁴ ) _r -(A ⁵ ) _s -A ⁶ -, wherein r is 0 or 1; s is 0 or 1. L is preferably a single bond or a group of the formula -(A ⁴ ) _r -(A ⁵ ) _s -A ⁶ -, where r is 0 or 1; s is 0 or 1.

A ⁴ , A ⁵ and A ⁶ are each independently a C ₆ -C ₂₄ arylene group which may be optionally substituted by G, or a C ₂ -C ₃₀ heteroarylene group which may be optionally substituted by G.

C ₆ -C ₂₄ arylene groups A ⁴ , A ⁵ and A ⁶ , which may be optionally substituted by G, are typically phenylene, naphthylene, especially 1-naphthylene, or 2-naphthylene, pyrenylene, 2- Or 9-fluorenylene, phenanthrylene or anthrylene, which may be unsubstituted or substituted.

C ₂ -C ₃₀ heteroarylene groups A ⁴ , A ⁵ and A ⁶ , which may be optionally substituted by G, represent a ring having 5 to 7 ring atoms, or a condensed ring system, wherein nitrogen, oxygen or sulfur are possible Heterocyclic groups having 5 to 30 atoms, which are heteroatoms and typically have 6 or more conjugated π-electrons, such as thienylene, benzothiophenylene, dibenzothiophenylene, thianthrenylene, furylene, fur Furylene, 2H-pyranylene, benzofuranylene, isobenzofuranylene, dibenzofuranylene, phenoxycynylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, Pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoindolylene, indolinylene, indazolylene, purinylene, quinolinylene, kinolylene, isokynolylene, phthalazinyl Ren, naphthyridinylene, kinoxalinylene, kinazolinylene, cynnolinylene, pteridinylene, carbazolylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenanthridinylene, acridinylene , Pyrimidinylene, phenanthrolinylene, phenazinylene, isothiazolylene, phenothiazinylene, isoxazolylene, furazinylene, carbazolylene or phenoxazinylene, which may be unsubstituted or Can be substituted.

Preferred C ₆ -C ₂₄ arylene groups are 1,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrylene, It may be unsubstituted or may be substituted.

Preferred C ₂ -C ₃₀ heteroarylene groups are pyridylene, triazinylene, pyrimidinylene, carbazolylene, dibenzofuranylene, which may be unsubstituted or in particular C ₆ -C ₁₀ aryl, or C ₁ C ₆ -C ₁₀ aryl substituted by -C ₄ alkyl, or C ₂ -C ₅ heteroaryl. C ₆ -C ₂₄ arylene and C ₂ -C ₃₀ heteroarylene groups may be substituted by G, preferably by one or more C ₁ -C ₈ alkyl groups.

의 기이고, 여기서 R¹⁵는 C₆-C₁₈아릴 기; 또는 1개 이상의 C₁-C₁₈알킬 기에 의해 치환된 C₆-C₁₈아릴 기이다.In a preferred embodiment, A ⁴ , A ⁵ and A ⁶ are independently of each other the formula

Wherein R ¹⁵ is a C ₆ -C ₁₈ aryl group; Or a C ₆ -C ₁₈ aryl group substituted by one or more C ₁ -C ₁₈ alkyl groups.

의 기이고, 여기서 A⁴, A⁵ 및 A⁶은 서로 독립적으로 화학식

의 기이고, 여기서In a preferred embodiment, L is of the formula -(A ⁴ ) _r -(A ⁵ ) _s -A ⁶ -or

Is a group, wherein A ⁴ , A ⁵ and A ⁶ are independently of each other the formula

Is the group of, where

R ⁴¹ may be the same or different at each occurrence, by F, C ₁ -C ₁₈ alkyl, which is substituted by E and / or D are interposed a C ₁ -C ₁₈ alkyl, C ₆ -C ₂₄ aryl, G Substituted C ₆ -C ₂₄ aryl, C ₂ -C ₂₀ heteroaryl, or C ₂ -C ₂₀ heteroaryl substituted by G,

m1 is 0, or an integer of 1 to 4,

m2 is 0, or an integer of 1 to 3,

r is 0 or 1; s is 0 or 1;

X ¹³ is -O-, -S- or -NR ¹⁵ -,

R ¹⁵ is a C ₁ -C ₁₈ alkyl group; A C ₁ -C ₁₈ alkyl group interrupted by -O-; A C ₆ -C ₁₈ aryl group; C ₆ -C ₁₈ aryl groups substituted by one or more C ₁ -C ₁₈ alkyl groups or C ₁ -C ₁₈ alkoxy groups; A C ₂ -C ₂₀ heteroaryl group, or a C ₂ -C ₂₀ heteroaryl group substituted by one or more C ₁ -C ₁₈ alkyl groups,

R ⁷ and R ⁸ are C ₁ -C ₁₈ alkyl groups,

E, D and G are as defined above.

Examples of preferred groups L are shown below:

,

,

의 기가 바람직하다.Chemical formula

Group of is preferred.

의 기를 포함함에 따라, 기 A¹, A² 및 A³은, 예를 들어 화학식

및

의 1개 이상의 기에 의해 치환될 수 있으며, 이로써 예를 들어 하기 화학식 III의 화합물이 생성된다.The term “C ₂ -C ₃₀ heteroaryl group” refers to, for example, the formula

Depending on the inclusion of the groups A ¹ , A ² and A ³ , for example the formula

And

May be substituted by one or more groups of, thereby giving, for example, compounds of formula III

<Formula III>

, 특히

의 기이고, A² 및 A³은 화학식

의 기이고, R¹ 및/또는 R^1'는 화학식In the above formula, A ¹ is the formula

, Especially

And A ² and A ³ are the formula

And R ¹ and/or R ^1'is a group of

의 기이고, R¹⁶은 C₆-C₁₈아릴 기; 또는 1개 이상의 C₁-C₁₈알킬 기에 의해 치환된 C₆-C₁₈아릴 기, 예컨대 예를 들어 페닐, 나프틸 또는 비페닐릴이고, 이는 1개 이상의 C₁-C₈알킬 기에 의해 임의로 치환될 수 있다. R⁹¹, R⁹², R⁹³, R⁹⁴ 및 R⁹⁵는 서로 독립적으로 H, 또는 임의로 E에 의해 치환될 수 있고/거나 D가 개재될 수 있는 C₁-C₂₅알킬 기; 바람직하게는 H 또는 C₁-C₈알킬 기이다.

And R ¹⁶ is a C ₆ -C ₁₈ aryl group; Or a C ₆ -C ₁₈ aryl group substituted by one or more C ₁ -C ₁₈ alkyl groups, such as for example phenyl, naphthyl or biphenylyl, which is optionally substituted by one or more C ₁ -C ₈ alkyl groups Can be. R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ are each independently H, or a C ₁ -C ₂₅ alkyl group optionally substituted by E and/or D may be interposed; It is preferably an H or C ₁ -C ₈ alkyl group.

R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently of each other H, C ₁ -C ₂₅ which may be optionally substituted by E and/or D may be interposed Alkyl group; It is a C ₆ -C ₂₄ aryl group which may be optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group that may be optionally substituted by G.

R ⁴³ may be the same or different at each occurrence, by F, C ₁ -C ₁₈ alkyl, which is substituted by E and / or D are interposed a C ₁ -C ₁₈ alkyl, C ₆ -C ₂₄ aryl, G Substituted C ₆ -C ₂₄ aryl, C ₂ -C ₂₀ heteroaryl, or C ₂ -C ₂₀ heteroaryl substituted by G.

m3 is 0 or an integer of 1 to 4.

X ³ is N or CR ⁴⁸ , X ⁴ is N or CR ⁴⁹ , X ⁵ is N or CR ⁵⁰ , provided that at least one of X ³ , X ⁴ and X ⁵ is N.

X ⁸ is -N= and X ⁹ is >NL-, or X ⁹ is =N- and X ⁸ is >NL-.

p is 0, or an integer of 1 or 2. q is 0 or an integer of 1 or 2.

의 기는, 예를 들어 화학식

,

,

또는

의 기이다.Chemical formula

The group of, for example the formula

,

,

or

It's a flag.

A ² and A ³ are each independently a C ₆ -C ₂₄ arylene group which may be optionally substituted by G, or a C ₂ -C ₃₀ heteroarylene group which may be optionally substituted by G. The same preferred definitions for A ² and A ³ apply to A ⁴ .

,

또는

의 기이고, 여기서Preferably, A ² and A ³ are independently of each other the formula

,

or

Is the group of, where

R ₄₁ may be the same or different at each occurrence, by F, C ₁ -C ₁₈ alkyl, which is substituted by E and / or D are interposed a C ₁ -C ₁₈ alkyl, C ₆ -C ₂₄ aryl, G Substituted C ₆ -C ₂₄ aryl, C ₂ -C ₂₀ heteroaryl, or C ₂ -C ₂₀ heteroaryl substituted by G,

m1 is 0, or an integer of 1 to 4,

m2 is 0, or an integer of 1 to 3,

X ¹³ is -O-, -S- or -NR ¹⁵ -,

R ¹⁵ is a C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-; A C ₆ -C ₁₈ aryl group; C ₆ -C ₁₈ aryl groups substituted by one or more C ₁ -C ₁₈ alkyl groups or C ₁ -C ₁₈ alkoxy groups; A C ₂ -C ₂₀ heteroaryl group, or a C ₂ -C ₂₀ heteroaryl group substituted by one or more C ₁ -C ₁₈ alkyl groups.

의 기는 화학식

의 기보다 덜 바람직하다.Chemical formula

Group of formula

It is less preferred than the group of.

의 기이고, 여기서 R¹⁵는 C₆-C₁₈아릴 기; 또는 1개 이상의 C₁-C₁₈알킬 기에 의해 치환된 C₆-C₁₈아릴 기, 특히

이다. 가장 바람직한 A² 및 A³은 화학식

의 기이다.More preferably, A ² and A ³ are independently of each other in the formula

Wherein R ¹⁵ is a C ₆ -C ₁₈ aryl group; Or C ₆ -C ₁₈ aryl groups substituted by one or more C ₁ -C ₁₈ alkyl groups, in particular

to be. Most preferred A ² and A ³ are the formula

It's a flag.

A ¹ is a “branching unit” having more than two connecting sites. Examples of “branching units” are the aforementioned C ₆ -C ₂₄ arylene groups, or C ₂ -C ₃₀ heteroarylene groups having 3 linking sites, which may be optionally substituted by G.

의 기이고, 여기서 R⁴¹은 상기 정의된 바와 같다. m5는 0 또는 1이고, m6은 0, 1 또는 2이다. m5는 바람직하게는 0이다. m6은 바람직하게는 0이다. 가장 바람직한 A¹은 화학식

의 기이다.An example of A ¹ is the formula

Is a group of, wherein R ⁴¹ is as defined above. m5 is 0 or 1, and m6 is 0, 1 or 2. m5 is preferably 0. m6 is preferably 0. Most preferred A ¹ is the formula

It's a flag.

의 예는 하기에 제시된다:Desirable group

Examples of are presented below:

R ¹ and R ^{1 'has} the formula independently of one another

,

,

의 기 또는 기 -(SiR²⁰R²¹R²²)이고, 여기서

A group or group of -(SiR ²⁰ R ²¹ R ²² ), wherein

X ⁸ is -N= and X ⁹ is >NL-,

X ⁹ is =N- and X ⁸ is >NL-,

R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently of each other H, C ₁ -C ₂₅ which may be optionally substituted by E and/or D may be interposed Alkyl group; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G,

R ¹⁶ is a C ₆ -C ₁₈ aryl group; Or a C ₆ -C ₁₈ aryl group substituted by one or more C ₁ -C ₁₈ alkyl groups,

R ²⁰ , R ²¹ and R ²² are each independently a C ₆ -C ₁₈ aryl group; Or a C ₆ -C ₁₈ aryl group substituted by one or more C ₁ -C ₁₈ alkyl groups,

R ⁴³ may be the same or different at each occurrence, by F, C ₁ -C ₁₈ alkyl, which is substituted by E and / or D are interposed a C ₁ -C ₁₈ alkyl, C ₆ -C ₂₄ aryl, G Substituted C ₆ -C ₂₄ aryl, C ₂ -C ₂₀ heteroaryl, or C ₂ -C ₂₀ heteroaryl substituted by G,

R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interrupted;

m3 is 0, or an integer of 1 to 4, m4 is 0, or an integer of 1 to 3,

L, E, D and G are as defined above.

