WO2010046259A1

WO2010046259A1 - Polycyclic compounds for electronic applications

Info

Publication number: WO2010046259A1
Application number: PCT/EP2009/063267
Authority: WO
Inventors: Peter Nesvadba; Frédérique Wendeborn; Thomas Schäfer; Beat Schmidhalter; Andrea Ricci; Peter Murer; Natalia Chebotareva
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-10-21
Filing date: 2009-10-12
Publication date: 2010-04-29
Anticipated expiration: 2011-04-21

Abstract

The present invention relates to electronic devices, especially electroluminescent devices, comprising compounds of formula (I), and/or (II), especially as host for phosphorescent emitters, electron transporting materials, or emitter materials. The hosts may function with phosphorescent materials to provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent devices.

Description

Polycyclic Compounds for Electronic Applications

The present invention relates to electronic devices, especially electroluminescent devices, comprising polycyclic compounds, especially as host for phosphorescent emitters, electron transporting materials, or emitter materials. The hosts may function with phosphorescent materials to provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent devices.

The geometric structure, dipole moment, linear polarizability and first hyperpolarizability of symmetrical substituted amino- and cyanobenzofurobenzofurans and dihydrobenzofurobenzofurans have been calculated by ab initio coupled perturbed Hartree- Fock methods in J. Heterocyclic Chemistry 1997, 34(1), 195.

US3243428 relates to compounds of formula

, wherein R¹³ and R¹⁴ are hydrogen, or lower alkyl, i.e. a straight, or branched chain alkyl group having 1 to 7 carbon atoms, and their use as estrogens.

Compounds of formula

, wherein R is CH₃, or acetyl, are disclosed by W.

Metlesics et al., J. Org. Chem 31 (1966) 3356-3362.

EP0433628 (DE3938282) relates to a process for the preparation of 3,8-dihydroxy-5a,1 Ob-

diphenyl-coumarano-2',3',2,3-coumarane (DDCC) by condensation of resorcinol with benzil in the presence of acid condensing agents. The DDCC obtained by the process can be used for the preparation of thermoplastic, aromatic polycarbonates.

JP10102056 relates to heat resistant stabilisers, such as

JP10273659 relates to a polymer stabilizer effective not only to stably keep a polymer in a high-temperature environment but also to develop excellent polymerization inhibiting effect on monomers such as styrene by including a heat- resistant compound having a specific structure. The polymer stabilizer consists of a compound having aromatic rings each having at least one OH group and condensed to each of 2, 3-positions and 4, 5-positions of furo[2,3- b]furan ring. One or both of the above condensed aromatic rings are benzene ring or naphthalene ring. A preferred example of the compound is 7a,12b-dihydronaphtho[2,1- b]benzophthalo [3,2-d]furan-10-ol. JP2004026706 discloses dihydric hydroxy compounds represented by formula

, wherein R₅-R₈ are each independently a hydroxy group or a Ci-

₄alkyl group and at least one of them is a hydroxy group; Rg is a hydrogen atom or an aryl group). The dihydric hydroxy compound is suitable as a raw material for a thermosetting resin, a thermoplastic resin, a photosensitive material such as a photoresist for a semiconductor, or a developer for heat-sensitive paper. The following compound is explicitly

disclosed

EP1847544 relates to an organic semiconductor device comprising an organic semiconductor material satisfying both the requirement of high electron field-effect mobility and high on/off current ratio. The organic semiconductor material is a compound of formula

, where Xi and X₂ are independently a chalcogen atom, n is an integer in a range of 1 to 3, and Ri and R₂ are independently a halogen, a C_1-18alkyl, a halogenated Ci-i₈alkyl; a Ci-i₈alkyloxy, a Ci-i₈alkylthio, an aryl, or an aryl having at least one selected from the group consisting of a halogen, a Ci-i₈alkyl, a halogenated Ci_i₈alkyl, a C_1- i₈alkyloxy, and a Ci_i₈alkylthio.

JP2007088016 relates to an organic semiconductor device and an organic thin-film transistor having high carrier mobility. The organic semiconductor material can contain, for example, a

compound expressed by formula

JP2007119392 relates to an organic electroluminescent element having more excellent performances of luminous efficiency, current efficiency, element life, external quantum efficiency, comprising a polycyclic condensed ring compound has a backbone represented

by general formula , wherein A₁ and A₂ are each sulfur, SO₂, silicon or carbon, one of A₁ and A₂ is sulfur or SO₂ and the other of A₁ and A₂ is silicon or carbon; ring structures B', C and D' are each independently a 5-membered ring or 6- membered ring; p is a value of 0 or 1 ; when A₁ or A₂ is carbon, p is 1. The following

compounds are explicitly disclosed

and

It is the object of the present invention to provide charge transporting materials with such chemical and physical properties which allow the fabrication of long lifetime OLED devices. It is still another object of the present invention to provide hosts for triplet emitters, especially hosts for blue triplet emitters, with such chemical and physical properties which allow the fabrication of long lifetime OLED devices.

It is still another object of the present invention to provide fluorescent emitters with such chemical and physical properties which allow the fabrication of long lifetime OLED devices.

Said object has been solved by compounds of the formula

wherein

₅163

X, X', Y and Y' are independently of each other O, S, SO₂, NR , Se, or Te,

the ring A,

, represents an optionally substituted aryl group which can optionally contain heteroatoms,

the ring B,

the ring C,

the ring D,

, represents an optionally substituted aryl group which can optionally contain heteroatoms, R¹ R¹ , R¹¹ and R¹¹ are independently of each other a group -L¹-X¹, or

R¹ and R¹ , or R¹¹ and R¹¹ together form a ring, or ring system, which may optionally be substituted,

R¹⁶³ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by CrCi₈alkyl, or d-Ci₈alkoxy; Ci-Ci₈alkyl,

Ci-Ci₈alkyl which is interrupted by -O-; or a group -(C(=O))-L¹-X¹, x is O, or 1 ; X¹ is d-Ciβalkyl, C_rCi_βalkyl which is interrupted by

, -NA¹A^1', -P(=O)A⁴A^4', - SiA⁶A⁷A⁸, a C₆-C₂₈aryl group, which can optionally be substituted, or a C₂-C₃₀heteroaryl group, especially an electron deficient heteroaryl group, which can optionally be substituted, Ar is C₆-Ci₄aryl, such as phenyl, or naphthyl, which may optionally be substituted by one or more groups selected from CrC₂5alkyl, which may optionally be interrupted by -O-, or d- C₂₅alkoxy,

L¹ is a single bond, or a bridging unit BU, such as

, or

A¹ and A¹ are independently of each other a C₆-C₂₄aryl group, a C₂-C₃₀heteroaryl group, which can optionally be substituted, or

A¹ and A¹ together with the nitrogen atom to which they are bonded form a heteroaromatic

ring, or ring system, such as

m is 0, 1 , or 2;

A⁴, A⁴ , A⁶, A⁷ and A⁸ are independently of each other a C₆-C₂₄aryl group, or a C₂-

C₃oheteroaryl group, which can optionally be substituted, ml can be the same or different at each occurence and is 0, 1 , 2, 3, or 4, especially 0, 1 , or

2, very especially 0 or 1 ,

R¹¹⁹ and R¹²⁰ are independently of each other CrCi₈alkyl, d-Ci₈alkyl which is substituted by

E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl,

C₂-C₂₀heteroaryl which is substituted by G, C₂-d₈alkenyl, C₂-d₈alkynyl, d-d₈alkoxy, d- d₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or

R ->1"19^M and R ₅1 ^I2^Λ0^J together form a group of formula - =_/C~_DR1^m21 _D R122 , wherein R¹²¹ and R¹²² are independently of each other H, Ci-Cisalkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-

C₂oheteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or

R¹¹⁹ and R¹²⁰ together form a five or six membered ring, which optionally can be substituted by Ci-Ci₈alkyl, d-Ci₈alkyl which is substituted by E and/or interrupted by D, C6-C₂₄aryl, C₆-

C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by

G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, Ci-Ci₈alkoxy, Ci-Ci₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or -C(=O)-R¹²⁷, and

R¹²³ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl, Ci-Ci₈alkyl which is interrupted by -O-;

R¹²⁷ is H; C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d-

Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

D is -CO-, -COO-, -S-, -SO-, -SO₂-, -0-, -NR⁶⁵-, -SiR⁷⁰R⁷¹-, -POR⁷²-, -CR⁶³=CR⁶⁴-, or -C≡d, and E is -OR⁶⁹, -SR⁶⁹, -NR⁶⁵R⁶⁶, -COR⁶⁸, -COOR⁶⁷, -CONR⁶⁵R⁶⁶, -CN, or halogen,

G is E, or Ci-Ci₈alkyl, -SO₂R⁷³,

R⁶³ and R⁶⁴ are independently of each other C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by d-

Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -0-; or

R⁶⁵ and R⁶⁶ are independently of each other C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by d- Ci₈alkyl, Ci-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -0-; or

R⁶⁵ and R⁶⁶ together form a five or six membered ring,

R⁶⁷ is C₆-Ci₈aryl; C₆-d₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -0-,

R⁶⁸ is H; C₆-Ci₈aryl; C₆-d₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d- Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -0-,

R⁶⁹ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl, Ci-Ci₈alkoxy; Ci-Ci₈alkyl; or

Ci-Ci₈alkyl which is interrupted by -0-,

R⁷⁰ and R⁷¹ are independently of each other Ci-Ci₈alkyl, C₆-d₈aryl, or C₆-d₈aryl, which is substituted by Ci-Ci₈alkyl, and R⁷² is Ci-Ci₈alkyl, C₆-d₈aryl, or C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl;

R⁷³ is Ci-Ci₈alkyl, or Ci-Ci₈alkyl which is interrupted by -O-; -CF₃, C₆-Ci₈aryl, C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy;

R⁴¹ can be the same or different at each occurence and is Cl, F, CN, NR⁴⁵R⁴⁵ , a Ci-C₂₅alkyl group, a C₄-d₈cycloalkyl group, a Ci-C₂₅alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR⁴⁵-, -O-, -S-, -C(=O)-O-, or -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R ,41 , or two or more groups R⁴¹ form a ring system;

R⁴⁵ and R⁴⁵ are independently of each other a Ci-C₂₅alkyl group, a C₄-Ci₈cycloalkyl group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR^{45 "}-, -O-, -S-, -C(=O)-O-, or, -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R⁴¹, and R⁴⁵ is a Ci-C₂₅alkyl group, or a C₄-Ci₈cycloalkyl group;

with the proviso that the ring A,

, are not substituted by a hydroxy group, an ester, an ether group, or an epoxy group, and with the further proviso that

the compounds of formula

are excluded, and with the further proviso that in case Y and Y' are a group NR¹⁶³, is different from an acetyl group, and a straight, or branched chain d-C₇alkyl group.

The rings A and B can be the same, or different, but are preferably the same.

The electronic device of the present invention is preferably an electroluminescent (EL) device. The compounds of formula I, or Il may be used in organic light emitting diodes (OLEDs) as hosts for phosphorescent compounds, as emitting and/or charge transport material.

Preferred are compounds of formula

X, X', Y and Y' are independently of each other O, S, SO₂, NR¹⁶³, Se, or Te,

R¹, R¹ , R¹¹ and R¹¹ are independently of each other a group X¹, or -L¹-X¹,

R 2 _D2' _D3 _D3' _D4 _D4' _D5 _D5' _D6 _D6' _D7 _D7' _D8 _D8' _D9 _D9' _D12 _D12' _D13 _D13' _D14 _D14' _D15 , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , ΓΛ , ΓΛ , ΓΛ , ΓΛ , ΓΛ , ΓΛ and R¹⁵ are independently of each other hydrogen, CrCi₈alkyl, a group X¹, -(C(=O))_X-L¹-X¹,

-OR¹⁶⁹, -SR¹⁶⁹, CF₃, or -SO₂R¹⁶⁸,

R¹⁰ , R^10', R¹⁶ and R^16' are independently of each other hydrogen, d-Ci₈alkyl, a group L¹-X¹,

-OR¹⁶⁹, -SR¹⁶⁹, Or-SO₂R¹⁶⁸,

R¹⁶³isC₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl;

Ci-Ci₈alkyl which is interrupted by -O-; or a group -(C(=O))_X-L¹-X¹, x is 0, or 1;

R¹⁶⁸ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl;

Ci-Ci₈alkyl which is interrupted by -O-, or CF₃, R¹⁶⁹ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl, or d-Ci₈alkoxy; Ci Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-, and X¹ and L¹ are as defined in claim 1.

In a preferred embodiment of the present invention at least one of R², R² , R³, R³ , R⁴, R⁴ , R⁵,

R^5' R⁶, R^6' R⁷, R^7' RR⁸⁸,, F R^8' R⁹, R^9' R¹², R^12' R¹³, R^13' R¹⁴, R^14' R¹⁵ and R^15' is a group of formula -(C(=O))_X-L¹-X¹.

In a preferred embodiment of the present invention R¹ and R¹' are the same and are a group L¹-X¹, R³ and R³' are the same and are a group -(C(=O))_X-L¹-X¹, and/or R⁴ and R⁴' are the same and are a group -(C(=O))_X-L¹-X¹.

In a preferred embodiment of the present invention R¹¹ and R¹¹' are the same and are a group L¹-X\ R¹³ and R¹³' are the same and are a group -(C(=O))_X-L¹-X¹, and/or R¹⁴ and R¹⁴' are the same and are a group -(C(=O))_X-L¹-X¹.

In a preferred embodiment of the present invention R⁷ and R⁷' are the same and are a group -(C(=O))_X-L¹-X\ R⁸ and R⁸' are the same and are a group -(C(=O))_X-L¹-X¹, and/or R¹⁰ and R¹⁰' are the same and are hydrogen.

In an even more preferred embodiment of the present invention at least one of R³ and R³ are a group of formula -(C(=O))_X-L¹-X¹ and R², R^2', R⁴, R^4', R⁵ and R^5' are hydrogen.

In an even more preferred embodiment of the present invention at least one of R⁴ and R⁴ are a group of formula -(C(=O))_X-L¹-X¹ and R², R^2', R³, R^3', R⁵ and R^5' are hydrogen.

In an even more preferred embodiment of the present invention at least one of R⁷ and R⁷ are a group of formula -(C(=O))_X-L¹-X¹ and R⁶, R^6', R⁸, R^8', R⁹ and R^9' are hydrogen.

The bridging unit BU is, for example, an arylene, or heteroarylene group, which optionally may be substituted.

L¹ is a single bond, -(CR⁴⁷=CR⁴⁸)_m2-, -(Ar³)_m3-, -[Ai^(Y¹ )_m5]_m4-, -[(Y¹)_m5Ar³]_m4-, or -[Ar³(Y²)_m5Ar⁴]_m4-, wherein Y¹ is -(CR⁴⁷=CR⁴⁸)-, Y² is NR⁴⁹, O, S, C=O, C(=O)O, wherein R⁴⁹ is C₆-Ci₈aryl which can optionally be substituted by Ci-Ci₈alkyl, or d-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-;

R⁴⁷ and R⁴⁸ are independently of each other hydrogen, CrC₂oalkyl, or C₆-C₂₄aryl, which can optionally be substituted by G, m5 is an integer of 1 to 10, m2 is an integer of 1 to 10, m3 is an integer of 1 to 5, m4 is an integer of 1 to 5,

Ar³ and Ar⁴ are independently of each other arylene, or heteroarylene, which can optionally be substituted by G, wherein G is as defined above.

Preferably, L¹ is a single bond, or a bridging unit BU of formula

wherein R¹¹⁹, R¹²⁰, R¹²³, ml and R⁴¹ are as defined above.

X, X', Y and Y' can be the same, or can be different and are O, S, SO₂, N-(C(=O))_X-BU-A¹A^1',

N-(C(=O))_X-R¹⁷⁰, or N-(C(=O))_X-BU-R¹⁷⁰, x is 0, or 1 , and A¹ and A¹ are as defined above,

R¹⁷⁰ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d-

Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-, and

or , wherein R¹¹⁹, R¹²⁰, R¹²³, ml and R⁴¹ are as defined above.

Compounds of the formula (I), (II), (III), or (IV) are preferred, wherein -(C(=O))_X-L¹-X¹ is a group of formula -P(=O)A⁴A^4', -C(=0)A⁵, -SiA⁶A⁷A⁸, -NA¹A^1', -BU-P(=O)A⁴A^4', -BU-SiA⁶A⁷A⁸,

wherein

A⁵, A¹, A^1', A³ and A^3' are independently of each other a C₆-C₂₄aryl group, or a C₂- C₃₀heteroaryl group, which can optionally be substituted, especially phenyl, naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl, which can optionally be substituted, such as

, and , or A¹ and A^1', or A³ and A^3' together with the nitrogen atom to which they are bonded form a heteroaromatic ring, or ring system, such

as

, or ; m' is 0, 1 , or 2; ml can be the same or different at each occurence and is 0, 1 , 2, 3, or 4, especially 0, 1 , or 2, very especially 0 or 1 ;

R⁶⁵ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by CrCi₈alkyl, d-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-; 7

A⁴, A^{4 '}, A⁶, A⁷ and A⁸ are independently of each other a group

^R

R¹¹⁶, R¹¹⁷ and R¹¹⁷ are independently of each other H, halogen, especially F, -CN, d-

Ci₈alkyl, d-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂oheteroaryl, C₂-C₂oheteroaryl which is substituted by G, C₂-

Ci₈alkenyl, C₂-Ci₈alkynyl, Ci-Ci₈alkoxy, Ci-Ci₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, -C(=O)-R¹²⁷, -C(=O)OR¹²⁷, or -C(=O)NR¹²⁷R¹²⁶, or substituents R¹¹⁶, R¹¹⁷ and R¹¹⁷ , which are adjacent to each other, can form a ring,

R¹²⁴ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl,

Ci-Ci₈alkyl which is interrupted by -O-;

R¹²⁶ and R¹²⁷ are independently of each other H; C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

, or , wherein R¹¹⁹, R¹²⁰, R¹²³, D, E, G, R⁴¹ and ml are as defined above.

Examples of a heteroaromatic ring, or ring system, which is formed by A¹ and A^1', or A³ and A³ together with the nitrogen atom to which they are bonded, are

or ; ml and m' are independently of

each other 0, 1 , or 2. Examples of are and

(rrT = 2), wherein R is H, or Ci-Cisalkyl, or phenyl, which is optionally

be substituted by

Examples of groups

are shown below:

, and wherein R⁴¹, R¹

R¹¹⁷, R¹¹⁹, R¹²⁰ and ml are as defined above. Specific examples are groups AM-1 to AM-13 mentioned in claim 10.

In a preferred embodiment the present invention is directed to compounds of formula Ia, or

Ib, wherein R and R are a group of formula -NA A , or

, or a group of formula

, wherein R¹¹⁶ and R¹¹⁷ are as defined above, R³, R³', R⁴ and R⁴ are a

group of formula -NA¹A^{1 '}, or

, and X is O. Examples of groups of formula -

NA¹A^1' or

are compounds AM-1 to AM-13. The group of formula

is preferably a phenyl group.

In another preferred embodiment the present invention is directed to compounds of formula Ia, or Ib, wherein R¹, R¹ R³, R³', R⁴ and R⁴ are independently of each other a group of

formula -NA¹A^1', or

or

, wherein R¹¹⁶ and R¹¹⁷ are as defined above, and X is O.

Examples of groups of formula -NA¹A¹ , or

are compounds AM-1 to AM-13.

Compounds of formula Ia are preferred against compounds of formula Ib.

In another preferred embodiment the present invention is directed to compounds of formula

(Ma), wherein R , R , R and R are independently of each

other a group of formula -NA 1 A_Λ 1', or

, or a group of formula

or wherein R and R are as

defined above, and Y is O. Examples of groups of formula -NA¹A^{1 '}, or

are compounds AM-1 to AM-13.

(Ilia), or (IVa) wherein R⁷, R^7', R¹⁰,

R , R and R are independently of each other a group of formula -NA 1 A_Λ 1 ' , or

or

, wherein R and R are as defined above, and X is O.

Examples of groups of formula -NA¹A¹ , or

are compounds AM-1 to AM-13.

The groups of formula

, and

preferably a group of formula

, and

In the above described preferred embodiments -NA . 1 A Λ 1 ' , or

are preferably a

group of formula

Cisalkyl which is interrupted by O, or phenyl, which is optionally substituted by

Compounds of the formula (I), (II), (III), or (IV) are preferred, wherein L -X is a group

R¹¹⁶, R¹¹⁷ and R^117' are as defined above and R^116' has the meaning of R¹¹⁶. Specific examples are groups AR-1 and AR-2 mentioned in claim 10. Compounds of the formula (I), (II), (III), or (IV) are preferred, wherein L -X is a group

and

R ,117' are as defined above. Specific examples are groups HE-1 to HE-9 mentioned in claim 10.

, wherein R¹¹⁶, R¹¹⁷, R¹¹⁹, R¹²⁰, and R¹²³ are as defined above.

Preferably, R¹¹⁶ and R¹¹⁷ are independently of each other H, Ci-Ci₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl, Ci-Ci₂alkyl which is substituted by E and/or interrupted by D, such as -CH₂OCH₃, -CH₂OCH₂CH₃, -CH₂OCH₂CH₂OCH₃, or -CH₂OCH₂CH₂OCH₂CH₃ , C₆-Ci₄aryl, such as phenyl, naphthyl, or biphenylyl, C₅- Ci₂cycloalkyl, such as cyclohexyl, C₆-Ci₄aryl which is substituted by G, such as -C₆H₄OCH₃, -C₆H₄OCH₂CH₃, -C₆H₃(OCH₃)₂, or -C₆H₃(OCH₂CH₃)₂, -C₆H₄CH₃, -C₆H₃(CH₃)₂, -C₆H₂(CH₃)₃, or -C₆H₄tBu.

Preferably, R¹¹⁹ and R¹²⁰ are independently of each other Ci-Ci₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, Ci-Ci₂alkyl which is substituted by E and/or interrupted by D, such as -CH₂(OCH₂CH₂)_WOCH₃, w = 1 , 2, 3, or 4, C₆-Ci₄aryl, such as phenyl, naphthyl, or biphenylyl, C₆-Ci₄aryl which is substituted by G, such as -C₆H₄OCH₃, -C₆H₄OCH₂CH₃, -C₆H₃(OCH₃)₂, -C₆H₃(OCH₂CH₃),, -C₆H₄CH₃, -C₆H₃(CH₃)₂, -C₆H₂(CH₃)₃, or -C₆H₄tBu, or R¹¹⁹ and R¹²⁰ together form a 4 to 8 membered ring, especially a 5 or 6 membered ring, such as cyclohexyl, or cyclopentyl, which can optionally be substituted by Ci-C₈alkyl. D is preferably -CO-, -COO-, -S-, -SO-, -SO₂-, -0-, -NR²⁵-, wherein R²⁵ is C_rCi₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C₆-Ci₄aryl, such as phenyl, naphthyl, or biphenylyl.

E is preferably -OR²⁹; -SR²⁹; -NR²⁵R²⁵; -COR²⁸; -COOR²⁷; -CONR²⁵R²⁵; or -CN; wherein R²⁵, R²⁷, R²⁸ and R²⁹ are independently of each other Ci-Ci₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-Ci₄aryl, such as phenyl, naphthyl, or biphenylyl, which may optionally be substituted. G has the same preferences as E, or is CrCi₈alkyl, especially Ci-Ci₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl. In a preferred embodiment the present invention is directed to compounds of formula

Preferably, X is O, S, SO₂, N-(C(=O))_x-BU-A¹A^r, N-(C(=O))_X-R¹⁷⁰, or N-(C(=O))_X-BU-R¹⁷⁰, x is 0, or 1 ,

R¹⁷⁰ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by CrCi₈alkyl, or d-Ci₈alkoxy; d- Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

, wherein

R²¹⁶ and R²¹⁷ are independently of each other H,

Ci-Ci₈alkyl, or Ci-Ci₈alkyl which is interrupted by O,

R¹⁰ , R^10', R¹⁶ and R^16' are independently of each other hydrogen, C_rCi₈alkyl, a group L¹-X¹, wherein L¹-X¹ is as defined above,

R³, R^3', R⁴, R^4', R⁷ and R^7' are independently of each other a group -(C(=O))_X-L¹-X¹, wherein -

(C(=O))_X-L¹-X¹ is a group of formula -C(=0)A⁵, -P(=O)A⁴A^4', -SiA⁶A⁷A⁸, -NA¹A^1', -BU-

P(=0)A⁴A⁴ , -BU-SiA^bA'A^b,

, or wherein

A , A ₁ A , A and A are independently of each other

, or A¹ and A^1', or A³ and A³ together with the nitrogen atom to which they are

bonded form a heteroaromatic ring, or ring system, such as

or

₁ A , A , A and A are independently of each other a group

R¹¹⁶, R^116', R¹¹⁷ and R^117' are independently of each other H, d-Ci₈alkyl, C_rCi₈alkyl which is interrupted by O,

R¹²³ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by CrCi₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl,

Ci-Ci₈alkyl which is interrupted by -O-; ml can be the same or different at each occurence and is 0, or 1 , and R is Ci-Ci₈alkyl, d-Ci₈alkyl which is interrupted by O, or phenyl, which is optionally be

substituted by

Compounds of formula (Ma) are more preferred, wherein

Y is O, SO₂, NR¹⁶³, or S, wherein R¹⁶³ is C_rC₄alkyl, C(=O)-R¹⁷⁰, or (C(=O)-BU-R¹⁷⁰,

R¹⁷⁰ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; C_r

Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

BU is

, or , wherein ml is

0,1 , or 2, and R ->41 is a Ci-C₂5alkyl group, or a Ci-C₂5alkoxy group,

R and R are independently of each other H,

, or a group L¹-X¹,

R¹³ and R^14' are independently of each other H, or a group L¹-X¹, wherein L¹-X¹, R²¹⁶ and R²¹⁷ are as defined above.