의 기 (k는 0, 1, 2 또는 3이고, R⁹¹은 H 또는 C₁-C₈알킬임), 예컨대 예를 들어More preferably, R ¹ and R ^1′ are independently of each other in the formula

A group of (k is 0, 1, 2 or 3 and R ⁹¹ is H or C ₁ -C ₈ alkyl), such as for example

이고, R¹⁶은 C₆-C₁₈아릴 기; 또는 1개 이상의 C₁-C₁₈알킬 기에 의해 치환된 C₆-C₁₈아릴 기, 특히

이다.

And R ¹⁶ is a C ₆ -C ₁₈ aryl group; Or C ₆ -C ₁₈ aryl groups substituted by one or more C ₁ -C ₁₈ alkyl groups, in particular

to be.

D is preferably -CO-, -COO-, -S-, -SO-, -SO ₂ -, -O-, -NR ⁶⁵ -, wherein R ⁶⁵ is C ₁ -C ₁₈ alkyl, such as methyl, Ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C ₆ -C ₁₄ aryl, such as phenyl, tolyl, naphthyl or biphenylyl.

E is preferably -OR ⁶⁹ ; -SR ⁶⁹ ; -NR ⁶⁵ R ⁶⁵ ; -COR ⁶⁸ ; -COOR ⁶⁷ ; -CONR ⁶⁵ R ⁶⁵ ; Or -CN; Wherein R ⁶⁵ , R ⁶⁷ , R ⁶⁸ and R ⁶⁹ are independently of each other C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl , Or 2-ethyl-hexyl, or C ₆ -C ₁₄ aryl, such as for example phenyl, naphthyl, especially 1-naphthyl, or 2-naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- , 4- or 9-fluorenyl, phenanthryl or anthryl (which may be unsubstituted or may be substituted, for example with one or more C ₁ -C ₈ alkyl groups); Or C ₂ -C ₃₀ heteroaryl, such as for example pyridyl, triazinyl, pyrimidinyl, 4-imidazo[1,2-a]benzimidazoyl, 5-benzimidazo[1,2-a ]Benzimidazoyl, carbazolyl (e.g. 3-(9-phenyl-carbazolyl) or 9-carbazolyl) or dibenzofuranyl (e.g. dibenzofuran-2- Mono or dibenzofuran-4-yl) (which may be unsubstituted or substituted by C ₆ -C ₁₀ aryl in particular substituted by C ₆ -C ₁₀ aryl, or C ₁ -C ₈ alkyl) to be.

G has the same preferred definition as E, or C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl or 2-ethyl -Hexyl or C ₁ -C ₁₈ perfluoroalkyl, such as for example -CF ₃ .

R ² , R ³ , R ⁴ , R ⁵ R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably H.

R ⁴¹ is preferably H, or C ₆ -C ₁₄ aryl, such as phenyl, tolyl, naphthyl or biphenylyl, which may be optionally substituted by C ₁ -C ₈ alkyl.

R ⁴³ is preferably H, or C ₆ -C ₁₄ aryl, such as phenyl, tolyl, naphthyl or biphenylyl, which may be optionally substituted by C ₁ -C ₈ alkyl.

m3 is preferably 0 or 1, most preferably 0. m4 is preferably 0 or 1, most preferably 0.

Examples of preferred compounds of formula I are compounds A-1 to A-18, B-1 to B-18, C-1 to C-18, and D-1 to D-19 as set forth in claim 9.

Halogen is fluorine, chlorine, bromine and iodine.

C ₁ -C ₂₅ alkyl (C ₁ -C ₁₈ alkyl) is typically linear or branched (if possible). Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1 ,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3 -Tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl , Tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. C ₁ -C ₈ alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2 ,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C ₁ -C ₄ alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl.

C ₁ -C ₂₅ alkoxy group (C ₁ -C ₁₈ alkoxy group) is a straight or branched alkoxy group, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-moiety Oxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, penta Decyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of C ₁ -C ₈ alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2 -Pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhex Siloxy, preferably C ₁ -C ₄ alkoxy, such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy to be.

The term “cycloalkyl group” typically refers to C ₄ -C ₁₈ cycloalkyl, in particular C ₅ -C ₁₂ cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclo Dodecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, which may be unsubstituted or substituted.

C ₆ -C ₂₄ aryl which may be optionally substituted (C ₆ -C ₁₈ aryl) is typically phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl or 2-naphthyl, biphenyl Ryl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl or anthryl, which may be unsubstituted or substituted.

C ₂ -C ₃₀ heteroaryl (C ₂ -C ₂₀ heteroaryl) refers to a ring or condensed ring system having 5 to 7 ring atoms, where nitrogen, oxygen or sulfur are possible heteroatoms, typically 6 or more conjugated Heterocyclic groups having 5 to 30 atoms with π-electrons such as thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzo Furanyl, dibenzofuranyl, phenoxycyenyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indozinyl, isoin Dolyl, indolyl, indazolyl, purinyl, quinolinyl, kinolyl, isokinolyl, phthalazinyl, naphthyridinyl, kinoxalinyl, kinazolinyl, cinnolinyl, pteridinyl, carbazolyl, Carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazolyl, 4-imidazo [1,2-a]benzimidazoyl, 5-benzimidazo[1,2-a]benzimidazoyl, carbazolyl or phenoxazinyl, which may be unsubstituted or substituted.

Possible substituents of the above mentioned groups are C ₁ -C ₈ alkyl, hydroxyl group, mercapto group, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, halogen, halo-C ₁ -C ₈ alkyl or cyano It's No Ki.

C ₆ -C ₂₄ aryl (C ₆ -C ₁₈ aryl) and C ₂ -C ₃₀ heteroaryl groups are preferably substituted by one or more C ₁ -C ₈ alkyl groups.

The term “aryl ether group” is typically a C _6-24 aryloxy group, ie OC _6-24 aryl, such as for example phenoxy or 4-methoxyphenyl.

If a substituent, such as for example R ⁴¹ appears more than once in a group, this may be different in each case.

The phrase “substituted by G” means that one or more, in particular 1 to 3 substituents G may be present.

As described above, the above-mentioned groups may be substituted by E and/or, if desired, D may be interposed. Intervention is of course possible only if the group contains two or more carbon atoms bonded to each other by a single bond; C ₆ -C ₁₈ aryl is not interposed; The intervening arylalkyl contains unit D in the alkyl moiety. C ₁ -C ₁₈ alkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (CH ₂ CH ₂ O) _1-9 -R ^x (where R ^x is H or C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkanoyl (e.g. CO-CH(C ₂ H ₅ )C ₄ H ₉ ), CH ₂ -CH(OR ^y' )-CH ₂ -OR ^y ( Wherein R ^y is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, C ₇ -C ₁₅ phenylalkyl, and R ^{y'encompasses the} same definition as R ^y or is H));

C ₁ -C ₈ alkylene-COO-R ^z , for example CH ₂ COOR ^z , CH(CH ₃ )COOR ^z , C(CH ₃ ) ₂ COOR ^z (where R ^z is H, C ₁ -C ₁₈ Alkyl, (CH ₂ CH ₂ O) _1-9 -R ^x , and R ^x encompasses the definitions given above);

CH ₂ CH ₂ -O-CO-CH=CH ₂ ; CH ₂ CH(OH)CH ₂ -O-CO-C(CH ₃ )=CH ₂ .

의 합성은, 예를 들어 문헌 [Achour, Reddouane; Zniber, Rachid, Bulletin des Societes Chimiques Belges 96 (1987) 787-92]에 기재되어 있다.

The synthesis of, for example, Achour, Reddouane; Zniber, Rachid, Bulletin des Societes Chimiques Belges 96 (1987) 787-92.

의 적합한 베이스 골격은 상업적으로 입수가능하거나 (특히 X가 S, O, NH인 경우에), 또는 당업자에게 공지된 방법에 의해 수득될 수 있다. WO2010079051 및 EP1885818을 참조한다.Chemical formula

Suitable base backbones of are commercially available (especially when X is S, O, NH) or can be obtained by methods known to those skilled in the art. See WO2010079051 and EP1885818.

Halogenation can be carried out by methods known to those skilled in the art. Formula II Bro at position 3 and 6 (dibrominated) or at position 3 or 6 (monobrominated) of the base skeleton at position 2,8 (dibenzofuran and dibenzothiophene) or position 3,6 (carbazole) Folk painting or iodination is preferred.

Optionally substituted dibenzofuran, dibenzothiophene and carbazole at position 2,8 (dibenzofuran and dibenzothiophene) or 3,6 position (carbazole) with bromine or NBS in glacial acetic acid or chloroform. It can be dibrominated. For example, bromination with Br ₂ can be carried out in glacial acetic acid or chloroform at low temperatures, for example 0°C. A suitable method is described, for example, in the case of X=NPh [M. Park, JR Buck, CJ Rizzo, Tetrahedron, 54 (1998) 12707-12714, and in the case of X=S [W. Yang et al., J. Mater. Chem. 13 (2003) 1351. In addition, 3,6-dibromocarbazole, 3,6-dibromo-9-phenylcarbazole, 2,8-dibromodibenzothiophene, 2,8-dibromodibenzofuran, 2-bro Mocarbazole, 3-bromodibenzothiophene, 3-bromodibenzofuran, 3-bromocarbazole, 2-bromodibenzothiophene and 2-bromodibenzofuran are commercially available.

Monobromination at the 4 position of dibenzofuran (and similarly for dibenzothiophene) is described, for example, in J. Am. Chem. Soc. 1984, 106, 7150. Dibenzofuran (dibenzothiophene) can be monobrominated at position 3 by a sequence known to those skilled in the art (including nitration, reduction and subsequent Sandmeyer reaction).

Monobromination at position 2 of dibenzofuran or dibenzothiophene and monobromination at position 3 of carbazole are carried out similarly to dibromination except that only 1 equivalent of bromine or NBS is added. do.

Alternatively, it is also possible to use dibenzofuran iodized, dibenzothiophene and carbazole.

This preparation is described, in particular, in Tetrahedron. Lett. 47 (2006) 6957-6960, Eur. J. Inorg. Chem. 24 (2005) 4976-4984, J. Heterocyclic Chem. 39 (2002) 933-941, J. Am. Chem. Soc. 124 (2002) 11900-11907, J. Heterocyclic Chem, 38 (2001) 77-87.

For nucleophilic substitution, Cl- or F-substituted dibenzofuran, dibenzothiophene and carbazole are needed. Chlorination is described, in particular, in J. Heterocyclic Chemistry, 34 (1997) 891-900, Org. Lett., 6 (2004) 3501-3504; J. Chem. Soc. [Section] C: Organic, 16 (1971) 2775-7, Tetrahedron Lett. 25 (1984) 5363-6, J. Org. Chem. 69 (2004) 8177-8182. Fluorination is described in J. Org. Chem. 63 (1998) 878-880 and J. Chem. Soc., Perkin Trans. 2, 5 (2002) 953-957.

의 도입은 염기의 존재 하에 수행된다. 적합한 염기는 당업자에게 공지되어 있으며, 바람직하게는 알칼리 금속 및 알칼리 토금속 수산화물, 예컨대 NaOH, KOH, Ca(OH)₂, 알칼리 금속 수소화물, 예컨대 NaH, KH, 알칼리 금속 아미드, 예컨대 NaNH₂, 알칼리 금속 또는 알칼리 토금속 탄산염, 예컨대 K₂CO₃ 또는 Cs₂CO₃, 및 알칼리 금속 알콕시드, 예컨대 NaOMe, NaOEt로 이루어진 군으로부터 선택된다. 또한, 상기 언급된 염기의 혼합물이 적합하다. NaOH, KOH, NaH 또는 K₂CO₃가 특히 바람직하다.group

The introduction of is carried out in the presence of a base. Suitable bases are known to the person skilled in the art, and preferably alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH) ₂ , alkali metal hydrides such as NaH, KH, alkali metal amides such as NaNH ₂ , alkali metals Or alkaline earth metal carbonates such as K ₂ CO ₃ or Cs ₂ CO ₃ , and alkali metal alkoxides such as NaOMe, NaOEt. In addition, mixtures of the above-mentioned bases are suitable. Particularly preferred are NaOH, KOH, NaH or K ₂ CO ₃ .