Compounds A-1 to A-74, which are shown in claim 10, are particularly preferred, wherein compounds A-6 to A-9, A-19 to A-21 , A-26 to A-29, A-30, A-31 , A-35, A-59 to A-68 are particularly suitable as hosts for blue triplet emitters, compounds A-1 , A-2, A-3 and A-36 to A-49 are particularly suitable as hosts for red triplet emitters and compounds A-55 and A-56 are particularly suitable as ambipolar hosts for red triplet emitters.

Compounds B-1 to B-41 , which are shown in claim 10, are particularly preferred, wherein compounds compounds B-6 to B-9 and B-28 to B-37 are particularly suitable as hosts for blue triplet emitters, compounds B-1 , B-2, B-3, B-15 to B-18 are particularly suitable as hosts for red triplet emitters, compounds B-24 and B-25 are particularly suitable as ambipolar hosts for red triplet emitters and compound B-22 is particularly suitable as fluorescent emitter.

Compounds C-1 to C-12, which are shown in claim 10, are particularly preferred and can advantageously be used as electron transport material.

Compounds D-1 to D-9, which are shown in claim 10, are particularly preferred and can advantageously be used as electron transport material.

Compounds E-1 to E-5, which are shown in claim 10, are particularly preferred, wherein compound E-1 can advantageously be used as a fluorescent dopant.

Compounds F- 1 to F-4, which are shown in claim 10, are particularly preferred, wherein compound F- 1 can advantageously be used as a fluorescent dopant.

Compounds G-1 to G-35, which are shown in claim 10, are particularly preferred.

Compounds H-1 to H-60, which are shown in claim 10, are particularly preferred.

Compounds 1-1 to H-41 , which are shown in claim 10, are particularly preferred.

Halogen is fluorine, chlorine, bromine and iodine.

Ci-C₂5alkyl (d-Ci₈alkyl) is typically linear or branched, where 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-methylhep- tyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl. Ci-C₈alkyl 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. CrC₄alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert. -butyl. Ci-C₂5alkoxy (Ci-Ci₈alkoxy) groups are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of Ci-C₈alkoxy are 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-ethylhexyloxy, preferably Ci-C₄alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy. The term "alkylthio group" means the same groups as the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulphur atom.

C₂-C₂₅alkenyl (C₂-Ci₈alkenyl) groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3- methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec- 4-enyl.

C_2-24alkynyl (C₂-Ci₈alkynyl) is straight-chain or branched and preferably C_2-8alkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4- yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1 ,4-pentadiyn-3-yl, 1 ,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.

Ci-Ci₈perfluoroalkyl, especially Ci-C₄perfluoroalkyl, is a branched or unbranched radical such as for example -CF₃, -CF₂CF₃, -CF₂CF₂CF₃, -CF(CF₃)₂, -(CF₂)₃CF₃, and -C(CF₃)₃.

The terms "haloalkyl, haloalkenyl and haloalkynyl" mean groups given by partially or wholly substituting the above-mentioned alkyl group, alkenyl group and alkynyl group with halogen, such as trifluoromethyl etc. The "aldehyde group, ketone group, ester group, carbamoyl group and amino group" include those substituted by an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted. The term "silyl group" means a group of formula -SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are independently of each other a Ci-C₈alkyl group, in particular a d-C₄ alkyl group, a C₆-C₂₄aryl group or a C₇-Ci₂aralkylgroup, such as a trimethylsilyl group. The term "siloxanyl group" means a group of formula -0-SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are as defined above, such as a trimethylsiloxanyl group. The term "cycloalkyl group" is typically C₄-Ci₈cycloalkyl (C₅-Ci₂cycloalkyl), such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted. The term "cycloalkenyl group" means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted. The cycloalkyl group, in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with Ci-C₄-alkyl, halogen and cyano.

Examples of such condensed cyclohexyl groups are:

wherein R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and

R ₁56 are independently of each other CrC₈-alkyl, Ci-Cβ-alkoxy, halogen and cyano, in particular hydrogen.

Aryl is usually C₆-C₃oaryl, preferably C₆-C₂₄aryl, which optionally can be substituted, such as, for example, phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl, or 2- naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, anthryl, tetracyl, pentacyl, hexacyl, or quaderphenylyl, which may be unsubstituted or substituted.

The term "aralkyl group" is typically C₇-C₂₄aralkyl, such as benzyl, 2-benzyl-2-propyl, β- phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl- dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-Ci₈aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C₇-Ci₂aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted.

The term "aryl ether group" is typically a C_6-24aryloxy group, that is to say O-C_6-24aryl, such as, for example, phenoxy or 4-methoxyphenyl. The term "aryl thioether group" is typically a C₆-₂₄arylthio group, that is to say S-C₆-₂₄aryl, such as, for example, phenylthio or 4-methoxyphenylthio. The term "carbamoyl group" is typically a Ci-i₈carbamoyl radical, preferably Ci_-8carbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert- butylcarbamoyl, dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

The terms "aryl" and "alkyl" in alkylamino groups, dialkylamino groups, alkylarylamino groups, arylamino groups and diarylgroups are typically Ci-C₂5alkyl and C₆-C₂₄aryl, respectively.

Alkylaryl refers to alkyl-substituted aryl radicals, especially C₇-Ci₂alkylaryl. Examples are tolyl, such as 3-methyl-, or 4-methylphenyl, or xylyl, such as 3,4-dimethylphenyl, or 3,5- dimethylphenyl.

Heteroaryl is typically C₂-C₃oheteroaryl (C₂-C₂6heteroaryl, especially C₂-C₂oheteroaryl), i.e. a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulphur are the possible hetero atoms, and is typically an unsaturated heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted or substituted.

Possible substituents of the above-mentioned groups are Ci-C₈alkyl, a hydroxyl group, a mercapto group, Ci-C₈alkoxy, Ci-C₈alkylthio, halogen, halo-Ci-C₈alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group or a silyl group, wherein d-C₈alkyl, d-C₈alkoxy, a cyano group, or a silyl group are preferred.

If a substituent, such as, for example R ₃41 occurs more than one time in a group, it can be different in each occurrence.

The wording "substituted by G" means that one, or more, especially one to three groups G might be present.

As described above, the aforementioned groups may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course possible only in the case of groups containing at least 2 carbon atoms connected to one another by single bonds; C₆-Ci₈aryl is not interrupted; interrupted arylalkyl or alkylaryl contains the unit D in the alkyl moiety. CrCisalkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (CH₂CH₂O)i-9-R^x, where R^x is H or d-doalkyl or C₂-Cioalkanoyl (e.g. CO-CH(C₂H₅)C₄H₉), CH₂-CH(OR^y')-CH₂- O-R^y, where R^y is d-Ci₈alkyl, C₅-d₂cycloalkyl, phenyl, C₇-Ci₅phenylalkyl, and R^y' embraces the same definitions as R^y or is H;

Ci-C₈alkylene-COO-R^z, e.g. CH₂COOR_Z1 CH(CH₃)COOR², C(CH₃)₂COOR^Z, where R^z is H, Ci-Ci₈alkyl, (CH₂CH₂O)i_-9-R^x, and R^x embraces the definitions indicated above; CH₂CH₂-O-CO-CH=CH₂; CH₂CH(OH)CH₂-O-CO-C(CH₃)=CH₂.

Preferred arylene radicals are 1 ,4-phenylene, 2,5-tolylene, 1 ,4-naphthylene, 1 ,9 antracylene, 2,7-phenantrylene and 2,7-dihydrophenantrylene.

Preferred heteroarylene radicals are 2,5-pyrazinylene, 3,6-pyridazinylene, 2,5-pyridinylene, 2,5-pyrimidinylene, 1 ,3,4-thiadiazol-2,5-ylene, 1 ,3-thiazol-2,4-ylene, 1 ,3-thiazol-2,5-ylene, 2,4-thiophenylene, 2,5-thiophenylene, 1 ,3-oxazol-2,4-ylene, 1 ,3-oxazol-2,5-ylene and 1 ,3,4- oxadiazol-2,5-ylene, 2,5-indenylene and 2,6-indenylene.

Compounds of formula

(VII), and/or (VIII) are intermediates for the synthesis of the compounds of formula I, new and form a further subject of the present invention, wherein X, X', Y, Y', R¹, R^1', R¹¹, R^11', R², R^2', R³, R^3', R⁴, R^4', R⁵, R^5', R⁶, R^6', R⁷, R^7', R⁸, R^8', R⁹, R^9', R¹², R^12', R¹³, R^13', R¹⁴, R^14', R¹⁵, R^15', R¹⁰, R^10', R¹⁶ and R^16' are as defined above and wherein at least one of the substituents R², R² , R³, R³ , R⁴, R⁴ , R⁵, R⁵ , R⁶, R⁶ , R⁷, R^7', R⁸, R^8', R⁹, R^9', R¹², R^12', R¹³, R^13', R¹⁴, R^14', R¹⁵, and R^15' is a group of formula 0-SO₂- CF₃.

The process for the preparation of compounds of the formula Va, Vb, Via, Vila, or Villa

defined in claim 1 , and R³, R^3', R⁴, R^4', R¹³, R^14', R⁷ and R^7' are a group of formula -0-SO₂- CF₃ involves reacting compounds of the formula Va, Via, and Vila, wherein R³, R³ , R⁴, R⁴ ,

R¹³, R^14', R⁷ and R^7' are OH, with a group of formula

. Compounds of formula

can be prepared by reacting

in the presence of an acid, such as hydrochloric acid, sulphuric acid, or methanesulfonic acid.

Compounds of formula

can be prepared by reacting

with in the presence of an acid, such as hydrochloric acid, sulphuric acid, or methanesulfonic acid.

Compounds of formula

can be prepared by reacting

with in the presence of an acid, such as hydrochloric acid, sulphuric acid, or methanesulfonic acid. Reference is made, for example, to DE3938282 and Rec. Trav. Chim. 87 (1968) 599-608.

The hydroxyl groups are subsequently transformed into trifluoromethanesulfonyl groups under classical conditions (Synthesis (1982) 85-126), which are in turn used as leaving groups in the palladium catalyzed reactions. Reference is made, for example, to Org. Lett. 2 (2000) 1403-1406.

The compounds of the formula Ia, Ib, (Ha), IMa and IVa, wherein

R³, R^3', R⁴, R^4', R¹³, R^14', R⁷ and R^7' are independently of each other -NA¹A^1',

, or , can, for example, be prepared according to a process, which comprises reacting a compound of formula Va, Vb, Via, Vila, or Villa, wherein R :>3, ι R->3^J', ι R->4⁴, ι R->4⁴', 1 R— ,13 , r R- ,1'4⁴', ι R->7' and R' stands for halogen, such as bromo or iodo,

with compound of formula HNA A

or )

in the presence of a base, such as sodium hydride, potassium carbonate, or sodium carbonate, and a catalyst, such as copper (0) or copper (I) (such as copper, copper-bronze, copper bromide iodide, or copper bromide), in a solvent, such as toluene, dimethyl formamide, or dimethyl sulfoxide, wherein A¹, A^1', R⁴¹, ml and m are as defined above.

This reaction, referred to as an Ullmann condensation, is described by Yamamoto & Kurata, Chem. and Industry, 737-738 (1981 ), J. Mater. Chem. 14 (2004) 2516, H. B. Goodbrand et al., J. Org. Chem. 64 (1999) 670 and k. D. Belfield et al., J. Org. Chem. 65 (2000) 4475 using copper as catalyst. Additionally palladium catalysts can be used for the coupling of aryl halogen compounds with amines, as described in M. D. Charles et al., Organic Lett. 7 (2005) 3965, A. F. Littke et. al., Angew. Chem. Int. Ed. 41 (2002) 4176 and literature cited therein.

Alternatively, the compounds of the formula Ia, Ib, Ha, HIa and IVa, wherein R³, R³ , R⁴, R⁴ ,

R , R , R and R are independently of each other -NA A ,

, or 1

, can, for example, be prepared according to a process, which comprises reacting a compound of formula Va, Vb, Via, Vila, or Villa, wherein R³, R³ , R⁴, R⁴ , R¹³, R¹⁴ , R⁷ and R⁷ stands for halogen, such as bromo, with a compound of formula

HNA¹A¹ ,

or in the presence of a base, such as sodium te/f-butylate in a solvent such as toluene or xylene and in the presence of a palladium catalyst such as palladium (II) acetate or palladium (II) tris- (dibenzylidene acetone). The reaction referred as the Buchwald coupling is described by A. S. Guram, R. A. Rennels, S. L. Buchwald, Angewandte Chemie International Edition in English 1995, 34, 1348-1350.