의, 화학식

의 할로겐화 화합물에의 구리-촉매화 커플링 (울만(Ullmann) 반응)에 의해 수행될 수 있다.Heteroarylation is, for example

Of, chemical formula

It can be carried out by copper-catalyzed coupling (Ullmann reaction) to a halogenated compound of.

N-arylation is described, for example, in H. Gilman and D. A. Shirley, J. Am. Chem. Soc. 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001) 181-186 and Eur. J. Org. Chem. (2007) 2147-2151]. The reaction can be carried out in a solvent or melt. Suitable solvents are, for example (polar) aprotic solvents such as dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), tridecane or alcohol.

의 합성은 WO2010079051에 기재되어 있다. 2-브로모-8-아이오도-디벤조푸란

의 합성은 EP1885818에 기재되어 있다.9-(8-bromodibenzofuran-2-yl)carbazole

The synthesis of is described in WO2010079051. 2-bromo-8-iodo-dibenzofuran

The synthesis of is described in EP1885818.

Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups can be readily prepared by increasing the number of pathways. An overview of synthetic pathways can be found, for example, in Angew. Chem. Int. Ed. 48 (2009) 9240-9261].

과 반응시킴으로써 수득될 수 있고 (문헌 [Prasad Appukkuttan et al., Synlett 8 (2003) 1204] 참조), 여기서 Y¹은 각 경우에 독립적으로 C₁-C₁₈알킬 기이고, Y²는 각 경우에 독립적으로 C₂-C₁₀알킬렌 기, 예컨대 -CY³Y⁴-CY⁵Y⁶- 또는 -CY⁷Y⁸-CY⁹Y¹⁰-CY¹¹Y¹²-이고, 여기서 Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ 및 Y¹²는 서로 독립적으로 수소 또는 C₁-C₁₈알킬 기, 특히 -C(CH₃)₂C(CH₃)₂-, -C(CH₃)₂CH₂C(CH₃)₂- 또는 -CH₂C(CH₃)₂CH₂-이고, Y¹³ 및 Y¹⁴는 서로 독립적으로 수소, 또는 C₁-C₁₈알킬 기이다.Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups by one conventional route are catalysts, such as, for example, in solvents such as dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene. For example in the presence of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), a complex (Pd(Cl) ₂ (dppf)) and a base such as potassium acetate, dihalide Benzofuran, dibenzothiophene and carbazole (OY ¹ ) ₂ BB(OY ¹ ) ₂ ,

Can be obtained by reacting with (see Prasad Appukkuttan et al., Synlett 8 (2003) 1204), where Y ¹ is independently in each case a C ₁ -C ₁₈ alkyl group, and Y ² is in each case Independently a C ₂ -C ₁₀ alkylene group, such as -CY ³ Y ⁴ -CY ⁵ Y ⁶ -or -CY ⁷ Y ⁸ -CY ⁹ Y ¹⁰ -CY ¹¹ Y ¹² -, wherein Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ and Y ¹² are independently of each other hydrogen or a C ₁ -C ₁₈ alkyl group, especially -C(CH ₃ ) ₂ C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ CH ₂ C(CH ₃ ) ₂ -or -CH ₂ C(CH ₃ ) ₂ CH ₂ -, and Y ¹³ and Y ¹⁴ are independently hydrogen, or C ₁ -C ₁₈ It is an alkyl group.

과 반응시킴으로써 제조될 수 있다 (문헌 [Synthesis (2000) 442-446] 참조).Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups can also be used with halogenated dibenzofuran, dibenzothiophene and carbazole with alkyl lithium reagents such as n-butyl lithium, or t- Reacted with butyl lithium, followed by a boronic acid ester, such as for example B (isopropoxy) ₃ , B (methoxy) ₃ or

It can be prepared by reacting with (see Synthesis (2000) 442-446).

과 반응시킴으로써 제조될 수 있다 (문헌 [J. Org. Chem. 73 (2008) 2176-2181]).Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups also react with dibenzofuran, dibenzothiophene and carbazole with lithium amides, such as for example lithium diisopropylamide (LDA). And then a boronic acid ester, such as for example B (isopropoxy) ₃ , B (methoxy) ₃ or

It can be prepared by reacting with (J. Org. Chem. 73 (2008) 2176-2181).

The synthesis of pyrimidine building blocks is described, for example, in WO2012/080052 (US61/422249):

은, 용매 중에서 및 촉매의 존재 하에 등몰량의 할로겐화 트리아진, 예컨대 예를 들어

과 반응시킬 수 있다. 촉매는 μ-할로(트리이소프로필포스핀)(η³-알릴)팔라듐(II) 유형 중 하나일 수 있다 (예를 들어, WO99/47474 참조).Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups, such as for example

Silver, in a solvent and in the presence of a catalyst, equimolar amounts of halogenated triazines, such as for example

And can react. The catalyst may be one of the μ-halo(triisopropylphosphine)(η ³ -allyl)palladium(II) type (see for example WO99/47474).

,

(여기서,

임)로 이루어진 군으로부터 선택된 리간드의 첨가가 바람직하다. 리간드는 Pd를 기준으로 하여 1:1 내지 1:10의 비로 첨가된다. 또한 바람직하게는, 촉매는 용액 또는 현탁액 중으로서 첨가된다. 바람직하게는, 적절한 유기 용매, 예컨대 상기 기재된 것, 바람직하게는 벤젠, 톨루엔, 크실렌, THF, 디옥산, 보다 바람직하게는 톨루엔 또는 그의 혼합물이 사용된다. 용매의 양은 통상적으로 보론산 유도체의 몰당 1 내지 10 l 범위에서 선택된다. 유기 염기, 예컨대 예를 들어 테트라알킬암모늄 히드록시드, 및 상 이동 촉매, 예컨대 예를 들어 TBAB는 붕소의 활성을 촉진할 수 있다 (예를 들어, 문헌 [Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407] 및 그에 인용된 참고문헌 참조). 반응 조건의 다른 변화는 문헌 [T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; 및 M. Remmers, M. Schulze, G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252 및 G. A. Molander und B. Canturk, Angew. Chem., 121 (2009) 9404 - 9425]에 제시되어 있다.Preferably, the Suzuki reaction is in the presence of an organic solvent such as an aromatic hydrocarbon or a common polar organic solvent such as benzene, toluene, xylene, tetrahydrofuran, or dioxane, or mixtures thereof, most preferably toluene. Performed. Typically, the amount of the solvent is selected in the range of 1 to 10 L per mole of the boronic acid derivative. Also preferably, the reaction is carried out under an inert atmosphere such as nitrogen or argon. In addition, it is preferred to carry out the reaction in the presence of an aqueous base such as an alkali metal hydroxide or carbonate, such as NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO ₃ , and the like, preferably aqueous K ₂ A CO ₃ solution is selected. Typically, the molar ratio of base to boronic acid or boronic acid ester derivative is selected in the range of 0.5:1 to 50:1, very particularly 1:1. In general, the reaction temperature is selected in the range of 40 to 180° C., preferably under reflux conditions. Preferably, the reaction time is selected in the range of 1 to 80 hours, more preferably 20 to 72 hours. In a preferred embodiment, conventional catalysts for coupling reactions or polycondensation reactions, preferably Pd-based catalysts are used, which are described in WO2007/101820. The palladium compound is added in a ratio of 1:10000 to 1:50, preferably 1:5000 to 1:200, based on the number of bonds to be closed. For example, the use of palladium(II) salts such as PdAc ₂ or Pd ₂ dba ₃ , and

,

(here,

It is preferred to add a ligand selected from the group consisting of). The ligand is added in a ratio of 1:1 to 1:10 based on Pd. Also preferably, the catalyst is added as a solution or suspension. Preferably, suitable organic solvents are used, such as those described above, preferably benzene, toluene, xylene, THF, dioxane, more preferably toluene or mixtures thereof. The amount of the solvent is usually selected in the range of 1 to 10 l per mole of the boronic acid derivative. Organic bases such as tetraalkylammonium hydroxide, and phase transfer catalysts such as TBAB can promote the activity of boron (see, eg Leadbeater &Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407] and references cited therein). Other changes in reaction conditions are described in TI Wallow and BM Novak in J. Org. Chem. 59 (1994) 5034-5037; And M. Remmers, M. Schulze, G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252 and GA Molander und B. Canturk, Angew. Chem., 121 (2009) 9404-9425.

Possible synthetic routes for compound A-1 or similar compounds are shown in the following scheme:

Lichang Zeng, Thomas Y.-H. Lee, Paul B. Merkel and Shaw H. Chen, J. Mater. Chem. 19 (2009) 8772-8781. The synthesis of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine is described in WO2011/019156.

Possible synthetic routes for compounds B-1 and B-13 are shown in the following scheme:

The synthesis of 4-chloro-2,6-diphenyl-pyrimidine is described in WO05/033084. The synthesis of 4,6-diaryl-2-chloropyrimidine can be carried out according to the method described in Journal of Heterocyclic Chemistry 43 (2006) 127-131, or similar thereto.

The compounds of formula I are particularly suitable for use in applications where charge carrier conductivity is required, and in particular from switching elements such as organic transistors, such as organic FETs and organic TFTs, organic solar cells and organic light-emitting diodes (OLEDs). Suitable for use in selected organic electronics applications, the compounds of formula I being particularly suitable for use in combination with phosphorescent emitters as matrix materials and/or hole/excitation blocker materials and/or electron transport materials in light emitting layers in OLEDs. Turned out. When the compounds of the formula (I) of the present invention are used in OLEDs, an OLED is obtained that has good efficiency and long life and can be operated particularly at low usage and operating voltages. The compounds of formula I of the invention are particularly suitable for use as electron transport, matrix and/or hole/excitation blocker materials for blue and green emitters, for example blue or dark blue emitters, which are in particular phosphorescent emitters. In addition, the compounds of formula I can be used as transport (conductor)/complementary materials in organic electronics applications selected from switching elements and organic solar cells.

In either the light-emitting layer or one of the light-emitting layers of the OLED, it is possible to combine the light-emitting material with a matrix material of the compound of formula I and, for example, a further matrix material with good hole conductor (hole transport) properties. This achieves high quantum efficiency of this light-emitting layer.

When the compound of formula (I) is used as a matrix material in the light-emitting layer, and additionally as a hole/excitation blocker material, due to the chemical identity or similarity of the material, an improved interface between the light-emitting layer and the adjacent hole/excitation blocker material is Obtained, which can lead to a reduction in voltage at equivalent luminance and an extension of the lifetime of the OLED. Moreover, the use of the same material for the hole/excitation blocker material and the matrix of the light emitting layer makes it possible to simplify the manufacturing process of the OLED, since the same source can be used in the deposition process of one of the compounds of formula I. to be.

Suitable structures for organic electronic devices are known to those skilled in the art and are specified below.

The organic transistor generally includes a semiconductor layer formed from an organic layer having hole transport capability and/or electron transport capability; A gate electrode formed from a conductive layer; And an insulating layer introduced between the semiconductor layer and the conductive layer. A transistor element is manufactured by mounting the source electrode and the drain electrode in this arrangement. In addition, additional layers known to the person skilled in the art may be present in the organic transistor.

Organic solar cells (photoelectric conversion elements) generally comprise an organic layer present between two plate-shaped electrodes arranged in parallel. The organic layer can be arranged on the comb-shaped electrode. There are no specific restrictions related to the area of the organic layer, and no specific restrictions related to the material of the electrode. However, when plate-shaped electrodes arranged in parallel are used, at least one electrode is preferably formed from a transparent electrode, for example an ITO electrode or a fluorine-doped tin oxide electrode. The organic layer is formed from two sub-layers, that is, a layer having a p-type semiconductor property or a hole transport capability, and a layer formed to have an n-type semiconductor property or an electron transport capability. It is also possible that additional layers known to the person skilled in the art are present in the organic solar cell. The layer having electron transport capability may comprise a compound of formula (I).