Alternatively, the compounds of the formula Ia, Ib, Ha, IMa and IVa, wherein R³, R³ , R⁴, R⁴ ,

R¹³, R^14', R⁷ and R⁷ are independently of each other -NA¹A¹ , or

, can, for example, be prepared according to a process, which comprises reacting a compound of formula Va, Vb, Via, Vila, or Villa, wherein R³, R³ , R⁴, R^4', R¹³, R^14', R⁷ and R^7' stands for -0-SO₂-CF₃ with a compound of formula HNA¹A^1',

or in the presence of a base, such as sodium hydride, cesium carbonate or potassium phosphate in a solvent such as toluene or dioxane and in the presence of a palladium catalyst such as palladium (II) tris-(dibenzylidene acetone). The reaction referred as the Buchwald coupling is described by D. W. Old, M. C. Harris, S. L. Buchwald Org. Lett. 2000, 2, 1403-1406. The compounds of the formula Ia, Ib, IMa and IVa, wherein R³, R^{3 '}, R⁴, R^{4 '}, R⁷ and R⁷ are a

group can be prepared according to, or in analogy to Adv. Funct.

Mater. 2006, 16, 1449. An example of such a reaction is shown below:

The reaction of the dibromide with the acetylene is done in the presence a catalyst, such as copper (0), copper (I) (such as copper, copper-bronze, copper iodide, or copper bromide), and/or palladium(O), such as, for example, tetrakis (triphenyl-phosphine) palladium(O), optionally in a solvent, such as toluene, dimethyl formamide, or dimethyl sulfoxide, and optionally a base, such as sodium hydride, potassium carbonate, sodium carbonate, or an amine base, such as piperidine. The reaction time and temperature depends on the starting materials and reaction conditions. Usually the dibromide is reacted with the alkine at a temperature of from 50⁰C to 100⁰C , especially 60 to 80°C for 1 h to 48 h hours. This reaction, referred to as an Sonogashira reaction (Pd/Cu-catalyzed cross-coupling of organohalides with terminal alkynes), Cadiot-Chodkiewicz coupling or Castro-Stephens reaction (the Castro-Stephens coupling uses stoichiometric copper, whereas the

Sonogashira variant uses catalytic palladium and copper), is described by Sonogashira K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467; Richard Heck (discovered the same transformation using palladium but without the use of copper) J. Organomet. Chem. 1975, 93, 259; McCrindle, R.; Ferguson, G.; Arsenaut, G. J.; McAlees, A. J.; Stephenson, D. K. J. Chem. Res. (S) 1984, 360; Sakamoto, T.; Nagano, T.; Kondo, Y.; Yamanaka, H. Chem.

Pharm. Bull. 1988, 36, 2248; Rossi, R. Carpita, A.; Belina, F. Org. Prep. Proc. Int. 1995, 27, 129; Ernst, A.; Gobbi, L.; Vasella, A. Tetrahedron Lett. 1996, 37, 7959; Campbell, I. B. In Organocopper Reagents; Taylor, R. J. K. Ed.; IRL Press: Oxford, UK, 1994, 217. (Review); Hundermark, T.; Littke, A.; Buchwald, S. L.; Fu, G. C. Org. Lett. 2000, 2, 1729; Dai, W.-M.; Wu, A. Tetrahedron Lett. 2001 , 42, 81 ; Alami, M.; Crousse, B.; Ferri, F. J. Organomet. Chem. 2001 , 624, 1 14; Bates, R. W.; Boonsombat, J. J. Chem. Soc, Perkin Trans. 1 2001 , 654; Batey, R. A.; Shen, M.; Lough, A. J. Org. Lett. 2002, 4, 141 1 ; Balova, I. A.; Morozkina, S. N.; Knight, D. W.; Vasilevsky, S. F. Tetrahedron Lett. 2003, 44, 107; Garcia, D.; Cuadro, A. M.; Alvarez-Builla, J.; Vaquero, J. J. Org. Lett. 2004, 6, 4175; Li, P.; Wang, L.; Li, H. Tetrahedron 2005, 61, 8633 and Lemhadri, M.; Doucet, H.; Santelli, M. Tetrahedron 2005, 61, 9839.

The intermediates of formula Va, Vb, Via, Vila, or Villa, wherein R³, R^3', R⁴, R^4', R¹³, R^14', R⁷

and R⁷ are a group

, are new and form a further subject of the present invention.

Alternatively, the intermediates of formula Va, Vb, Via, Vila, or Villa, wherein R³, R^3', R⁴, R^4',

R and R are a group , can be prepared by reacting compounds of formula

Va, Vb, Via, Vila, or Villa, wherein R³, R^3', R⁴, R^4', R¹³, R^14', R⁷ and R^7' are a group of

formula

In one embodiment of the present invention the EL device, comprises a cathode, an anode, and there between a light emitting layer containing a host material and a phosphorescent light-emitting material, wherein the host material is a compound of formula I, or II. In another embodiment of the present invention the EL device, comprises a cathode, an anode, and an electron transport material, wherein the electron transport material is, or comprises a compound of formula I, or II.

In another embodiment of the present invention the EL device, comprises a cathode, an anode, and an emitting layer, wherein the emitting layer consists of, or comprises a compound of formula I, or II.

In addition, the present invention is also directed to the use of the compounds of formula I, or Il for electrophotographic photoreceptors, photoelectric converters, solar cells, image sensors, dye lasers and electroluminescent devices.

Suitably, the light-emitting layer of the OLED device comprises a host material and one or more guest materials for emitting light. One of the host materials may be a compound of formula I, or II. The light-emitting guest material(s) is usually present in an amount less than the amount of host materials and is typically present in an amount of up to 15 wt % of the host, more typically from 0.1 to 10 wt % of the host, and commonly from 2 to 8% of the host. For convenience, the phosphorescent complex guest material may be referred to herein as a phosphorescent material. The emissive layer may comprise a single material, that combines transport and emissive properties. Whether the emissive material is a dopant or a major constituent, emissive layer may comprise other materials, such as dopants that tune the emission of the emissive layer. The emissive layer may include a plurality of emissive materials capable of, in combination, emitting a desired spectrum of light.

Other Host Materials for Phosphorescent Materials The host material useful in the invention may be used alone or in combination with other host materials. Other host materials should be selected so that the triplet exciton can be transferred efficiently from the host material to the phosphorescent material. Suitable host materials are described in WO00/70655; 01/39234; 01/93642; 02/074015; 02/15645, and US200201 17662. Suitable hosts include certain aryl amines, triazoles, indoles and carbazole compounds. Examples of hosts are 4,4'-N,N'-dicarbazole-biphenyl (CBP), 2,2'-dimethyl-4,4'- N,N'-dicarbazole-biphenyl, m-(N,N'-dicarbazole)benzene, and poly(N-vinylcarbazole), including their derivatives.

Desirable host materials are capable of forming a continuous film. The light-emitting layer may contain more than one host material in order to improve the device's film morphology, electrical properties, light emission efficiency, and lifetime. The light emitting layer may contain a first host material that has good hole-transporting properties, and a second host material that has good electron-transporting properties.

Phosphorescent Materials Phosphorescent materials may be used alone or, in certain cases, in combination with each other, either in the same or different layers. Examples of phosphorescent and related materials are described in WO00/57676, WO00/70655, WO01/41512, WO02/15645, US2003/0017361 , WO01/93642, WO01/39234, US6,458,475, WO02/071813, US6.573.651 , US2002/019751 1 , WO02/074015, US6.451.455, US2003/0072964, US2003/0068528, US6,413,656, 6,515,298, 6,451 ,415, 6,097,147, US2003/0124381 , US2003/0059646, US2003/0054198, EP1239526, EP1238981 , EP1244155, US2002/0100906, US2003/0068526, US2003/0068535, JP2003073387, JP2003073388, US2003/0141809, US2003/0040627, JP2003059667, JP2003073665 and US2002/0121638.

The emission wavelengths of cyclometallated Ir(III) complexes of the type

IrL₃ and IrL₂L', such as the green-emitting fac-tris(2-phenylpyridinato-N,C²)iridium(lll) and bis(2-phenylpyridinato-N,C²)lridium(lll) (acetylacetonate) may be shifted by substitution of electron donating or withdrawing groups at appropriate positions on the cyclometallating ligand L, or by choice of different heterocycles for the cyclometallating ligand L. The emission wavelengths may also be shifted by choice of the ancillary ligand L'. Examples of red emitters are the bis(2-(2'-benzothienyl)pyridinato-N,C³)iridium(EI)(acetylacetonate) and tris(1-phenylisoquinolinato-N,C)iridium(lll). A blue-emitting example is bis(2-(4,6- ddiifflloouurroopphheennyyll))--ppyyrriiddiinnaattoo--NN,,CC²²))llrriiddiiuum(lll)(picolinate), or bis(3,5-difluoro-2-(2-pyridyl)phenyl-

(2-carboxypyridyl)iridium(lll) (Flrpic).

Red electrophosphorescence has been reported, using bis(2-(2'-benzo[4,5- a]thienyl)pyridinato-N, C³)iridium(acetylacetonate)[Btp₂lr(acac)] as the phosphorescent material (Adachi, C, Lamansky, S., Baldo, M. A., Kwong, R. C, Thompson, M. E., and Forrest, S. R., App. Phys. Lett., 78, 1622 1624 (2001 ).

Other important phosphorescent materials include cyclometallated Pt(II) complexes such as cis-bis(2-phenylpyridinato-N,C²)platinum(ll), cis-bis(2-(2'-thienyl)pyridinato-N,C³) platinum(ll), cis-bis(2-(2'-thienyl)quinolinato-N,C^5') platinum(ll), or (2-(4,6-diflourophenyl)pyridinato-NC2') platinum(ll)acetylacetonate. Pt(ll)porphyrin complexes such as 2,3,7,8,12,13,17,18- octaethyl-21 H, 23H-porphine platinum(H) are also useful phosphorescent materials. Still other examples of useful phosphorescent materials include coordination complexes of the trivalent lanthanides such as Th³⁺ and Eu³⁺ (J. Kido et al, Appl. Phys. Lett., 65, 2124 (1994)).

Other important phosphorescent materials are described in WO06/000544 and WO08/101842.

Examples of phosphorescent materials are compounds A-1 to B-234, B-1 to B-234, C-1 to C- 44 and D-1 to D-234, which are described in WO08/101842, and compounds A1-A144 and B1-B144, which are described in WO09/100991.

Blocking Layers

In addition to suitable hosts, an OLED device employing a phosphorescent material often requires at least one exciton or hole blocking layers to help confine the excitons or electron- hole recombination centers to the light-emitting layer comprising the host and phosphorescent material, or to reduce the number of charge carriers (electrons or holes). In one embodiment, such a blocking layer would be placed between the electron-transporting layer and the light-emitting layer. In this case, the ionization potential of the blocking layer should be such that there is an energy barrier for hole migration from the host into the electron-transporting layer, while the electron affinity should be such that electrons pass more readily from the electron-transporting layer into the light-emitting layer comprising host and phosphorescent material. It is further desired, but not absolutely required, that the triplet energy of the blocking material be greater than that of the phosphorescent material. Suitable hole-blocking materials are described in WO00/70655 and WO01 /93642. Two examples of useful materials are bathocuproine (BCP) and bis(2-methyl-8-quinolinolato)(4- phenylphenolato)aluminum(lll) (BAIQ). Metal complexes other than BaIq are also known to block holes and excitons as described in US20030068528. US20030175553 describes the use of fac-tris(1-phenylpyrazolato-N,C 2)iridium(lll) (Irppz) in an electron/exciton blocking layer. An example of an electron blocking material is 1 ,1-bis[4-[Λ/,Λ/-di(p-tolyl)amino]phenyl]- cyclohexane (TAPC).

Embodiments of the invention can provide advantageous features such as operating efficiency, higher luminance, color hue, low drive voltage, and improved operating stability. Embodiments of the organometallic compounds useful in the invention can provide a wide range of hues including those useful in the emission of white light (directly or through filters to provide multicolor displays). General Device Architecture

The compounds of the present invention can be employed in many OLED device configurations using small molecule materials, oligomeric materials, polymeric materials, or combinations thereof. These include very simple structures comprising a single anode and cathode to more complex devices, such as passive matrix displays comprised of orthogonal arrays of anodes and cathodes to form pixels, and active-matrix displays where each pixel is controlled independently, for example, with thin film transistors (TFTs).

There are numerous configurations of the organic layers. The essential requirements of an OLED are an anode, a cathode, and an organic light-emitting layer located between the anode and cathode. Additional layers may be employed as more fully described hereafter.

A typical structure, especially useful for of a small molecule device, is comprised of a substrate, an anode, a hole-injecting layer, a hole-transporting layer, a light-emitting layer, optionally a hole- or exciton-blocking layer, an electron-transporting layer, and a cathode. These layers are described in detail below. Note that the substrate may alternatively be located adjacent to the cathode, or the substrate may actually constitute the anode or cathode. The organic layers between the anode and cathode are conveniently referred to as the organic EL element. Also, the total combined thickness of the organic layers is desirably less than 500 nm.