It is likewise possible for the compound of formula I to be present as an electron transport material in both the light emitting layer (preferably as a matrix material) and in the hole blocking layer (as a hole/excitation blocker) and/or in the electron transport layer.

The present invention provides an anode An and a cathode Ka, and an emissive layer E arranged between the anode An and the cathode Ka, and, where appropriate, at least one hole/excitation blocking layer, at least one electron/excitation blocking layer, at least one hole injection layer, one At least one additional layer selected from the group consisting of at least one hole transport layer, at least one electron injection layer and at least one electron transport layer, wherein at least one compound of formula (I) is in the light emitting layer E and/or at least one additional layer. It further provides an organic light emitting diode which is present. At least one compound of formula I is preferably present in the light emitting layer and/or the hole blocking layer and/or the electron transport layer.

Structure of the OLED of the present invention

Accordingly, the organic light emitting diode (OLED) of the present invention generally has the following structure:

An anode (An) and a cathode (Ka), and a light emitting layer disposed between the anode (An) and the cathode (Ka) E.

The inventive OLED can be formed, for example-in a preferred embodiment-from the following layers:

1. Anode

2. Hole transport (conductor) layer

3. Light emitting layer

4. Hole/excitation blocking layer

5. Electron transport (conductor) layer

6. Cathode

Layer sequences different from the above-mentioned structures are also possible, which are known to the person skilled in the art. For example, an OLED may not have all of the mentioned layers; For example, OLEDs with layers (1) (anode), (3) (light-emitting layer) and (6) (cathode) are likewise suitable, in this case layers (2) (hole conductor layer) and (4) The functions of (hole/excitation blocking layer) and (5) (electron conductor layer) are estimated by adjacent layers. OLEDs having layers (1), (2), (3) and (6), or layers (1), (3), (4), (5) and (6) are likewise suitable. In addition, the OLED can have an electron/excitation blocking layer between the anode (1) and the hole conductor layer (2).

In addition, a plurality of the above-mentioned functions (electron/excitation blocker, hole/excitation blocker, hole injection, hole conduction, electron injection, electron conduction) are combined in one layer, which is, for example, a single material present in this layer. It is possible to be done by For example, the material used in the hole conductor layer can block excitons and/or electrons simultaneously, in one embodiment.

Moreover, among those specified above, the individual layers of the OLED can be re-formed from two or more layers. For example, the hole conductor layer may be formed from a layer into which holes are injected from an electrode, and a layer that transports holes from the hole-injection layer into the light emitting layer. The electron conductive layer may likewise consist of a plurality of layers, for example a layer into which electrons are injected by an electrode, and a layer that receives electrons from the electron injection layer and transports them into the light emitting layer.

In order to obtain a particularly efficient OLED, for example, the HOMO (highest occupied molecular orbital) of the hole transport layer must correspond to the work function of the anode, and the LUMO (lowest unoccupied molecular orbital) of the electron transport layer must correspond to the work function of the cathode. It should be matched, provided the above mentioned layers are present in the inventive OLED.

The anode 1 is an electrode that provides positive charge carriers. It can be formed, for example, from a material comprising a metal, a mixture of various metals, a metal alloy, a metal oxide or a mixture of various metal oxides. Alternatively, the anode can be a conductive polymer. Suitable metals include metals and main group metals, transition metals and lanthanoid metals, in particular metals of groups Ib, IVa, Va and VIa of the periodic table of the elements, and metals and alloys of transition metals of group VIIIa. When the anode is to be transparent, a mixed metal oxide of groups IIb, IIIb and IVb of the Periodic Table of the Elements (IUPAC version) is generally used, for example indium tin oxide (ITO). Similarly anode (1) is described, for example, in Nature, Vol. 357, pages 477 to 479 (June 11, 1992)], it is possible to include organic materials, for example polyaniline. At least one of the anode or the cathode must be at least partially transparent to be able to emit the light formed. The material used for the anode 1 is preferably ITO.

Suitable hole transport materials for the layer (2) of the inventive OLEDs are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, Vol. 18, pages 837 to 860, 1996]. Both hole-transporting molecules and polymers can be used as hole transporting materials. Typically used hole-transport molecules are tris[N-(1-naphthyl)-N-(phenylamino)]triphenylamine (1-naphDATA), 4,4′-bis[N-(1-naph Tyl)-N-phenylamino]biphenyl (α-NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4' ,-Diamine (TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N'-bis(4-methylphenyl)-N,N'-bis(4- Ethylphenyl)-[1,1'-(3,3',-dimethyl)biphenyl]-4,4'-diamine (ETPD), tetrakis(3-methylphenyl)-N,N,N',N' -2,5-phenylenediamine (PDA), α-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehyde diphenylhydrazone (DEH), triphenylamine ( TPA), bis[4-(N,N-diethylamino)-2-methylphenyl)(4-methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]-5 -[p-(diethylamino)phenyl]pyrazoline (PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB), N,N,N',N '-Tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TTB), 4,4',4"-tris(N,N-diphenylamino)triphenyl Amine (TDTA), 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA), N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl ) Benzidine (β-NPB), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-spirobifluorene (spiro-TPD), N,N'-bis (Naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-spirobifluorene (spiro-NPB), N,N'-bis(3-methylphenyl)-N,N'-bis (Phenyl)-9,9-dimethylfluorene (DMFL-TPD), di[4-(N,N-ditolylamino)phenyl]cyclohexane, N,N'-bis(naphthalen-1-yl)-N ,N'-bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-2,2-dimethylbenzidine, N, N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine, N,N'-bis(3-methyl Phenyl)-N,N'-bis(phenyl)benzidine, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 4,4' ,4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4"-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine, Pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile (PPDN), N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine ( MeO-TPD), 2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobifluorene (MeO-spiro-TPD), 2,2'-bis[N ,N-bis(4-methoxyphenyl)amino]-9,9-spirobifluorene (2,2'-MeO-spiro-TPD), N,N'-diphenyl-N,N'-di[ 4-(N,N-ditolylamino)phenyl]benzidine (NTNPB), N,N'-diphenyl-N,N'-di[4-(N,N-diphenylamino)phenyl]benzidine (NPNPB) , N,N'-di(naphthalen-2-yl)-N,N'-diphenylbenzene-1,4-diamine (β-NPP), N,N'-bis(3-methylphenyl)-N,N '-Bis(phenyl)-9,9-diphenylfluorene (DPFL-TPD), N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-di Phenylfluorene (DPFL-NPB), 2,2',7,7'-tetrakis (N,N-diphenylamino)-9,9'-spirobifluorene (spiro-TAD), 9,9- Bis[4-(N,N-bis(biphenyl-4-yl)amino)phenyl]-9H-fluorene (BPAPF), 9,9-bis[4-(N,N-bis(naphthalene-2- Yl)amino)phenyl]-9H-fluorene (NPAPF), 9,9-bis[4-(N,N-bis(naphthalen-2-yl)-N,N'-bisphenylamino)phenyl]-9H -Fluorene (NPBAPF), 2,2',7,7'-tetrakis[N-naphthalenyl(phenyl)amino]-9,9'-spirobifluorene (spiro-2NPB), N,N' -Bis(phenanthrene-9-yl)-N,N'-bis(phenyl)benzidine (PAPB), 2,7-bis[N,N-bis(9,9-spirobifluoren-2-yl) Amino]-9,9-spirobifluorene (spiro-5), 2,2'-bis[N,N-bis(biphenyl-4-yl)amino]9,9-spirobifluorene (2, 2'-spiro-DBP), 2,2'-bis(N,N-diphenylamino)-9,9-spirobifluorene (spiro-BPA), 2,2',7,7'-tetra( N,N-ditolyl)aminospirobifluorene (spiro-TTB), N,N,N',N'-tetranaphthalen-2-ylbenzidine (TNB), porphyrin compound and phthalocyanine, such as copper phthalocyanine and titanium oxide It is selected from the group consisting of phthalocyanines. The hole-transporting polymer typically used is selected from the group consisting of polyvinylcarbazole, (phenylmethyl)polysilane and polyaniline. Likewise it is possible to obtain hole-transporting polymers by doping hole-transporting molecules into polymers such as polystyrene and polycarbonate. Suitable hole-transporting molecules are those already mentioned above.

It is also possible-in one embodiment-to use the carbene complex as the hole transport material, and the band gap of the at least one hole transport material is generally larger than the band gap of the illuminant material used. In the context of this application, “band gap” is understood to mean triplet energy. Suitable carbene complexes are, for example, carbene complexes as described in WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727. One example of a suitable carbene complex is Ir(dpbic) ₃ having the formula:

This is described for example in WO2005/019373. In principle, it is possible for the hole transport layer to contain one or more compounds of formula (I) as hole transport materials.

The light-emitting layer 3 comprises one or more illuminant materials. In principle, it may be a fluorescent or phosphorescent emitter, and suitable emitter materials are known to the person skilled in the art. The at least one emitter material is preferably a phosphorescent emitter. Phosphorescent emitter compounds which are preferably used are based on metal complexes, in particular complexes of metals Ru, Rh, Ir, Pd and Pt, especially of Ir, which have increased in importance. The compound of formula I can be used as a matrix in the light emitting layer.

Metal complexes suitable for use in the OLED of the present invention are, for example, documents WO　02/60910　A1, US　2001/0015432　A1, US　2001/0019782　A1, US　2002/0055014　A1, US　2002/0024293　A1, US　2002/0024293　A1, US　2002 A1, EP　1　191　612　A2, EP　1191　613　A2, EP　1　211　257　A2, US　2002/0094453　A1, WO　02/02714　A2, WO　15A2, WO1645A1/415A2, WO01A15 WO　2005/019373　A2, WO　2005/113704　A2, WO　2006/115301　A1, WO　2006/067074　A1, WO　2006/056418, WO　2006 121811　A1, WO　2007095118　2007/115970, WO　2007/115970, WO　2007/1159970 000727, WO2010129323, WO2010056669 and WO10086089.

Further suitable metal complexes are commercially available metal complexes tris(2-phenylpyridine)iridium(III), iridium(III) tris(2-(4-tolyl)pyridinato-N,C ^2′ ), bis (2-phenylpyridine) (acetylacetonato) iridium (III), iridium (III) tris (1-phenylisoquinoline), iridium (III) bis (2,2'-benzothienyl) pyridinato- N,C ^3' ) (acetylacetonate), tris (2-phenylquinoline) iridium (III), iridium (III) bis (2- (4,6-difluorophenyl) pyridinato-N, C ² ) Picolinate, iridium (III) bis (1-phenylisoquinoline) (acetylacetonate), bis (2-phenylquinoline) (acetylacetonato) iridium (III), iridium (III) bis (di- Benzo[f,h]quinoxaline)(acetylacetonate), iridium(III) bis(2-methyldi-benzo[f,h]quinoxaline)(acetylacetonate) and tris(3-methyl-1-phenyl) -4-Trimethylacetyl-5-pyrazolino)terbium (III), bis[1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinoline] (acetylacetonato)iridium (III) , Bis(2-phenylbenzothiazoleato)(acetylacetonato)iridium(III), bis(2-(9,9-dihexylfluorenyl)-1-pyridine)(acetylacetonato)iridium( III), bis(2-benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III).

In addition, the following commercially available materials are suitable: tris (dibenzoylacetonato) mono (phenanthroline) europium (III), tris (dibenzoyl methane)-mono (phenanthroline) europium (III), Tris (dibenzoylmethane) mono (5-aminophenanthroline) europium (III), tris (di-2-naphthoylmethane) mono (phenanthroline) europium (III), tris (4-bromobenzoylmethane) Mono (phenanthroline) europium (III), tris (di (biphenyl) methane) mono (phenanthroline) europium (III), tris (dibenzoyl methane) mono (4,7-diphenylphenanthroline) europium (III), Tris (dibenzoylmethane) mono (4,7-di-methylphenanthroline) europium (III), Tris (dibenzoylmethane) mono (4,7-dimethylphenanthroline disulfonic acid) europium (III) Disodium salts, tris[di(4-(2-(2-ethoxyethoxy)ethoxy)benzoylmethane)]mono(phenanthroline)uropium(III) and tris[di[4-(2-(2) -Ethoxyethoxy)ethoxy)benzoylmethane)]mono(5-aminophenanthroline) europium(III), osmium(II) bis(3-(trifluoromethyl)-5-(4-tert-butyl) Pyridyl)-1,2,4-triazolato)diphenylmethylphosphine, osmium (II) bis(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4- Triazole) dimethylphenylphosphine, osmium (II) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1,2,4-triazolato)dimethylphenylphosphine, Osmium(II) bis(3-(trifluoromethyl)-5-(2-pyridyl)pyrazolato)dimethylphenylphosphine, tris[4,4'-di-tert-butyl(2,2') -Bipyridine]ruthenium(III), osmium(II) bis(2-(9,9-dibutylfluorenyl)-1-isoquinoline (acetylacetonate).

(IX)의 화합물을 포함하며, 이는 WO 2005/019373 A2에 기재되어 있고, 여기서 기호는 하기 의미를 갖는다:The light-emitting layer preferably has the formula

(IX) compounds, which are described in WO 2005/019373 A2, where the symbols have the following meanings:

M is Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re, Cu, Ag and Au in any possible oxidation state for each metal atom. A metal atom selected from the group consisting of;

Carbene is an uncharged or monoanionic, and a carbene ligand which may be single, bidentate or tridentate, and the carbene ligand may also be a biscarbene or triscarbene ligand;

L is a monoanionic or dianionic ligand, which may be single or bidentate;

K is phosphine; Phosphonate and its derivatives, arsenate and its derivatives; Phosphite; CO; Pyridine; It is an uncharged monodentate or bidentate ligand selected from the group consisting of nitrile and conjugated diene forming a π complex with M ¹ ;

n1 is the number of carbene ligands, where n1 is at least 1, and when n1> 1 the carbene ligands in the complex of formula I may be the same or different;

m1 is the number of ligands L, where m1 can be 0 or> 1, and when m1> 1 then ligands L can be the same or different;

o is the number of ligands K, where o can be 0 or> 1, and when o> 1 the ligands K can be the same or different;

Here, the sum of n1 + m1 + o depends on the oxidation state and coordination number of the metal atom, and on the number of digits of the ligand carbene, L and K, and also on the charge of the ligand, carbene and L, provided that n1 is 1 or more.

(IXa)의 금속-카르벤 착물이 보다 바람직하며, 이는 WO2011/073149에 기재되어 있고, 여기서 M, n1, Y, A², A³, A⁴, A⁵, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, R⁵⁶, R⁵⁷, R⁵⁸, R⁵⁹, K, L, m1 및 o는 각각 하기와 같이 정의된다:Carbene complexes, which are suitable triplet light emitters, are described, for example, in WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981, WO2008/000727, WO2009050281, WO2009050290, WO2011051404 and WO2011073149. Chemical formula

More preferred are the metal-carbene complexes of (IXa), which are described in WO2011/073149, where M, n1, Y, A ² , A ³ , A ⁴ , A ⁵ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , K, L, m1 and o are each defined as follows:

M is Ir or Pt,

n1 is an integer selected from 1, 2 and 3,

Y is NR ⁵¹ , O, S or C(R ²⁵ ) ₂ ,

A ² , A ³ , A ⁴ and A ⁵ are each independently N or C, where 2 A = nitrogen atom, at least one carbon atom is present between two nitrogen atoms in the ring,

R ⁵¹ is a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally holding at least one functional group, and having 1 to 20 carbon atoms, optionally interrupted by at least one heteroatom and optionally holding at least one functional group, Cycloalkyl radical having 3 to 20 carbon atoms, substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally retaining one or more functional groups and having 6 to 30 carbon atoms, optionally one or more heteroatoms A substituted or unsubstituted heteroaryl radical interposed and optionally having at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,

R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ are each a free electron pair when A ² , A ³ , A ⁴ and/or A ⁵ is N, or A ² , A ³ , A ⁴ and/or A ^{When 5} is C, each independently hydrogen, a linear or branched alkyl radical having one or more heteroatoms optionally interposed, one or more functional groups, and having 1 to 20 carbon atoms, one or more heteroatoms are optionally interposed Cycloalkyl radical optionally having at least one functional group and having 3 to 20 carbon atoms, substituted or unsubstituted aryl having at least one heteroatom optionally interposed and optionally having at least one functional group and having 6 to 30 carbon atoms A radical, a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms, a group having a donor or acceptor function, optionally interposed with one or more heteroatoms, optionally holding one or more functional groups, or

R ⁵³ and R ⁵⁴ together with A ³ and A ⁴ form an optionally substituted unsaturated ring having a total of 5 to 18 carbon atoms and/or heteroatoms, optionally interrupted by one or more additional heteroatoms,

R ⁵⁶ , R ⁵⁷ , R ⁵⁸ and R ⁵⁹ are each independently hydrogen, a linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally holding one or more functional groups, and having 1 to 20 carbon atoms, 1 Cycloalkyl radical, optionally interrupted by at least one heteroatom, optionally holding at least one functional group, and having 3 to 20 carbon atoms, optionally interrupted by at least one heteroatom, optionally holding at least one functional group, and having 3 to 20 carbon atoms A cycloheteroalkyl radical having, a substituted or unsubstituted aryl radical having one or more heteroatoms optionally interposed, one or more functional groups optionally having 6 to 30 carbon atoms, one or more heteroatoms optionally interposed, one or more functional groups Is a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms, and having a donor or acceptor function, or

R ⁵⁶ and R ⁵⁷ , R ⁵⁷ and R ⁵⁸ or R ⁵⁸ and R ⁵⁹ , together with the carbon atom to which they are attached, are optionally interrupted by one or more heteroatoms and have a total of 5 to 18 carbon atoms and/or heteroatoms. Forming a substituted saturated, unsaturated or aromatic ring, and/or

When A ⁵ is C, R ⁵⁵ and R ⁵⁶ together optionally contain a heteroatom, an aromatic unit, a heteroaromatic unit and/or a functional group, and have a total of 1 to 30 carbon atoms and/or heteroatoms. , Forming a linear or branched bridge, wherein substituted or unsubstituted 5- to 8-membered rings comprising carbon atoms and/or heteroatoms are optionally fused,

R ²⁵ is independently a linear or branched alkyl radical optionally interrupted by one or more heteroatoms, optionally holding one or more functional groups, and having 1 to 20 carbon atoms, optionally interrupted by one or more heteroatoms, and optionally one or more functional groups. A cycloalkyl radical having 3 to 20 carbon atoms, a substituted or unsubstituted aryl radical optionally interrupted by one or more heteroatoms, optionally holding one or more functional groups and having 6 to 30 carbon atoms, one or more hetero A substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms, wherein the atom is optionally interposed, optionally retaining one or more functional groups,

K is an uncharged single or double digit ligand,

L is a monoanionic or dianionic ligand, preferably a monoanionic ligand, which may be single or double digit,

m1 is 0, 1 or 2, wherein when m1 is 2, the K ligands may be the same or different,

o is 0, 1 or 2, wherein when o is 2, the L ligands may be the same or different.

The compound of formula IX is preferably a compound of the formula:

Homoligandic metal-carbene complexes may exist in the form of facets or meridian isomers, and isomers are preferred.

In the case of heteroligandic metal-carbene complexes, four different isomers may exist, with pseudo-surface isomers being preferred.

The light-emitting layer may include additional components in addition to the illuminant material. For example, a fluorescent dye may be present in the light emitting layer to change the light emission color of the illuminant material. Also-in a preferred embodiment-a matrix material may be used. This matrix material can be a polymer, for example poly(N-vinylcarbazole) or polysilane. However, the matrix material may be a small molecule, for example 4,4'-N,N'-dicarbazolebiphenyl (CDP=CBP) or a tertiary aromatic amine, such as TCTA. In a preferred embodiment of the invention, one or more compounds of formula I are used as matrix material.

In one embodiment of the invention, a compound of formula (X) is used as a matrix material with a carbene complex as a triplet emitter in the light emitting layer.

<Formula X>

In the above formula,

X is NR, S, O or PR;

R is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl;

A ¹ is -NR ⁶ R ⁷ , -P(O)R ⁸ R ⁹ , -PR ¹⁰ R ¹¹ , -S(O) ₂ R ¹² , -S(O)R ¹³ , -SR ¹⁴ or -OR ¹⁵ ;

R ²¹ , R ²² and R ²³ are each independently aryl, heteroaryl, alkyl, cycloalkyl, or heterocycloalkyl, wherein at least one of the groups R ¹ , R ² or R ³ is aryl or heteroaryl;

R ⁴ and R ⁵ are independently of each other an alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, group A ¹ , or a group having donor or acceptor properties;

n2 and m1 are each independently 0, 1, 2 or 3;

R ⁶ , R ⁷ together with the nitrogen atom form a cyclic moiety having 3 to 10 ring atoms, which may be unsubstituted, or alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and donors or And/or may be substituted with one or more substituents selected from groups having acceptor properties; May be cyclized with one or more additional cyclic moieties having 3 to 10 ring atoms, wherein the cyclized moiety may be unsubstituted, or alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and donors Or may be substituted with one or more substituents selected from groups having acceptor properties;

은 WO2010079051 (PCT/EP2009/067120; 특히 19 내지 26 페이지, 및 27 내지 34 페이지, 35 내지 37 페이지 및 42 내지 43 페이지 상의 표)에 기재되어 있다.R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl. Compounds of formula X, such as for example

Is described in WO2010079051 (PCT/EP2009/067120; in particular the tables on pages 19-26, and pages 27-34, pages 35-37 and 42-43).

Additional matrix materials based on dibenzofuran are described, for example, in US2009066226, EP1885818B1, EP1970976, EP1998388 and EP2034538. Examples of particularly preferred matrix materials are shown below:

및

은 WO2012/130709에 기재되어 있다.In the aforementioned compounds, T is O or S, preferably O. When T is present more than once in a molecule, all groups T have the same meaning. Additional matrix materials, such as for example

And

Is described in WO2012/130709.

In a preferred embodiment, the light emitting layer comprises from 2 to 40% by weight, preferably from 5 to 35% by weight, of at least one of the aforementioned illuminant materials and from 60 to 98% by weight, preferably from 75 to 95% by weight, of said Formed from at least one of the mentioned matrix materials-in one embodiment, at least one compound of formula (I)-wherein the sum of the illuminant material and the matrix material is added to be 100% by weight.

또는

의 화합물 및 바람직하게는 화학식

의 2종의 카르벤 착물을 포함한다. 상기 실시양태에서, 발광 층은 2 내지 40 중량%, 바람직하게는 5 내지 35 중량%의

및 60 내지 98 중량%, 바람직하게는 65 내지 95 중량%의 화학식 I의 화합물 및

로부터 형성되고, 여기서 카르벤 착물 및 화학식 I의 화합물의 합계가 100 중량%가 되도록 첨가한다.In a particularly preferred embodiment, the light emitting layer has the formula

or

Of the compounds and preferably the formula

It contains two kinds of carbene complexes. In this embodiment, the light emitting layer is 2 to 40% by weight, preferably 5 to 35% by weight

And from 60 to 98% by weight, preferably from 65 to 95% by weight of a compound of formula I and

Wherein the sum of the carbene complex and the compound of formula (I) is 100% by weight.

Thus, in the OLED with the compound of formula I, the matrix material and/or hole/excitation blocker material and/or electron/excitation blocker material and/or hole injection material and/or electron injection material and/or hole transport material and/or electron Metal complexes suitable for use as transport materials, preferably matrix materials and/or hole/excitation blocker materials, are, for example, also WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, It is a carbene complex as described in WO 2007/115981 and WO 2008/000727. Here, the disclosures of the cited WO applications are explicitly referenced, and these disclosures should be considered to be included in the content of the present application.