In a preferred embodiment the device comprises in this order glass substrate, an anode (indium tin oxide (ITO)), optionally a hole injection layer (2-TNATA (4,4^',4^"-tris(N-(naphtha- 2-yl)-N-phenyl-amino)triphenylamine), a hole transport layer (4,4'-bis[N-(1-naphtyl)-N- phenylamino]biphenyl (α-NPD) co-evaporated with molybdenum oxide in an ratio of about

1 :10), an electron blocking layer (TAPC [1 ,1-bis[4-[Λ/,Λ/-di(p-tolyl)amino]phenyl]cyclohexane]) , an emissive layer (Cpd. A-1 , A-8, B-8, A-30, or A-6 as host doped with 10% of blue emitter (Flrpic [bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(lll)]), a hole blocking layer (BAIq [bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium]), a electron transport layer (BPhen (4,7-diphenyl-1 ,10-phenanthroline) doped with 6% Cs), and a cathode (Al, or LiF/AI).

Substrate

The substrate can either be light transmissive or opaque, depending on the intended direction of light emission. The light transmissive property is desirable for viewing the EL emission through the substrate. Transparent glass or plastic is commonly employed in such cases. The substrate can be a complex structure comprising multiple layers of materials. This is typically the case for active matrix substrates wherein TFTs are provided below the OLED layers. It is still necessary that the substrate, at least in the emissive pixilated areas, be comprised of largely transparent materials such as glass or polymers. For applications where the EL emission is viewed through the top electrode, the transmissive characteristic of the bottom support is immaterial, and therefore can be light transmissive, light absorbing or light reflective. Substrates for use in this case include, but are not limited to, glass, plastic, semiconductor materials, silicon, ceramics, and circuit board materials. Again, the substrate can be a complex structure comprising multiple layers of materials such as found in active matrix TFT designs. It is necessary to provide in these device configurations a light- transparent top electrode. Anode

When the desired electroluminescent light emission (EL) is viewed through the anode, the anode should be transparent or substantially transparent to the emission of interest. Common transparent anode materials used in this invention are indium-tin oxide (ITO), indium-zinc oxide (IZO) and tin oxide, but other metal oxides can work including, but not limited to, aluminum- or indium-doped zinc oxide, magnesium-indium oxide, and nickel- tungsten oxide. In addition to these oxides, metal nitrides, such as gallium nitride, and metal selenides, such as zinc selenide, and metal sulfides, such as zinc sulfide, can be used as the anode. For applications where EL emission is viewed only through the cathode, the transmissive characteristics of the anode are immaterial and any conductive material can be used, transparent, opaque or reflective. Example conductors for this application include, but are not limited to, gold, iridium, molybdenum, palladium, and platinum. Desired anode materials are commonly deposited by any suitable means such as evaporation, sputtering, chemical vapor deposition, or electrochemical means. Anodes can be patterned using well- known photolithographic processes. Optionally, anodes may be polished prior to application of other layers to reduce surface roughness so as to minimize shorts or enhance reflectivity. Cathode When light emission is viewed solely through the anode, the cathode used in this invention can be comprised of nearly any conductive material. Desirable materials have good film- forming properties to ensure good contact with the underlying organic layer, promote electron injection at low voltage, and have good stability. Useful cathode materials often contain a low work function metal (<4.0 eV) or metal alloy. One useful cathode material is comprised of a Mg:Ag alloy wherein the percentage of silver is in the range of 1 to 20%, as described in US- A-4, 885,221. Another suitable class of cathode materials includes bilayers comprising the cathode and a thin electron-injection layer (EIL) in contact with an organic layer (e.g., an electron transporting layer (ETL)) which is capped with a thicker layer of a conductive metal. Here, the EIL preferably includes a low work function metal or metal salt, and if so, the thicker capping layer does not need to have a low work function. One such cathode is comprised of a thin layer of LiF followed by a thicker layer of Al as described in US-A- 5,677,572. An ETL material doped with an alkali metal, for example, Li-doped AIq, is another example of a useful EIL. Other useful cathode material sets include, but are not limited to, those disclosed in US-A-5,059,861 , 5,059,862 and 6,140,763.

When light emission is viewed through the cathode, the cathode must be transparent or nearly transparent. For such applications, metals must be thin or one must use transparent conductive oxides, or a combination of these materials. Optically transparent cathodes have been described in more detail in US-A-4,885,21 1 , 5,247,190, JP 3,234,963, U.S. Pat. Nos. 5,703,436, 5,608,287, 5,837,391 , 5,677,572, 5,776,622, 5,776,623, 5,714,838, 5,969,474, 5,739,545, 5,981 ,306, 6,137,223, 6,140,763, 6,172,459, EP1076368, US-A-6,278,236 and 6,284,3936. Cathode materials are typically deposited by any suitable method such as evaporation, sputtering, or chemical vapor deposition. When needed, patterning can be achieved through many well known methods including, but not limited to, through-mask deposition, integral shadow masking as described in US-A-5,276,380 and EP0732868, laser ablation, and selective chemical vapor deposition.

Hole-Injecting Layer (HIL)

A hole-injecting layer may be provided between anode and hole-transporting layer. The hole- injecting material can serve to improve the film formation property of subsequent organic layers and to facilitate injection of holes into the hole-transporting layer. Suitable materials for use in the hole-injecting layer include, but are not limited to, porphyrinic compounds as described in US-A-4,720,432, plasma-deposited fluorocarbon polymers as described in US- A-6,208,075, and some aromatic amines, for example, m-MTDATA (4,4',4"-tris[(3- methylphenyl)phenylamino]triphenylamine), or 2-TNATA (4,4^',4^"-tris(N-(naphtha-2-yl)-N- phenyl-amino)triphenylamine). Alternative hole-injecting materials reportedly useful in organic EL devices are described in EP0891 121 and EP1029909.

Hole-Transporting Layer (HTL)

The hole-transporting layer of the organic EL device contains at least one hole-transporting compound such as an aromatic tertiary amine, where the latter is understood to be a compound containing at least one trivalent nitrogen atom that is bonded only to carbon atoms, at least one of which is a member of an aromatic ring. In one form the aromatic tertiary amine can be an arylamine, such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine. Exemplary monomeric triarylamines are illustrated in US-A-3, 180,730. Other suitable triarylamines substituted with one or more vinyl radicals and/or comprising at least one active hydrogen containing group are disclosed in US-A-3, 567, 450 and 3,658,520. A more preferred class of aromatic tertiary amines are those which include at least two aromatic tertiary amine moieties as described in US-A-4,720,432 and 5,061 ,569. Such compounds include those represented by structural formula

, wherein Q¹ and Q² are independently selected aromatic tertiary amine moieties and G is a linking group such as an arylene, cycloalkylene, or alkylene group of a carbon to carbon bond. In one embodiment, at least one of Q¹ or Q² contains a polycyclic fused ring structure, e.g., a naphthalene. When G is an aryl group, it is conveniently a phenylene, biphenylene, or naphthalene moiety.

A useful class of triarylamines satisfying structural formula (A) and containing two triarylamine moieties is represented by structural formula

^ A

, where Q and Q each independently represents a hydrogen atom, an aryl group, or an alkyl group or Q³ and Q⁴ together represent the atoms completing a cycloalkyl group; and Q⁵ and Q⁶ each independently represents an aryl group, which is in turn substituted with a diaryl substituted amino group, as indicated by structural formula

, wherein Q⁷ and Q⁸ are independently selected aryl groups. In one embodiment, at least one of Q⁷ or Q⁸ contains a polycyclic fused ring structure, e.g., a naphthalene.

Another class of aromatic tertiary amines are the tetraaryldiamines. Desirable tetraaryldiamines include two diarylamino groups, such as indicated by formula (C), linked through an arylene group. Useful tetraaryldiamines include those represented by formula

, wherein each Are is an independently selected arylene group, such as a phenylene or anthracene moiety, n is an integer of from 1 to 4, and Ar, Q⁹, Q¹⁰, and Q¹¹ are independently selected aryl groups. In a typical embodiment, at least one of Ar, Q⁹, Q¹⁰, and Q¹¹ is a polycyclic fused ring structure, e.g., a naphthalene. The various alkyl, alkylene, aryl, and arylene moieties of the foregoing structural formulae (A), (B), (C), (D), can each in turn be substituted. Typical substituents include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and halogen such as fluoride, chloride, and bromide. The various alkyl and alkylene moieties typically contain from about 1 to 6 carbon atoms. The cycloalkyl moieties can contain from 3 to about 10 carbon atoms, but typically contain five, six, or seven ring carbon atoms, e.g. cyclopentyl, cyclohexyl, and cycloheptyl ring structures. The aryl and arylene moieties are usually phenyl and phenylene moieties.

The hole-transporting layer can be formed of a single or a mixture of aromatic tertiary amine compounds. Specifically, one may employ a triarylamine, such as a triarylamine satisfying the formula (B), in combination with a tetraaryldiamine, such as indicated by formula (D). When a triarylamine is employed in combination with a tetraaryldiamine, the latter is positioned as a layer interposed between the triarylamine and the electron injecting and transporting layer. Illustrative of useful aromatic tertiary amines are the following: 1 ,1-Bis(4- di-p-tolylaminophenyl)cyclohexane, 1 ,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane, N,N,N',N'-tetraphenyl-4,4'"-diamino-1 ,1 ':4',1 ":4", 1 '"-quaterphenyl bis(4-dimethylamino-2- methylphenyl)phenylmethane, 1 ,4-bis[2-[4-[N,N-di(p-toly)amino]phenyl]vinyl]benzene (BDTAPVB), N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'- diaminobiphenyl, N,N,N',N'-tetra-1-naphthyl-4,4'-diaminobiphenyl, N,N,N',N'-tetra-2-naphthyl- 4,4'-diaminobiphenyl, N-phenylcarbazole, 4,4'-bis[N-(1 -naphthyl)-N-phenylamino]biphenyl (NPB), 4,4'-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl (TNB), 4,4'-bis[N-(1-naphthyl)- N-phenylamino]p-terphenyl, 4,4'-bis[N-(2-naphthyl)-N-phenylamino]biphenyl, 4,4'-bis[N-(3- acenaphthenyl)-N-phenylamino]biphenyl, 1 ,5-bis[N-(1 -naphthyl)-N-phenylamino] naphthalene, 4,4'-bis[N-(9-anthryl)-N-phenylamino]biphenyl, 4,4'-bis[N-(1 -anthryl)-N- phenylamino]-p-terphenyl, 4,4'-bis[N-(2-phenanthryl)-N-phenylamino]biphenyl, 4,4'-bis[N-(8- fluoranthenyl)-N-phenylamino]biphenyl, 4,4'-bis[N-(2-pyrenyl)-N-phenylamino]biphenyl, 4,4'- bis[N-(2-naphthacenyl)-N-phenylamino]biphenyl, 4,4'-bis[N-(2-perylenyl)-N-phenylamino] biphenyl, 4,4'-bis[N-(1 -coronenyl)-N-phenylamino]biphenyl, 2,6-bis(di-p-tolylamino) naphthalene, 2,6-bis[di-(1 -naphthyl)amino]naphthalene, 2,6-bis[N-(1 -naphthyl)-N-(2- naphthyl)amino]naphthalene, N,N,N',N'-tetra(2-naphthyl)-4,4"-diamino-p-terphenyl, 4,4'-bis {N-phenyl-N-[4-(1-naphthyl)-phenyl]amino}biphenyl, 2,6-bis[N,N-di(2-naphthyl)amino]fluorine, 4,4',4"-tris[(3-methylphenyl)phenylamino]triphenylamine (MTDATA), and 4,4'-Bis[N-(3- methylphenyl)-N-phenylamino]biphenyl(TPD). A hole transport layer may be used to enhance conductivity. NPD and TPD are examples of intrinsic hole transport layers. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1 as disclosed in US6,337,102 or DE10058578. Another class of useful hole-transporting materials includes polycyclic aromatic compounds as described in EP1009041. Tertiary aromatic amines with more than two amine groups may be used including oligomeric materials. In addition, polymeric hole-transporting materials can be used such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole, polyaniline, and copolymers such as poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also called PEDOT/PSS.

Fluorescent Light-Emitting Materials and Layers (LEL)

In addition to the phosphorescent materials, other light emitting materials may be used in the OLED device, including fluorescent materials. Although the term "fluorescent" is commonly used to describe any light emitting material, in this case we are referring to a material that emits light from a singlet excited state. Fluorescent materials may be used in the same layer as the phosphorescent material, in adjacent layers, in adjacent pixels, or any combination. Care must be taken not to select materials that will adversely affect the performance of the phosphorescent materials. One skilled in the art will understand that triplet excited state energies of materials in the same layer as the phosphorescent material or in an adjacent layer must be appropriately set so as to prevent unwanted quenching. As more fully described in US-A-4, 769,292 and 5,935,721 , the light-emitting layer (LEL) of the organic EL element includes a luminescent fluorescent or phosphorescent material where electroluminescence is produced as a result of electron-hole pair recombination in this region. The light-emitting layer can be comprised of a single material, but more commonly consists of a host material doped with a guest emitting material or materials where light emission comes primarily from the emitting materials and can be of any color. The host materials in the light-emitting layer can be an electron-transporting material, as defined below, a hole-transporting material, as defined above, or another material or combination of materials that support hole-electron recombination. Fluorescent emitting materials are typically incorporated at 0.01 to 10% by weight of the host material. The host and emitting materials can be small non-polymeric molecules or polymeric materials such as polyfluorenes and polyvinylarylenes (e.g., poly(p-phenylenevinylene), PPV). In the case of polymers, small molecule emitting materials can be molecularly dispersed into a polymeric host, or the emitting materials can be added by copolymerizing a minor constituent into a host polymer. Host materials may be mixed together in order to improve film formation, electrical properties, light emission efficiency, lifetime, or manufacturability. The host may comprise a material that has good hole-transporting properties and a material that has good electron-transporting properties. Host and emitting materials known to be of use include, but are not limited to, those disclosed in US-A-4,768,292, 5,141 ,671 , 5,150,006, 5,151 ,629, 5,405,709, 5,484,922, 5,593,788, 5,645,948, 5,683,823, 5,755,999, 5,928,802, 5,935,720, 5,935,721 , and 6,020,078.

Metal complexes of 8-hydroxyquinoline and similar derivatives (Formula E) constitute one class of useful host compounds capable of supporting electroluminescence, and are particularly suitable for light emission of wavelengths longer than 500 nm, e.g., green, yellow, orange, and red.

, wherein M represents a metal; v is an integer of from 1 to 4; and ZZ independently in each occurrence represents the atoms completing a nucleus having at least two fused aromatic rings. From the foregoing it is apparent that the metal can be monovalent, divalent, trivalent, or tetravalent metal. The metal can, for example, be an alkali metal, such as lithium, sodium, or potassium; an alkaline earth metal, such as magnesium or calcium; an earth metal, such aluminum or gallium, or a transition metal such as zinc or zirconium. Generally any monovalent, divalent, trivalent, or tetravalent metal known to be a useful chelating metal can be employed. ZZ completes a heterocyclic nucleus containing at least two fused aromatic rings, at least one of which is an azole or azine ring. Additional rings, including both aliphatic and aromatic rings, can be fused with the two required rings, if required. To avoid adding molecular bulk without improving on function the number of ring atoms is usually maintained at 18 or less.

Illustrative of useful chelated oxinoid compounds are the following: CO-1 : Aluminum trisoxine [alias, tris(8-quinolinolato)aluminum(lll)] CO-2: Magnesium bisoxine [alias, bis(8-quinolinolato)magnesium(ll)] CO-3: Bis[benzo{f}-8-quinolinolato]zinc(ll) CO-4: Bis(2-methyl-8-quinolinolato)aluminum(lll)-μ-oxo-bis(2-methyl-8-quinol- inolato)aluminum(lll)

CO-5: Indium trisoxine [alias, tris(8-quinolinolato)indium]

CO-6: Aluminum tris(5-methyloxine) [alias, tris(5-methyl-8-quinolinolato) aluminum(lll)] CO-7: Lithium oxine [alias, (8-quinolinolato)lithium(l)] CO-8: Gallium oxine [alias, tris(8-quinolinolato)gallium(lll)]

CO-9: Zirconium oxine [alias, tetra(8-quinolinolato)zirconium(IV)]

Useful fluorescent emitting materials include, but are not limited to, derivatives of anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, and quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrilium and thiapyrilium compounds, fluorene derivatives, periflanthene derivatives, indenoperylene derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, and carbostyryl compounds. Illustrative examples of useful materials include, but are not limited to, compounds L1 to L52 described in US7,090,930B2.

Electron-Transporting Layer (ETL)

Preferred thin film-forming materials for use in forming the electron-transporting layer of the organic EL devices of this invention are metal chelated oxinoid compounds, including chelates of oxine itself (also commonly referred to as 8-quinolinol or 8-hydroxyquinoline). Such compounds help to inject and transport electrons and exhibit both high levels of performance and are readily fabricated in the form of thin films. Exemplary of contemplated oxinoid compounds are those satisfying structural formula (E), previously described. Other electron-transporting materials include various butadiene derivatives as disclosed in US4,356,429 and various heterocyclic optical brighteners as described in US4,539,507. Benzazoles satisfying structural formula (G) are also useful electron transporting materials. Triazines are also known to be useful as electron transporting materials. Doping may be used to enhance conductivity. AIq₃ is an example of an intrinsic electron transport layer. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1 :1 , as disclosed in US 6,337,102.

Deposition of Organic Layers

The organic materials mentioned above are suitably deposited by any means suitable for the form of the organic materials. In the case of small molecules, they are conveniently deposited through thermal evaporation, but can be deposited by other means such as from a solvent with an optional binder to improve film formation. If the material is soluble or in oligomeric/polymeric form, solution processing is usually preferred e.g. spin-coating, ink-jet printing. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing. Patterned deposition can be achieved using shadow masks, integral shadow masks (US5,294,870), spatially-defined thermal dye transfer from a donor sheet (US5,688,551 , 5,851 ,709 and 6,066,357) and inkjet method (US6,066,357).

Encapsulation

Most OLED devices are sensitive to moisture or oxygen, or both, so they are commonly sealed in an inert atmosphere such as nitrogen or argon, along with a desiccant such as alumina, bauxite, calcium sulfate, clays, silica gel, zeolites, alkaline metal oxides, alkaline earth metal oxides, sulfates, or metal halides and perchlorates. Methods for encapsulation and desiccation include, but are not limited to, those described in US6,226,890. In addition, barrier layers such as SiO_x, Teflon, and alternating inorganic/polymeric layers are known in the art for encapsulation.

Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, lights for interior or exterior illumination and/or signalling, fully transparent displays, flexible displays, laser printers, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, theatre or stadium screen, or a sign. Various control mechanism may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix.

Various features and aspects of the present invention are illustrated further in the examples that follow. While these examples are presented to show one skilled in the art how to operate within the scope of this invention, they are not to serve as a limitation on the scope of the invention where such scope is only defined in the claims. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, temperatures are in degrees centigrade and pressures are at or near atmospheric pressure.

Examples

Example 1

a) 30 g of 1 (76 mmol) and 480 ml of dichloromethane are put together in a 1.5 I sulfuration flask. Dry pyridine (15.3 ml, 190 mmol) is added at room temperature. Then trifluoromethane- sulfonic anhydride (30.7 ml, 183 mmol) in 150 ml of dichloromethane is added dropwise at room temperature within nine hours. The reaction medium is poured onto water, the organic phase is separated and the water phase is extracted with dichloromethane. The organic phase is washed with 5%-HCI, dried over magnesium sulfate and evaporated under reduced pressure. Crystallisation from heptane/ethylacetate results in 38.7 g (77%) of the desired compound S-1. ¹H NMR (CDCI₃, 300 MHz) 7.26-7.25 (m, 1 H), 7.10-6.96 (m, 13H), 6.66 (dd, Ji = 1.5 Hz, J₂ = 7.8 Hz, 2H); ¹³C NMR (CDCI₃, 75 MHz) 159.6, 149.9, 137.7, 134.8, 131.2, 129.3, 129.0, 128.1 , 128.0, 127.9, 127.7, 126.3, 126.0, 118.7 (q, J_c-F = 319 Hz), 1 15.9, 104.7, 69.3

b) 3 g of S-1 (4.6 mmol), 95.6 mg of triphenylphosphine (0.4 mmol) and 3.8 ml of triethylamine (28 mmol) are added to 10 ml of 4-methyl-2-pentanone under an argon atmosphere. Then 40.9 mg (0.2 mmol) of palladium(ll)acetate are added, followed by the addition of 0.688 ml of formic acid (18 mmol). The reaction mixture is heated at 90⁰C for two hours. The same amount of triphenylphosphine and triethylamine and the same amount of palladium acetate are added subsequently, followed by the addition of the same amount of formic acid. After two hours heating at 90⁰C, the reaction is finished. Active carbon is added to the medium, followed by dilution with ethylacetate. The organic phase is washed three times with water, dried over magnesium sulfate and evaporated under reduced pressure to give 2.0 g of a brown solid. Chromatography over silica gel with cyclohexane 98-95% / ethylacetate 2-5% affords 1.2 g of a white solid (72%). ¹H NMR (CDCI₃, 300 MHz) 7.28-6.92 (m, 16H), 6.75-6.72 (m, 2H); ¹³C NMR (CDCI₃, 75 MHz) 158.9, 139.7, 136.6, 131.6, 129.4, 129.0, 128.5, 127.6, 127.4, 127.1 , 126.6, 125.7, 125.2, 122.6, 1 10.3, 70.3.

c) 3 g of S-1 (4.6 mmol), 1.12 g phenylacetylene (10.9 mmol), 260 mg of copper iodide (1.4 mmol) and 4.04 g of tetrabutylammonium iodide (10.9 mmol) are added to 12 ml of a 1 :5- mixture of triethylamine/acetonitrile under argon atmosphere. Then, 526 mg of tetrakis(triphenylphosphine)palladium (0.5 mmol) are added at room temperature. The reaction mixture is stirred at reflux for 12 hours. Water and ethylacetate are added, the water phase is extracted twice with ethylacetate and the organic phase is dried over magnesium sulfate and evaporated under reduced pressure to give 8.9 g of a red oil. Chromatography over silica gel with cyclohexane/ethylacetate 95:5 results in 2 g of an orange powder (77%). ¹H NMR (CDCI₃, 300 MHz) 7.56-7.53 (m, 4H), 7.37-6.97 (m, 20 H), 6.74-6.71 (m, 2H); ¹³C NMR (CDCI₃, 75 MHz) 158.8, 138.8, 136.0, 131.71 , 131.65, 129.2, 128.8, 128.44, 128.39, 127.8, 127.5, 127.4, 126.5, 126.3, 125.0, 124.3, 123.1 , 113.2, 89.8, 89.0, 70.05.

d) 1.5 g of S-3 (2.7 mmol) are dissolved in 10 ml of DMSO. Iodine is added at room temperature. Then, the solution is heated at 140⁰C for 18 hours. A yellow solid formed. The yellow solid is filtered off, washed with a 1 %-solution of Na₂S₂O₃ and water. The solid is dried under vacuum to afford 1.54 g (92%) of a yellow solid. ¹H NMR (CDCI₃, 300 MHz) 7.98 (dd, J₁ = 1.2 Hz, J₂ = 8.4 Hz, 4H), 7.73 (d, J = 1.2 Hz, 2H), 7.70-7.64 (m, 4H), 7.55-7.50 (m, 2H), 7.35 (d, J = 7.8 Hz, 2H), 7.15-6.98 (m, 8H), 6.67 (dd, J₁ = 1.5 Hz, J₂ = 8.1 Hz, 2H); ¹³C NMR (CDCI₃, 75 MHz) 194.1 , 193.4, 159.4, 137.8, 137.5, 135.1 , 135.0, 134.6, 132.8, 120.0, 129.2, 129.1 , 129.0, 128.1 , 127.9, 127.7, 126.8, 126.4, 125.7, 125.4, 1 1 1.0, 70.2.

e) 1.9 g of S-4 (3 mmol) and 689 mg of 1.2-phenylenediamine (6.4 mmol) are suspended in 57 ml of a mixture of ethanol/chloroform 2:1 under an atmosphere of nitrogen. The reaction mixture is heated to reflux, four drops of 97%-sulphuric acid are added and the reaction mixture is heated at reflux for 3/4 hours. The reaction mixture is cooled down by an ice bath. The formed precipitate is filtered off and washed with a cold mixture of ethanol/chloroform 2:1 affording 1.85 g of a white-yellow powder (80%). ¹H NMR (CDCI₃, 300 MHz) 8.21 (dd, J₁ = 3.6 Hz, J₂ = 6.6 Hz, 4H), 7.81 (dd, J₁ = 3.3 Hz, J₂ = 6.3 Hz, 4H), 7.62-7.58 (m, 4H), 7.42- 7.34 (m, 8H), 7.20-6.96 (m, 12H), 6.71 (dd, J₁ = 1.5 Hz, J₂ = 7.8 Hz, 2H); ¹³C NMR (CDCI₃, 75 MHz) 159.0, 153.5, 152.8, 141.4, 141.1 , 140.5, 138.9, 138.8, 135.9, 132.0, 130.2, 130.1 , 129.9, 129.3, 129.22, 129.17, 129.0, 128.7, 128.3, 127.7, 127.4, 127.3, 126.5, 125.0, 124.7, 1 11.8, 69.8.