The hole/excitation blocking layer (4) may comprise a compound of formula I, such as for example compound (A-9). When the hole/excitation blocking layer (4) does not contain any compound of formula (I), the OLED is-in the presence of a hole blocking layer-a hole blocking material typically used in OLEDs, such as 2,6-bis( N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (batokuproin, (BCP)), bis(2-methyl-8- Quinolinato)-4-phenylphenylato)aluminum (III) (BAIq), phenothiazine S,S-dioxide derivative and 1,3,5-tris (N-phenyl-2-benzylimidazolyl) Benzene) (TPBI), and TPBI is also suitable as an electron-conducting material. Further suitable hole blockers and/or electron transport materials are 2,2',2"-(1,3,5-benzenetriyl)tris(1-phenyl-1-H-benzimidazole), 2-(4 -Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, 8-hydroxyquinolinoleitoritium, 4-(naphthalen-1-yl)-3,5- Diphenyl-4H-1,2,4-triazole, 1,3-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl] Benzene, 4,7-diphenyl-1,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole, 6,6 '-Bis[5-(biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2'-bipyridyl, 2-phenyl-9,10-di(naphthalene -2-yl)anthracene, 2,7-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]-9,9-dimethylflu Orene, 1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene, 2-(naphthalen-2-yl)-4,7-di Phenyl-1,10-phenanthroline, tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane, 2,9-bis(naphthalen-2-yl)-4,7- Diphenyl-1,10-phenanthroline, 1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline. In a further embodiment, a compound comprising an aromatic or heteroaromatic ring bonded through a group comprising a carbonyl group as a hole/excitation blocking layer (4) or as a matrix material in the light emitting layer (3) (WO2006/100298 As described), consisting of disilylcarbazole, disilylbenzofuran, disilylbenzothiophene, disilylbenzophospol, disilylbenzothiophene S-oxide and disilylbenzothiophene S,S-dioxide. Disilyl compounds selected from the group (e.g., as specified in PCT applications PCT/EP2008/058207 and PCT/EP2008/058106, which have not yet been published on the priority date of this application), and disilyl as disclosed in WO2008/034758 It is possible to use compounds.

It is also possible-in one embodiment-to use the carbene complex as the hole transport material, and the band gap of the at least one hole transport material is generally larger than the band gap of the illuminant material used. In the context of this application, “band gap” is understood to mean triplet energy. Suitable carbene complexes are, for example, carbene complexes as described in WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727. One example of a suitable carbene complex is fac-iridium-tris(1,3-diphenylbenzimidazoline-2-ylidene-C,C ^2I ) (Ir(dpbic) ₃ ) having the formula:

, 이는 예를 들어 WO2005/019373에 개시되어 있다. 바람직하게는, 정공 수송 층은 산화몰리브데넘 (MoO_x), 특히 MoO₃, 또는 산화레늄 (ReO_x), 특히 ReO₃으로 도핑된 Ir(dpbic)₃을 포함한다. 도펀트는 도펀트 및 카르벤 착물의 양을 기준으로 하여 0.1 중량%부터, 바람직하게는 1 내지 8 중량%, 보다 바람직하게는 3 내지 5 중량%의 양으로 함유된다.

, Which are disclosed for example in WO2005/019373. Preferably, the hole transport layer comprises Ir(dpbic) ₃ doped with molybdenum oxide (MoO _x ), in particular MoO ₃ , or rhenium oxide (ReO _x ), in particular ReO ₃ . The dopant is contained in an amount from 0.1% by weight, preferably 1 to 8% by weight, more preferably 3 to 5% by weight, based on the amount of the dopant and carbene complex.

Suitable electron transport materials for layer (5) of the inventive OLED include compounds of formula (I), such as, for example, compounds (A-9); Metal chelated oxinoid compounds such as 2,2',2"-(1,3,5-phenylene)tris[1-phenyl-1H-benzimidazole] (TPBI), tris(8-quinolinol Lato) aluminum (Alq ₃ ), a compound based on phenanthroline, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA = BCP) or 4,7-diphenyl-1 ,10-phenanthroline (DPA), and azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and 3 -(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), 8-hydroxyquinolinolatolithium (Liq), 4 ,7-diphenyl-1,10-phenanthroline (BPhen), bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum (BAlq), 1,3-bis[2 -(2,2'-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]benzene (Bpy-OXD), 6,6'-bis[5-(biphenyl-4) -Yl)-1,3,4-oxadiazo-2-yl]-2,2'-bipyridyl (BP-OXD-Bpy), 4-(naphthalen-1-yl)-3,5-di Phenyl-4H-1,2,4-triazole (NTAZ), 2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline (NBphen), 2,7 -Bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]-9,9-dimethylfluorene (Bby-FOXD), 1,3 -Bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene (OXD-7), tris(2,4,6-trimethyl-3-(pyridine-) 3-yl)phenyl)borane (3TPYMB), 1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline ( 2-NPIP), 2-phenyl-9,10-di(naphthalen-2-yl)anthracene (PADN), 2-(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline (HNBphen) Layer (5) can act both as a buffer layer or a barrier layer to facilitate electron transport and to prevent quenching of excitons at the interface of the layer of the OLED. The mobility of electrons And reduce the quenching of excitons. In a preferred embodiment, BCP is used as the electron transport material. In another preferred embodiment, the electron transport layer comprises one or more compounds of formula I as electron transport material.

Among the materials mentioned above as hole transport materials and electron transport materials, some can perform several functions. For example, some of the electron-conducting materials are also hole-blocking materials at the same time when they have a low HOMO. These can be used, for example, for the hole/excitation blocking layer 4. However, likewise the function as a hole/excitation blocker can also be exerted by the layer 5, so that the layer 4 may not be used.

The charge transport layer can also be electronically doped to improve the transport properties of the materials used in order to make the layer thickness larger firstly (prevent pinhole/short circuit) and secondarily to minimize the operating voltage of the device. For example, the hole transport material can be doped with electron acceptors; For example, phthalocyanine or arylamine, such as TPD or TDTA, can be doped with tetrafluorotetracyanquinodimethane (F4-TCNQ) or MoO ₃ or WO ₃ . The electron transport material may for example be doped with an alkali metal, for example Alq ₃ with lithium. In addition, electron transport can be doped with a salt such as Cs ₂ CO ₃ or 8-hydroxyquinolato-lithium (Liq). Electron doping is known to a person skilled in the art and is described, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1, 1 July 2003 (p-doped organic layers); AG Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo. Appl. Phys. Lett., Vol. 82, No. 25, 23 June 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103. For example, the hole transport layer may be doped with MoO ₃ or WO ₃ in addition to a carbene complex, for example Ir(dpbic) ₃ . For example, the electron transport layer may comprise BCP doped with Cs ₂ CO ₃ .

Cathode 6 is an electrode that acts to introduce electron or negative charge carriers. Suitable materials for the cathode are alkali metals of group Ia of the periodic table of the elements (old version of IUPAC), for example alkaline earth metals of group Li, Cs, IIa, for example calcium, barium or magnesium, metals of group IIb (lanthanide and actinides, For example, it is selected from the group consisting of samarium). It is also possible to use metals such as aluminum or indium, and combinations of all the metals mentioned. In addition, alkali metal-comprising organometallic compounds or alkali metal fluorides such as LiF, CsF or KF may be applied between the organic layer and the cathode to reduce the operating voltage.

The OLED according to the invention may additionally comprise additional layers known to the person skilled in the art. For example, a layer that facilitates transport of positive charges and/or matches the band gap of the layers with each other can be applied between the layer 2 and the light-emitting layer 3. Alternatively, this additional layer can act as a protective layer. In a similar way, an additional layer may be present between the light-emitting layer 3 and the layer 4 to facilitate transport of negative charges and/or match the band gap of the layers with each other. Alternatively, this layer can act as a protective layer.

In a preferred embodiment, the inventive OLED comprises, in addition to layers (1) to (6), at least one of the following layers mentioned below:

-A hole injection layer between the anode (1) and the hole-transport layer (2) having a thickness of 2 to 100 nm, preferably 5 to 50 nm;

-An electron blocking layer between the hole-transport layer (2) and the light emitting layer (3);

-An electron injection layer between the electron-transport layer (5) and the cathode (6).

Materials for the hole injection layer are copper phthalocyanine, 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris( N-(2-naphthyl)-N-phenylamino)triphenylamine (2T-NATA), 4,4',4"-tris(N-(1-naphthyl)-N-phenylamino)triphenylamine (1T-NATA), 4,4',4"-tris(N,N-diphenylamino)triphenylamine (NATA), titanium oxide phthalocyanine, 2,3,5,6-tetrafluoro-7,7 ,8,8-tetracyanoquinodimethane (F4-TCNQ), pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile (PPDN), N,N, N',N'-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD), 2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobiflu Orene (MeO-spiro-TPD), 2,2'-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobifluorene (2,2'-MeO-spiro-TPD ), N,N'-diphenyl-N,N'-di-[4-(N,N-ditolylamino)phenyl]benzidine (NTNPB), N,N'-diphenyl-N,N'-di -[4-(N,N-diphenylamino)phenyl]benzidine (NPNPB), N,N'-di(naphthalen-2-yl)-N,N'-diphenylbenzene-1,4-diamine (α -NPP). In principle, it is possible for the hole injection layer to contain one or more compounds of formula (I) as hole injection material. In addition, polymeric hole-injecting materials such as poly(N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline, self-doped polymers such as for example sulfated poly(thiophene-3-[2) [(2-methoxyethoxy)ethoxy]-2,5-diyl) (Plexcore® OC conductive ink commercially available from Plextronics), and copolymers such as poly(3, 4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (also referred to as PEDOT/PSS) can be used.

As the material for the electron injection layer, for example LiF can be selected. In principle, it is possible for the electron injection layer to contain one or more compounds of formula I as electron injection material.

It is also possible to increase the efficiency of charge carrier transport by surface-treating some of the layers used in the OLEDs of the present invention.

The OLEDs of the present invention can be produced by methods known to those skilled in the art. In general, the OLEDs of the present invention are produced by continuous deposition of individual layers onto a suitable substrate. Suitable substrates are, for example, glass, inorganic semiconductors or polymer films. For the deposition, it is possible to use conventional techniques such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD), and the like. In an alternative method, the organic layer of the OLED can be applied from a solution or dispersion in a suitable solvent using coating techniques known to those skilled in the art.

In general, the different layers have the following thickness: anode (1) 50 to 500 nm, preferably 100 to 200 nm; Hole-conductive layer (2) 5 to 100 nm, preferably 20 to 80 nm, light emitting layer (3) 1 to 100 nm, preferably 10 to 80 nm, hole/excitation blocking layer (4) 2 to 100 nm , Preferably 5 to 50 nm, electron-conductive layer (5) 5 to 100 nm, preferably 20 to 80 nm, cathode (6) 20 to 1000 nm, preferably 30 to 500 nm. The relative position of the recombination zones of holes and electrons in the inventive OLED with respect to the cathode and thus the emission spectrum of the OLED can be influenced by the relative thickness of each layer, among other factors. This means that the thickness of the electron transport layer should preferably be selected so that the location of the recombination zone matches the optical resonator properties of the diode and thus the emission wavelength of the illuminant. In OLEDs, the ratio of the layer thickness of the individual layers depends on the material used. It is possible for the electron-conducting layer and/or the hole-conducting layer to have a thickness greater than the specified layer thickness when they are electrically doped.

The use of compounds of formula I in one or more layers of the OLED, preferably in the light emitting layer (preferably as a matrix material), and/or the electron transport layer, and/or the hole/excitation blocking layer, has high efficiency and low use and operation. It makes it possible to obtain OLEDs with voltage. Often, OLEDs obtained by the use of compounds of formula I additionally have a high lifetime. The efficiency of the OLED can be further improved by optimizing other layers of the OLED. For example, a high-efficiency cathode, such as Ca or Ba, can be used in combination with an intermediate layer of LiF, where appropriate. Molded substrates and novel hole-transport materials that result in a reduction in operating voltage or an increase in quantum efficiency are likewise usable in the inventive OLEDs. Moreover, additional layers may be present in the OLED to adjust the energy level of the different layers and facilitate electroluminescence.