Example 2

a) 2.44 g of S-2 (6.7 mmol) are suspended at room temperature under nitrogen in 1 10 ml of acetic acid. 7.86 g (20.1 mmol) of benzyltrimethylammonium tribromide are added and the reaction is heated at 100⁰C during one night. After cooling of the reaction mixture, water, ethylacetate and sodium hydrogen sulfate (5%-solution) are added. After stirring, dichloromethane is added. The aqueous phase is extracted twice with dichloromethane and the combined organic phases are washed twice with sodium hydrogen sulfate (5%-solution) and three times with water. The organic phase is dried over magnesium sulfate and evaporated under reduced pressure, affording 3.47 g of beige crystals (99%). ¹H NMR (CDCI₃, 300 MHz) 7.40 (dd, J₁ = 2.1 Hz, J₂ = 8.4 Hz, 2H), 7.31 (d, J = 2.1 Hz, 2H), 7.10-6.99 (m, 10H), 6.71-6.68 (m, 2H).

b) 1.7 g of S-5 (3.27 mmol) are stirred together with 1.23 g of carbazole (7.19 mmol), 1.29 g of sodium te/f-butylate (13.08 mmol) and 0.053 g of tris-(te/f-butyl) phosphine (1 M in toluene, 0.26 mmol) in 40 ml of xylene at room temperature under argon atmosphere. Then 0.073 g of palladium(ll) acetate (0.33 mmol) are added and the reaction is heated at 150⁰C for one night. The reaction mixture is poured into water and the aqueous phase is extracted with dichloromethane. The organic phase is dried over magnesium sulfate and evaporated under reduced pressure. The solid obtained is heated twice in a mixture of cyclohexane and ethylacetate to furnish 1.4 g of a white solid (63%). ¹H NMR (CDCI₃, 300 MHz) 8.08 (d, J = 9 Hz, 4H), 7.54 (dd, J₁ = 2.1 Hz, J₂ = 8.4 Hz, 2H), 7.42-7.15 (m, 24H), 6.90-6.87 (m, 2H).

Example 3

5.0 g of S-1 (7.59 mmol), 2.79 g of carbazole (16.7 mmol), 4.51 g of potassium phosphate (21.25 mmol) and 0.54 g (1.37 mmol) of 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)- biphenyl in 65 ml of toluene are stirred under argon atmosphere at room temperature. Then, 0.42 g of tris(dibenzylideneacetone) palladium(ll) (0.46 mmol) are added and the reaction is heated at 100⁰C over night. Water and ethyl acetate are added to the reaction mixture and the suspension filtered. The separated organic phase is washed twice with water and the combined aqueous phases are extracted with ethyl acetate. The combined organic phases are dried over magnesium sulfate and evaporated under reduced pressure. Chromatography over silica gel with cyclohexane/ethylacetate 98:2 results in 1.63 g of a white yellow powder (31 %). ¹H NMR (CDCI₃, 300 MHz) 8.17 (d, J = 7.8 Hz, 4H), 7.63 (d, J = 8.4 Hz, 4H), 7.51- 7.43 (m, 8H), 7.35-7.26 (m, 8H), 7.15-7.1 1 (m, 6H), 6.96-6.93 (m, 2H).

Example 4

4.0 g of S-1 (6.07 mmol), 2.22 g (18.21 mmol) of phenylboronic acid, 3.36 g (24.28 mmol) of dry potassium carbonate in 61 ml of toluene are stirred under argon atmosphere at room temperature. Then, 0.42 g (0.36 mmol) of palladium tetrakis(triphenylphosphine) is added and the reaction is heated at 90⁰C for one hour. Water and ethyl acetate are added to the reaction mixture. Then, the separated aqueous phase is extracted twice with ethyl acetate, and the combined organic phases are washed twice with water, dried over magnesium sulfate, filtered and evaporated under reduced pressure. A chromatography over silica gel (cyclohexane/ethylacetate 98:2) results in 1.57 g of a white powder (50%). ¹H NMR (CDCI₃, 300 MHz) 7.62-7.59 (m, 4H), 7.51-7.42 (m, 4H), 7.38-7.18 (m, 10H), 7.12-6.97 (m, 6H), 6.87- 6.81 (m, 2H).

Example 5

4.0 g of S-1 (6.07 mmol), 4.48 g (18.21 mmol) of 1-pyreneboronic acid, 3.36 g (24.28 mmol) of dry potassium carbonate in 81 ml of dioxane are stirred under argon atmosphere at room temperature. Then, 0.42 g (0.36 mmol) of palladium tetrakis(triphenylphosphine) are added and the reaction is heated at 90⁰C for one night. The following day, 0.04 equivalents of palladium tetrakis(triphenylphosphine) are further added and the reaction is kept at 90⁰C for one more night. 100ml of a 1 % aqueous solution of NaCN are added at room temperature to the medium which is boiled for 20 min. Then, methylene chloride is added. The organic phase is washed by water and the organic phase is then dried over magnesium sulfate, filtered and evaporated under reduced pressure. A chromatography over silica gel (cyclohexane/ethylacetate 98:2), and a purification by preparative HPLC furnished 0.5 g of a white powder (1 1%). ¹H NMR (CDCI₃, 300 MHz) 8.39 (d, J = 9.3 Hz, 2H), 8.27 (d, J = 7.8 Hz, 2H), 8.23-8.20 (m, 4H), 8.15-8.01 (m, 10H), 7.51-7.48 (m, 4H), 7.40-7.34 (m, 4H), 7.17-7.12 (m, 6H), 7.05-7.01 (m, 2H).

Example 6

a) 40.0 g (109 mmol) of 4,4-dibromobenzyl and 24.0 g (218 mmol) of resorcinol are stirred in a mixture of 185 ml of xylene and 45 ml of ethyl acetate. The medium is heated at 55°C and HCI gas bubbled through the reaction mixture during eight hours. After cooling, a beige suspension is obtained. This suspension is filtered, washed with 90 ml of cold xylene and 170 ml of water. The product is dried at 90⁰C under reduced pressure. 54.2 g of a beige-gray powder are obtained (90%). ¹H NMR (CDCI₃, 300 MHz) 7.22 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H), 6.95 (d, J = 8.1 Hz, 2H), 6.63 (d, J = 8.4 Hz, 2H), 6.59 (d, J = 2.1 Hz, 2H), 6.49 (dd, J = 2.1 Hz and J = 8.1 , 2H).

b) 15 g of S-6 (27.2 mmol) and 240 ml of dichloromethane are put together in a 750ml sulfuration flask. 5.38 ml (68.0 mmol) of dry pyridine are added at room temperature. Then 1 1 ml (65.3 mmol) of trifluoromethanesulfonic anhydride in 76 ml of dichloromethane are added dropwise at room temperature over two hours and the medium is stirred further at room temperature over night. The reaction medium is poured onto water, the organic phase is separated and the water phase is extracted with CH₂CI₂. The organic phase is washed with 5%-HCI, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude product is shortly boiled in a 10:1 -mixture of heptane/ethyl acetate, filtered and washed with 100 ml of cold heptane, giving 16.6 g (75%) of S-7. ¹H NMR (CDCI₃, 300 MHz) 7.27 (d, J = 9.1 Hz, 2H), 7.21 (m, 4H), 7.07 (d, J = 2.4 Hz, 2H), 6.98 (m, 4H), 6.54 (d, J = 8.3 Hz, 2H).

c) 3.0 g of S-7 (3.67 mmol), 2.5 g (14.97 mmol) of carbazole, 4.36 g (20.55 mmol) of potassium phosphate and 0.43 g (1.10 mmol) of 2-dicyclohexylphosphino-2'-(N,N-dimethyl- amino)biphenyl in 57 ml of toluene are stirred under argon atmosphere at room temperature. Then, 0.34 g (0.37 mmol) of tris(dibenzylideneacetone) palladium(ll) is added and the reaction is heated at 100⁰C over night. At room temperature, a 1 % aqueous solution of NaCN is added to the medium which is boiled for 20 min. Then, methylene chloride is added. The organic phase is washed by water and the organic phase is then dried over magnesium sulfate, filtered and evaporated under reduced pressure to give 4.87 g of yellow-orange crystals. Those are dissolved in methylene chloride and are separated in batches through a preparative HPLC (heptane/ethyl acetate 7:3). The pure fractions are unified to give 2.22 g of white crystals of A-30 (59%). ¹H NMR (CDCI₃, 300 MHz) 8.18 (d, J = 7.5 Hz, 4H), 8.09 (d, J = 7.8 Hz, 4H), 7.71-7.60 (m, 4H), 7.54-7.44 (m, 16H), 7.37-7.16 (m, 16H), 7.05-6.96 (m, 4H).

Example 7

4.9 g of S-7 (6 mmol), 6.90 g (24.60 mmol) 3,6-di-te/f-butyl carbazole, 7.13 g (33.60 mmol) potassium phosphate and 0.71 g (1.8 mmol) 2-dicyclohexylphosphino-2'-(N,N-dimethyl- amino)biphenyl in 90 ml toluene are stirred under argon atmosphere at room temperature. Then, 0.55 g (0.6 mmol) of tris(dibenzylideneacetone) palladium(ll) is added and the reaction is heated at 100⁰C over night. The conversion is then only about half, so 0.71 g ligand and 0.55 g palladium catalyst are once more added at room temperature and the reaction is stirred at 100⁰C for 7h more. At room temperature, a 1 % aqueous solution of NaCN is added to the medium which is boiled for 20 min. Then, methylene chloride is added. The organic phase is washed by water and the organic phase is then dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude material is purified by chromatography on silica gel (Hexane:CH2CI2 70:30) and further recrystallized from isopropanol to give 1 g of white crystals (1 1%).

Example 8

5.39 g of S-1 (7.59 mmol), 7.62 g (27.27 mmol) of 3,6-di-te/f-butyl-9H-carbazole, 5.60 g (45.81 mmol) of potassium phosphate and 0.96 g (2.45 mmol) of 2-dicyclohexylphosphino-2'- (N,N-dimethylamino)biphenyl in 134 ml of toluene are stirred under argon atmosphere at room temperature. Then, 0.75 g of tris(dibenzylideneacetone) palladium(ll) (0.82 mmol) are added and the reaction is heated at 100⁰C over night. At room temperature, a 1 % aqueous solution of NaCN is added to the medium which is boiled for 20 min. Cooling down to room temperature leads to phase separation. The aqueous phase is extracted with ethyl acetate. The unified organic phases are washed by water, dried over magnesium sulfate, filtered and evaporated under redeuced pressure. The crude material is first purified by chromatography over silica gel (cyclohexane/ethylacetate 99:1 ) and then by preparative HPLC to give 1.55 g of white crystals (21%). ¹H NMR (CDCI₃, 300 MHz) 8.15 (d, J = 1.2 Hz, 4H), 7.56-7.44 (m, 10H), 7.40 (d, J = 1.8 Hz, 2H), 7.32-7.25 (m, 4H), 7.14-7.08 (m, 6H), 6.93-6.91 (m, 2H), 1.48 (s, 36 H).

Example 9

a) 2.41 g (7.2 mmol) of 3,6-dibromocarbazole and 5.00 g (17.29 mmol) of 4-(Λ/,/V- diphenylamino)-1-phenylboronic acid are stirred in 1 10 ml of THF under argon. 9.95 g of potassium carbonate dissolved in 36 ml of water are added and everything is further stirred under argon. Then 0.21 g (0.18 mmol) of palladium tetrakis(triphenylphosphine) are added and the reaction is heated at reflux over night. At room temperature, a 1 % aqueous solution of NaCN is added to the medium which is boiled for 20 min. At room temperature, ethyl acetate is added and the organic phase is washed with water, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude material is purified by chromatography over silica gel (cyclohexane/ethyl acetate 5:1 ) to give 4.48 g of white crystals (95%). ¹H NMR (CDCI₃, 300 MHz) 8.30 (d, J = 1.5 Hz, 2H), 8.07 (s, 1 H), 7.66 (dd, J = 1.8 Hz, J = 8.4 Hz, 2H), 7.61-7.57 (m, 4H), 7.48 (d, J = 8.4 Hz, 2H), 7.30-7.25 (m, 8H), 7.20-7.14 (m, 12H), 7.05-7.00 (m, 4H).

b) 4.00 g of S-8 (6.12 mmol), 1.86 g of S-1 (658.55 g.mol-1 , 2.78 mmol), 0.21 g (0.5 mmol) of 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl and 1.65 g (7.78 mmol) of potassium phosphate are stirred under argon in 23 ml of toluene. 0.16 g (0.17 mmol) of tris(dibenzylideneacetone) palladium(ll) are added and the reaction is stirred at 100⁰C over night. 0.21 g of ligand and 0.17 g of palladium catalyst are once more added at room temperature and the reaction is stirred at 100⁰C for one more day. At room temperature, a 1 % aqueous solution of NaCN is added to the medium which is boiled for 20 min. Dichloro- methane is added and the organic phase is washed with water, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude product is purified by chromatography over silica gel (dichlormethane/cyclohexane 1 :1 ) to give 2.5 g of beige crystals (54%).