The OLED may further comprise one or more second light emitting layers. The total emission of the OLED may consist of the emission of two or more light emitting layers, and may also include white light.

OLED can be used in any device where electroluminescence is useful. Suitable devices are preferably selected from fixed and mobile visual display devices and lighting devices. The fixed visual display device is, for example, a visual display device in a computer, a visual display device of a television, a printer, a kitchen appliance and an advertisement panel, a lighting and a guide panel. Mobile visual display devices are, for example, visual display devices of cell phones, laptops, digital cameras, MP3 players, vehicles, and destination displays of buses and trains. Additional devices in which the inventive OLED can be used include, for example, a keyboard; Clothing items; furniture; It is wallpaper.

In addition, the present invention relates to fixed visual display devices, such as computers, visual display devices of televisions, printers, kitchen utensils and advertising panels, lighting, guidance, comprising at least one organic light emitting diode of the invention or at least one light emitting layer of the invention Visual display devices in panels, and visual display devices in mobile visual display devices such as cell phones, laptops, digital cameras, MP3 players, vehicles, and destination displays of buses and trains; Lighting devices; keyboard; Clothing items; furniture; It relates to a device selected from the group consisting of wallpaper.

The following examples are included for illustrative purposes only, and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.

Example

Example 1

a) 11.3 g (50.0 mmol) 3-(2-aminophenyl)-1H-benzimidazol-2-one was added to 50 g polyphosphoric acid at 180°C. The reaction mixture was stirred at 220° C. for 3 hours under nitrogen and poured into water. The product was filtered and washed with water and methanol. 50 ml 30% sodium hydroxide solution was added to a suspension of the product in 200 ml THF. The mixture was stirred for 30 minutes, the organic phase was separated, dried over magnesium sulfate and the solvent was distilled off. 9.26 g of 6H-benzimidazole[1,2-a]benzimidazole was obtained (yield: 89%).

The synthesis of 5H-benzimidazo[1,2-a]benzimidazole and 3-(2-aminophenyl)-1H-benzimidazol-2-one is described in Bull. Soc. Chem. Belg. 96 (1987) 787.

b) 9.7 ml (24.1 mmol) of n-butyl-lithium 2.5 M in hexane was added to 5 g (24.21 mmol) of 6H-benzimidazole[1,2-a]benzimidazole in 100 ml anhydrous THF under argon -78 Added at °C. The reaction mixture was stirred at -78 °C for 15 min and then warmed to -25 °C. The reaction mixture is then cooled to 0° C. and a solution of 2-chloro-4,6-diphenyl-1,3,5-triazine (synthesis thereof is described in WO2010/067894) in 50 ml THF is added. And the reaction mixture was stirred at 0° C. for 15 minutes and then heated at 60° C. for 24 hours under argon. The product was filtered, washed with THF, dissolved in DMSO and poured into water. After filtration, 7.89 g of compound A-9 was obtained (yield: 79%).

Example 2

The synthesis of compound A-10 was carried out similarly to the synthesis of compound A-9.

Example 3

The synthesis of compound A-11 was carried out similarly to the synthesis of compound A-9.

Example 4

The synthesis of compound A-12 was carried out similarly to the synthesis of compound A-9.

Example 5

The synthesis of 4H-imidazo[1,2-a]benzimidazole is described in ARKIVOC 2002 (v) 48-61. The synthesis of compounds F-1a and F-1b was carried out similarly to the synthesis of compound A-9. The main isomer F-1a could be precipitated from the reaction mixture and filtered. The mother liquor contained the isomers F-1a and F-1b, which could be separated by HPLC.

Isomer F-1a:

Isomer F-1b:

Example 6

a) 1-bromo-3-iodo-benzene 7.78 g (25 mmol), cesium carbonate 16.3 g (50.0 mmol), copper iodide (I) 1.24 g (6.50 mmol) and L-proline 1.50 g (13.0 mmol) was added to 5.18 g (25.0 mmol) of 5H-benzimidazo[1,2-a]benzimidazole in 100 ml dimethylsulfoxide (DMSO) under nitrogen. The reaction mixture was stirred at 100° C. for 18 hours under nitrogen and poured into water. The organic phase was extracted with dichloromethane. The organic phase was dried over magnesium sulfate. The solvent was distilled off. Column chromatography on silica gel with toluene gave the product (yield 8.35 g (92%)).

b) Synthesis of 2,4-diphenyl-6-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]pyrimidine is WO2012/ It is described in Example 1 of 080052. 5-(3-bromophenyl)benzimidazolo[1,2-a]benzimidazole 1.77 g (4.89 mmol) and tertiary potassium phosphate monohydrate 5.63 g (24.4 mmol), 25 ml dioxane, 50 ml 2.55 g of 2,4-diphenyl6-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]pyrimidine with toluene and 12 ml water (5.86 mmol). The mixture was degassed with argon. 2-dicyclohexylphosphino2',6'-dimethoxybiphenyl (SPhos) 120 mg (0.293 mmol) and palladium (II) acetate 110 mg (0.049 mmol) were added. The reaction mixture was degassed with argon and stirred at 100° C. for 18 hours under argon. 25 ml of 1% sodium cyanide solution was added, and the reaction mixture was refluxed for 1 hour. Dichloromethane and water were added and the organic phase was separated. The organic phase was washed with water and dried over magnesium sulfate. Column chromatography on silica gel with toluene/ethyl acetate (15/1 and then 10/1) gave the crude product, which was crystallized from toluene (yield: 1.08 g (38%)).

Example 7

a) 20.0 g (78.8 mmol) of 1,3-dibromo-5-fluoro-benzene in 200 ml DMF, 16.3 g (78.8 mmol) of 6H-benzimidazolo[1,2-a]benzimidazole and Potassium carbonate 43.5 g (0.315 mmol) was stirred at 170° C. for 17 hours. The reaction mixture was filtered at high temperature, and after cooling, the precipitate was filtered from the mother liquor. The product was washed with water and ethanol, and decocated with diethyl ether and ethanol (yield 21.2 g (61%)).

b) 5-(3,5-dibromophenyl)benzimidazolo[1,2-a]benzimidazole 1.50 g (3.40 mmol) and tertiary potassium phosphate monohydrate 4.12 g (17.0 mmol), 15 ml 2,4-diphenyl-6-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) with dioxane, 60 ml toluene and 12 ml water To 3.54 g (8.16 mmol) of phenyl]pyrimidine was added. The mixture was degassed with argon. 84 mg (0.20 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) and 76 mg (0.034 mmol) of palladium (II) acetate were added. The reaction mixture was degassed with argon and stirred at 100° C. for 4 hours under argon. 25 ml of 1% sodium cyanide solution was added, and the reaction mixture was refluxed for 1 hour. Dichloromethane and water were added and the organic phase was separated. The organic phase was washed with water and dried over magnesium sulfate. The product was decocated twice with acetic acid. Product E-2 was washed with saturated sodium hydrogen carbonate solution and dried (69% yield).

Application Example 1-Hole blocker and electron transport material (ETM)

The ITO substrate used as the anode was first washed with an acetone/isopropanol mixture in an ultrasonic bath. To remove any organic residues that may be present, the substrate was exposed to a continuous ozone flow in an ozone oven for an additional 25 minutes. This treatment also improved the hole injection properties of ITO. The Flexcore® OC AJ20-1000 (commercially available from Flextronics Inc.) was then spin-coated and dried to form a hole injection layer (-40 nm).

(Ir(dpbic)₃; 제조에 대해, 출원 WO2005/019373에서 Ir 착물 (7) 참조)을 20 nm의 두께를 갖는 기판에 적용하고, 여기서 최초 10 nm를 MoO_x (~10%)로 도핑하여 전도도를 개선하였다.Thereafter, the organic materials specified below were applied by evaporation to a clean substrate at a rate of approximately 0.5-5 nm/min at about 10 ^-7 -10 ^-9 mbar. As a hole transport and exciton blocker,

(Ir(dpbic) ₃ ; For preparation, see Ir complex (7) in application WO2005/019373) is applied to a substrate having a thickness of 20 nm, where the first 10 nm is doped with MoO _x (~10%) The conductivity was improved.

, 10 중량%의 화합물 Ir(dpbic)₃ 및 60 중량%의 화합물

(H-1)의 혼합물을 30 nm의 두께로 증착에 의해 적용하였다.Subsequently, 30% by weight of the illuminant compound,

, 10% by weight of compound Ir(dpbic) ₃ and 60% by weight of compound

A mixture of (H-1) was applied by vapor deposition to a thickness of 30 nm.

(A-9)를 차단제로서 5 nm의 두께로 증착에 의해 적용하였다. Cs₂CO₃으로 도핑된 이 재료의 추가의 층을 전자 수송 층으로서 20 nm의 두께로 증착에 의해 적용하고, 최종적으로 100 nm-두께의 Al 전극으로 장치를 완성하였다. 모든 조립 부품을 불활성 질소 분위기 하에 유리 뚜껑 및 게터로 밀봉하였다.Subsequently, the material

(A-9) was applied by evaporation with a thickness of 5 nm as a blocking agent. An additional layer of this material, doped with Cs ₂ CO ₃ , was applied by evaporation to a thickness of 20 nm as an electron transport layer, and finally the device was completed with a 100 nm-thick Al electrode. All assembled parts were sealed with a glass lid and getter under an inert nitrogen atmosphere.

Application Example 2-Hole Blocker and Host

Sample preparation was carried out as in Application Example 1, but the setup was changed as follows:

(Ir(dpbic)₃; 제조에 대해, 출원 WO2005/019373에서 Ir 착물 (7) 참조)을 20 nm의 두께를 갖는 기판에 적용하고, 여기서 최초 10 nm를 MoO_x (~10%)로 도핑하여 전도도를 개선하였다.As a hole transport and exciton blocker,

(Ir(dpbic) ₃ ; For preparation, see Ir complex (7) in application WO2005/019373) is applied to a substrate having a thickness of 20 nm, where the first 10 nm is doped with MoO _x (~10%) The conductivity was improved.

, 10 중량%의 화합물 Ir(dpbic)₃ 및 60 중량%의 화합물

(A-10)의 혼합물을 40 nm의 두께로 증착에 의해 적용하였다. 후속적으로, 재료 (A-10)을 차단제로서 5 nm의 두께로 증착에 의해 적용하였다. Cs₂CO₃으로 도핑된 BCP

의 추가의 층을 전자 수송 층으로서 20 nm의 두께로 증착에 의해 적용하고, 최종적으로 100 nm-두께의 Al 전극으로 장치를 완성하였다.Subsequently, 30% by weight of the illuminant compound,

, 10% by weight of compound Ir(dpbic) ₃ and 60% by weight of compound

The mixture of (A-10) was applied by evaporation to a thickness of 40 nm. Subsequently, material (A-10) was applied by evaporation to a thickness of 5 nm as a barrier agent. BCP doped with Cs ₂ CO ₃

An additional layer of was applied by evaporation to a thickness of 20 nm as an electron transport layer, and finally the apparatus was completed with a 100 nm-thick Al electrode.

Application Example 3-Hole Blocker and ETM

(A-11)을 화합물 (A-9) 대신에 5 nm 두께로 침착시켰다. 또한, 5% Cs₂CO₃으로 도핑된 화합물 (A-11)을 화합물 (A-9) 및 Cs₂CO₃ 대신에 전자 수송 층으로서 20 nm의 두께로 적용하였다.Sample preparation was carried out as in Application Example 1, but the setup was changed as follows: The light emitting layer was 40 nm instead of 30 nm thick. Compound as a hole blocking material

(A-11) was deposited to a thickness of 5 nm instead of compound (A-9). In addition, compound (A-11) doped with 5% Cs ₂ CO ₃ was applied in a thickness of 20 nm as an electron transport layer instead of compound (A-9) and Cs ₂ CO ₃ .

Application Example 4-ETM

(Ir(dpbic)₃; 제조에 대해, 출원 WO2005/019373 중 Ir 착물 (7) 참조)을 20 nm의 두께를 갖는 기판에 적용하고, 여기서 최초 10 nm를 MoO_x (~10%)로 도핑하여 전도도를 개선하였다.Sample preparation was carried out as in Application Example 1, but the setup was changed as follows: As a hole transport and exciton blocker,

(Ir(dpbic) ₃ ; For preparation, see Ir complex (7) in application WO2005/019373) was applied to a substrate having a thickness of 20 nm, where the first 10 nm was doped with MoO _x (~10%) The conductivity was improved.

, 5 중량%의 화합물 Ir(dpbic)₃ 및 85 중량%의 화합물

(H-2)의 혼합물을 40 nm의 두께로 증착에 의해 적용하였다. 후속적으로, 재료 (H-2)를 차단제로서 5 nm의 두께로 증착에 의해 적용하였다. 이후에, 50 중량%의 재료

(B-5) 및 재료

(Liq)의 혼합물을 전자 수송 층으로서 20 nm의 두께로 증착에 의해 적용하였다. 100 nm-두께의 Al 전극으로 장치를 완성하였다.Subsequently, 10% by weight of the illuminant compound,

, 5% by weight of compound Ir(dpbic) ₃ and 85% by weight of compound

A mixture of (H-2) was applied by evaporation to a thickness of 40 nm. Subsequently, material (H-2) was applied by evaporation to a thickness of 5 nm as a barrier agent. Thereafter, 50% by weight of material

(B-5) and materials

A mixture of (Liq) was applied by evaporation to a thickness of 20 nm as an electron transport layer. The device was completed with a 100 nm-thick Al electrode.

Application Example 5-Hole Blocker and ETM

Fabrication and construction of the OLED was the same as in Application Example 4, except that the hole blocking material (B-5) was used instead of the hole blocking material (H-2).

To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristics were measured together with the emitted light output. By calibrating the light output with a photometer, it was possible to convert it into a photometric parameter. To measure the lifetime, the OLED was operated at a constant current density and the decrease in light output was recorded. The lifetime is defined as the time it takes for the luminescence to decrease by half of the initial luminescence.

Application Example 1 to V in a 300 cd / m ² measured for the five of the apparatus, are shown in the following chromaticity coordinates according to the EQE (%), and the CIE at 300 cd / m ² Table:

¹⁾ External quantum efficiency (EQE) is the # of generated photons emitted from a substance or device / # of electrons flowing through it.

Claims (18)

Materials for use in OLEDs, comprising a compound of formula I:
<Formula I>

In the above formula,
X ⁶ is -N= and X ⁷ is -NR ⁶ -, or
X ⁷ is =N- and X ⁶ is -NR ⁶ -,
R ⁶ is the formula

or

Is a group of;
A ¹ is a "branching unit" having 3 linking sites,
A ² and A ³ are independently of each other a C ₆ -C ₂₄ arylene group optionally substituted by G, or a C ₂ -C ₃₀ heteroarylene group optionally substituted by G; Wherein at least one group -(SiR ⁷ R ⁸ )- may be interposed in the groups A ¹ , A ² and A ³ ;
R ¹ and R ^1′ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interposed; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G,
R ⁷ and R ⁸ are independently of each other a C ₁ -C ₂₅ alkyl group, or a C ₆ -C ₂₄ aryl group optionally substituted by G;
L is a single bond or a linking group;
X ¹ is N or CR ⁹ ,
X ² is N or CR ¹⁰ ,
X ³ is N or CR ⁴⁸ ,
X ⁴ is N or CR ⁴⁹ ,
X ⁵ is N or CR ⁵⁰ , provided that at least one of X ³ , X ⁴ and X ⁵ is N,
R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁹ , R ¹⁰ , R ^9′ and R ^10′ are independently of each other H, optionally C ₁ -C ₂₅ alkyl which may be substituted by E and/or D may be interposed group; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G; or
R ⁹ and R ¹⁰ and/or R ^9'and R ^10' together form a ring, which may be optionally substituted,
p is 0, or an integer of 1 or 2; q is 0 or an integer of 1 or 2;
D is -CO-, -COO-, -S-, -SO-, -SO ₂ -, -O-, -NR ⁶⁵ -, -SiR ⁷⁰ R ⁷¹ -, -POR ⁷² -, -CR ⁶³ =CR ⁶⁴ -Or -C≡C-,
E is -OR ⁶⁹ , -SR ⁶⁹ , -NR ⁶⁵ R ⁶⁶ , -COR ⁶⁸ , -COOR ⁶⁷ , -CONR ⁶⁵ R ⁶⁶ , -CN or halogen,
G is E, or a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₂₄ aryl group, a C ₆ -C ₂₄ aryl group substituted by C ₁ -C ₁₈ alkyl; A C ₂ -C ₃₀ heteroaryl group, or a C ₂ -C ₃₀ heteroaryl group substituted by C ₁ -C ₁₈ alkyl;
R ⁶³ and R ⁶⁴ are each independently H, C ₆ -C ₁₈ aryl; C ₁ -C ₁₈ alkyl, C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl; Or C ₁ -C ₁₈ alkyl interrupted by -O-;
R ⁶⁵ and R ⁶⁶ are each independently a C ₆ -C ₁₈ aryl group; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; A C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-; or
R ⁶⁵ and R ⁶⁶ together form a 5 or 6 membered ring,
R ⁶⁷ is a C ₆ -C ₁₈ aryl group; A C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; A C ₁ -C ₁₈ alkyl group; Or -O- is a C ₁ -C ₁₈ alkyl group interrupted,
R ⁶⁸ is H; A C ₆ -C ₁₈ aryl group; A C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; A C ₁ -C ₁₈ alkyl group; Or -O- is a C ₁ -C ₁₈ alkyl group interrupted,
R ⁶⁹ is C ₆ -C ₁₈ aryl; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; A C ₁ -C ₁₈ alkyl group; Or -O- is a C ₁ -C ₁₈ alkyl group interrupted,
R ⁷⁰ and R ⁷¹ are each independently a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl,
R ⁷² is a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl, provided that the following compounds are excluded from the compounds of formula I :

. The material according to claim 1, wherein the compound of formula I is a compound of formula I'
<Formula I'>

In the above formula,
X ¹ , X ² , X ⁶ and X ⁷ are as defined in claim 1;
R ² , R ³ , R ⁴ and R ⁵ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interposed; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G; Here, E, D and G are as defined in claim 1. The material according to claim 1, wherein the compound of formula I is a compound of formula II.
<Formula II>

In the above formula,
X ⁶ is -N= and X ⁷ is -NR ⁶ -, or
X ⁷ is =N- and X ⁶ is -NR ⁶ -,
R ⁶ is the formula

or

Is a group of, wherein A ¹ is the formula

or

And A ² and A ³ are the formula

or

Is the flag of
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interposed; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G,
^{L, X 3, X 4,} X 5, R 1 and R ^{1 'are} as defined in claim ^{1, R 2, R 3, R} 4 and R ⁵ are each independently H, optionally be substituted by E A C ₁ -C ₂₅ alkyl group which may and/or may be interrupted by D; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G; Here, E, D and G are as defined in claim 1. The material of claim 3, wherein R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are H. The method of claim 1, wherein, R ¹ and R ^{1 'are} independently from each other the formula

,

A group or group of -(SiR ²⁰ R ²¹ R ²² ), wherein
X ⁸ is -N= and X ⁹ is >NL-,
X ⁹ is =N- and X ⁸ is >NL-,
R ² , R ³ , R ⁴ , R ⁵ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently of each other H, optionally substituted by E and/or C ₁ -C ₂₅ where D may be interposed Alkyl group; A C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G,
R ¹⁶ is a C ₆ -C ₁₈ aryl group; Or a C ₆ -C ₁₈ aryl group substituted by one or more C ₁ -C ₁₈ alkyl groups,
R ²⁰ , R ²¹ and R ²² are each independently a C ₆ -C ₁₈ aryl group; Or a C ₆ -C ₁₈ aryl group substituted by one or more C ₁ -C ₁₈ alkyl groups,
R ⁴³ a may be the same or different at each occurrence, F, C ₁ -C ₁₈ alkyl, which is substituted by E / D, or an intervening C ₁ -C ₁₈ alkyl, C ₆ -C ₂₄ aryl, by G Substituted C ₆ -C ₂₄ aryl, C ₂ -C ₂₀ heteroaryl, or C ₂ -C ₂₀ heteroaryl substituted by G,
R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ and R ⁹⁵ are independently of each other H, a C ₁ -C ₂₅ alkyl group which may optionally be substituted by E and/or D may be interposed;
m3 is 0, or an integer of 1 to 4, m4 is 0, or an integer of 1 to 3,
L, E, D and G are as defined in claim 1
material. The formula of claim 5, wherein R ¹ and R ^1′ are independently of each other

,

Wherein R ¹⁶ is a C ₆ -C ₁₈ aryl group; Or a C ₆ -C ₁₈ aryl group substituted by one or more C ₁ -C ₁₈ alkyl groups.
material. The method of claim 1, wherein L is a single bond, the formula -(A ⁴ ) _r -(A ⁵ ) _s -A ⁶ -or

Is the group of, where
A ⁴ , A ⁵ and A ⁶ are independently of each other the formula

,

or

Is the group of, where
R ⁴¹ a may be the same or different at each occurrence, F, C ₁ -C ₁₈ alkyl, which is substituted by E / D, or an intervening C ₁ -C ₁₈ alkyl, C ₆ -C ₂₄ aryl, by G Substituted C ₆ -C ₂₄ aryl, C ₂ -C ₂₀ heteroaryl, or C ₂ -C ₂₀ heteroaryl substituted by G,
m1 is 0, or an integer of 1 to 4,
m2 is 0, or an integer of 1 to 3,
r is 0 or 1; s is 0 or 1;
X ¹³ is -O-, -S- or -NR ¹⁵ -,
R ¹⁵ is a C ₁ -C ₁₈ alkyl group; A C ₁ -C ₁₈ alkyl group interrupted by -O-; A C ₆ -C ₁₈ aryl group; C ₆ -C ₁₈ aryl groups substituted by one or more C ₁ -C ₁₈ alkyl groups or C ₁ -C ₁₈ alkoxy groups; A C ₂ -C ₂₀ heteroaryl group, or a C ₂ -C ₂₀ heteroaryl group substituted by one or more C ₁ -C ₁₈ alkyl groups,
R ⁷ and R ⁸ are C ₁ -C ₁₈ alkyl groups,
E, D and G are as defined in claim 1
material. The formula of claim 7, wherein A ⁴ , A ⁵ and A ⁶ are independently of each other

Is the group of, where
R ¹⁵ is a C ₆ -C ₁₈ aryl group; Or a C ₆ -C ₁₈ aryl group substituted by one or more C ₁ -C ₁₈ alkyl groups.
material. The material according to claim 1, comprising the following compound.

¹⁾ R ¹ is the formula

It's a flag.
²⁾ R ¹ is the formula

It's a flag.
^{3) The} dotted line is the formula

Represents a bond to a group of.

An electronic device comprising the material according to claim 1. The electronic device according to claim 10, which is an electroluminescent device. A light-emitting layer comprising the material according to claim 1. The light-emitting layer according to claim 12, comprising the material according to any one of claims 1 to 9 as a host material in combination with a phosphorescent light-emitting body. A device selected from electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaic), switching elements, organic light-emitting field effect transistors (OLEFETs), image sensors and dye lasers comprising the material according to claim 1. An electron transport layer comprising the material according to claim 1. A hole blocking layer comprising the material according to claim 1. An exciton blocking layer comprising the material according to claim 1. An organic electronic device according to claim 10, a light emitting layer according to claim 12, an electron transport layer according to claim 15, or a hole blocking layer according to claim 16, or an exciton blocking layer according to claim 17. A display device, and a mobile visual display device; Lighting devices; keyboard; Clothing items; furniture; A device selected from the group consisting of wallpaper.