Example 10

a) 3.09 g (9.23 mmol) of 3,6-dibromocarbazole and 2.78 g (22.2 mmol) of phenylboronic acid are stirred in 140 ml of THF under argon. 12.76 g (92.30 mmol) of potassium carbonate in 46 ml of water are added. 0.27 g (0.23 mmol) of palladium tetrakis(triphenylphosphine) are added under argon and the reaction is stirred under reflux over night. At room temperature, a 1 % aqueous solution of NaCN is added to the medium which is boiled for 20 min. At room temperature, ethyl acetate is added and the organic phase is washed with water, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude material is purified by chromatography over silica gel (cyclohexane/ethyl acetate 4:1 ) to give 2.17 g of a white solid (74%). ¹H NMR (CDCI₃, 300 MHz) 8.34 (d, J = 1.8 Hz, 2H), 8.11 (s, 1 H), 7.74- 7.68 (m, 6H), 7.52-7.45 (m, 6H), 7.37-7.32 (m, 2H).

b) 4.00 g of S-9 (12.5 mmol), 3.75 g of S-1 (5.69 mmol), 0.40 g (1.02 mmol) 2-of dicyclo- hexylphosphino-2'-(N,N-dimethylamino)biphenyl and 3.38 g (15.93 mmol) of potassium phosphate are stirred under argon in 47 ml toluene. 0.31 g (0.34 mmol) of tris(dibenzylidene- acetone) palladium(ll) are added and the reaction is stirred at 100⁰C for 24h. At room temperature, a 1 % aqueous solution of NaCN is added to the medium which is boiled for 20 min. Ethyl acetate is added and the organic phase is washed with water, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude product is purified by chromatography over silica gel (dichloromethane/cyclohexane 1 :1 ) and further purified by preparative HPLC to give 1.6 g of a white solid (28%). ¹H NMR (CDCI₃, 300 MHz) 8.42 (m, 4H), 7.77-7.69 (m, 16H), 7.56-7.44 (m, 12H), 7.41-7.30 (m, 8H), 7.17-7.13 (m, 6H), 6.99-6.96 (m, 2H).

Device fabrication and Application Examples

Devices are fabricated by thermal evaporation under high vacuum (<10^"6 mbar). The anode consists of 120 nm of indium tin oxide (ITO) previously deposited on a glass substrate. The cathode consisted of 100 nm of aluminium. All devices were tested immediately after preparation, without encapsulation, in a nitrogen atmosphere of a glove box (<1 ppm of H₂O and O₂). All materials used were of sublimed quality.

Application Examples

The organic stack consists sequentially, from the ITO surface, of 60 nm of HTM composed of Λ/, Λ/'-bis(naphthalen-1-yl)-Λ/,Λ/'-bis(phenyl)-2,2'-dimethylbenzidine (NPD) co-evaporated in a

1 :10-rate ratio with molybdenum(VI) oxide, followed by 100 A of TAPC [1 ,1-bis[4-[Λ/,Λ/-di(p- tolyl)amino]phenyl]cyclohexane] as the electron blocking layer; The emissive layer consists of 20 nm of compound A-2, A-8, B-8, A-30, or A-6 as host doped with 10% of blue emitter

Flrpic [bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(lll)], followed by 10 nm of BAIq [bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium] as the hole blocking layer and 60 nm of ETM composed of BPhen (4,7-diphenyl-1 ,10-phenanthroline) doped with 6%

Cs.

The luminous efficiency, the power efficiency and the onset voltage (all measured at 1000 cd/m²) for the devices prepared as above are reported in the table below:

Claims

A compound of the formula

( ) ( ) wherein

the ring A,

the ring B,

the ring C,

the ring D,

R¹ R¹ , R¹¹ and R¹¹ are independently of each other a group -L¹-X¹, or

R¹⁶³ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by CrCi₈alkyl, or d-Ci₈alkoxy; d-

Ci₈alkyl, Ci-Ci₈alkyl which is interrupted by -O-; or a group -(C(=O))_X-L¹-X¹, x is 0, or 1 ;

X¹ is Ci-Ci₈alkyl, C_rCi₈alkyl which is interrupted by

, -NA¹A^1', - P(=O)A⁴A⁴ , -SiA⁶A⁷A⁸, a C6-C₂₈aryl group, which can optionally be substituted, or a C₂- C₃oheteroaryl group, especially an electron deficient heteroaryl group, which can optionally be substituted,

Ar is C₆-Ci₄aryl, such as phenyl, or naphthyl, which may optionally be substituted by one or more groups selected from Ci-C₂₅alkyl, which may optionally be interrupted by - O-, or Ci-C₂₅alkoxy,

L¹ is a single bond, or a bridging unit BU, such as

A¹ and A¹ together with the nitrogen atom to which they are bonded form a )

heteroaromatic ring, or ring system, such as , or

2;

A⁴, A⁴ , A⁶, A⁷ and A⁸ are independently of each other a C₆-C₂₄aryl group, or a C₂- C₃oheteroaryl group, which can optionally be substituted, ml can be the same or different at each occurence and is 0, 1 , 2, 3, or 4, especially 0, 1 , or 2, very especially 0 or 1 ,

R¹¹⁹ and R¹²⁰ are independently of each other CrCi₈alkyl, d-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂oh eteroary I, C₂-C₂₀heteroaryl which is substituted by G, C₂-Ci₈alkenyl, C₂- Ci₈alkynyl, Ci-Ci₈alkoxy, Ci-Ci₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or

R¹¹⁹ and R¹²⁰ together form a group of formula =CR¹²¹R¹²², wherein R¹²¹ and R¹²² are independently of each other H, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂-C₂₀h eteroary I, or C₂-C₂₀h eteroary I which is substituted by G, or R¹¹⁹ and R¹²⁰ together form a five or six membered ring, which optionally can be substituted by Ci-Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂oheteroaryl, C₂-C₂oheteroaryl which is substituted by G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, Ci-Ci₈alkoxy, Ci-Ci₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or -C(=O)-R¹²⁷, and

R¹²³ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d- Ci₈alkyl, Ci-Ci₈alkyl which is interrupted by -O-;

Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

D is -CO-, -COO-, -S-, -SO-, -SO₂-, -0-, -NR⁶⁵-, -SiR⁷⁰R⁷¹-, -POR⁷²-, -CR⁶³=CR⁶⁴-, or -

C≡C-, and E is -OR⁶⁹, -SR⁶⁹, -NR⁶⁵R⁶⁶, -COR⁶⁸, -COOR⁶⁷, -CONR⁶⁵R⁶⁶, -CN, or halogen,

G is E, or Ci-Ci₈alkyl, -SO₂R⁷³,

R⁶³ and R⁶⁴ are independently of each other C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-; or R⁶⁵ and R⁶⁶ are independently of each other C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, Ci-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -0-; or

R⁶⁵ and R⁶⁶ together form a five or six membered ring,

R⁶⁷ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d-

Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -0-, R⁶⁸ is H; C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by C_rCi₈alkyl, or Ci-Ci₈alkoxy; d-

Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -0-,

R⁶⁹ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl, Ci-Ci₈alkoxy; d-

Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -0-,

R⁷⁰ and R⁷¹ are independently of each other Ci-Ci₈alkyl, C₆-d₈aryl, or C₆-d₈aryl, which is substituted by Ci-Ci₈alkyl, and

R⁷² is Ci-Ci₈alkyl, C₆-d₈aryl, or C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl;

R⁷³ is Ci-Ci₈alkyl, or Ci-Ci₈alkyl which is interrupted by -O-; -CF₃, C₆-d₈aryl, C₆-

Ci₈aryl, which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy;

R⁴¹ can be the same or different at each occurence and is Cl, F, CN,

, NR⁴⁵R⁴⁵ , a d-C₂₅alkyl group, a C₄-Ci₈cycloalkyl group, a d-

C₂₅alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR⁴⁵-, -0-, -S-, -C(=0)-0-, or -0-C(=0)-0-, and/or wherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R⁴¹, or two or more groups R form a ring system;

R and R ->45' are independently of each other a Ci-C₂₅alkyl group, a C₄-Ci₈cycloalkyl group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR^{45 "}-, -O-, -S-, -C(=O)-O-, or, -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R⁴¹, and R⁴⁵ is a Ci-C₂₅alkyl group, or a C₄-Ci₈cycloalkyl group;

with the proviso that the ring A,

, and the ring B, , are not substituted by a hydroxy group, an ester, an ether group, or an epoxy group, and with the further

proviso that the compounds of formula

are excluded, and with the further proviso that in case Y and Y' are a group NR¹⁶³, is different from an acetyl group, and a straight, or branched chain Ci-C₇alkyl group.

The compound according to claim 1, which is a compound of formula

(IV), wherein

X, X', Y and Y' are independently of each other O, S, SO₂, NR¹⁶³, Se, or Te, R¹, R¹ , R¹¹ and R¹¹ are independently of each other a group X¹, or -L¹-X¹,

R2 _D2' _D3 _D3' _D4 _D4' _D5 _D5' _D6 _D6' _D7 _D7' _D8 _D8' _D9 _D9' _D12 _D12' _D13 _D13' _D14 , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , Γ\ , ΓΛ , ΓΛ , ΓΛ , ΓΛ ,

R¹⁴, R¹⁵ and R¹⁵ are independently of each other hydrogen, CrCi₈alkyl, a group X¹, -

(C(=O))_X-L¹-X¹, -OR¹⁶⁹, -SR¹⁶⁹, CF₃, Or-SO₂R¹⁶⁸,

R¹⁰ , R¹⁰, R¹⁶ and R¹⁶ are independently of each other hydrogen, CrCi₈alkyl, a group

L¹-X¹, -OR¹⁶⁹, -SR¹⁶⁹, Or-SO₂R¹⁶⁸,

R¹⁶³isC₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d-

Ci₈alkyl; Ci-Ci₈alkyl which is interrupted by -O-; or a group -(C(=O))_X-L¹-X¹, x is 0, or 1;

R¹⁶⁸ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d-

Ci₈alkyl; Ci-Ci₈alkyl which is interrupted by-O-, or CF₃,

R¹⁶⁹ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d-

Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-, and X¹ and L¹ are as defined in claim 1.

3. The compound of formula (I) and/or (II) according to claim 1 , wherein X, X', Y and Y' can be the same, or can be different and are O, S, SO₂, N-(C(=O))_X-BU-A¹A^1', N- (C(=O))_X-R¹⁷⁰, or N-(C(=O))_X-BU-R¹⁷⁰, x is 0, or 1 , and A¹ and A¹ are as defined in claim 1.

R¹⁷⁰ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by CrCi₈alkyl, or d-Ci₈alkoxy; d- Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-, and

, or wherein R¹¹⁹, R¹²⁰, R¹²³, ml and R⁴¹ are as defined in claim 1.

4. The compound of the formula (I), (II), (III) or (IV) according to claim 2, wherein -

(C(=O))_X-L¹-X¹ is a group of formula -P(=O)A⁴A^4', -C(=0)A⁵, -SiA⁶A⁷A⁸, -NA¹A^1', -BU-

P(=0)A⁴A⁴ , -BU-S ;iAΛ 6^bAΛ 7'AΛ 8^b

, or , wherein

A⁵, A¹, A¹ , A³ and A³ are independently of each other a C₆-C₂₄aryl group, or a C₂- C₃oheteroaryl group, which can optionally be substituted, especially phenyl, naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl, which can optionally be

substituted, such as

and

, or A¹ and A¹ , or A³ and A³ together with the nitrogen atom to which they are bonded form a heteroaromatic ring, or ring system, such as

2; ml can be the same or different at each occurence and is 0, 1 , 2, 3, or 4, especially 0, 1 , or 2, very especially 0 or 1 ;

R⁶⁵ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by CrCi₈alkyl, d-Ci₈alkoxy; d- Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-;

A⁴, A⁴ , A⁶, A⁷ and A⁸ are independently of each other a group

^κ ;

Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-

C₂₄aryl which is substituted by G, C₂-C₂oheteroaryl, C₂-C₂oheteroaryl which is substituted by G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, Ci-Ci₈alkoxy, Ci-Ci₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, -C(=O)-R¹²⁷, -C(=O)OR¹²⁷, or -

C(=O)NR¹²⁷R¹²⁶, or substituents R¹¹⁶, R¹¹⁷ and R¹¹⁷ , which are adjacent to each other, can form a ring,

R¹²⁴ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d-

Ci₈alkyl, Ci-Ci₈alkyl which is interrupted by -O-; R¹²⁶ and R¹²⁷ are independently of each other H; C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or d-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

or wherein R¹¹⁹, R¹²⁰, R¹²³, D, E, G and

R ₃41 are as defined in claim 1 and ml is as defined above.

The compound of the formula (I), (II), (III) or (IV) according to claim 2, wherein L¹-X¹ is a group

, or , wherein

R¹ , R¹¹' and R¹¹' are as defined in claim 4 and R^{η ηb} has the meaning of R¹ .

6. The compound of the formula (I), (II), (III) or (IV) according to claim 2, wherein L -X is a group

R

, wherein R , R and R are as defined in claim 4. The compound of the formula (I), (II), (III) or (IV) according to claim 2, wherein L 1-X v1 is a group

wherein R^{η ηb}, R¹¹', R^{η ηa}, R^1ZO, and R^η^ are as defined in claim

4.

The compound according to any of claims 1 to 6, which is a compound of formula

O, S, SO₂, N-(C(=O))_x-BU-A ^ 1^ηAΛ 1^η' , M N- /(rC~~/(—=nOι\)\)_X- DR1^η7'0^u, o _ _r M N- /(rC-z(—=nOiw))_x- DBMU- DR1^η70 x is 0, or 1 , is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by CrCi₈alkyl, or d-Ci₈alkoxy; C_r Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

wherein R²¹⁶ and R²¹⁷ are independently of each other H, Ci-Ci₈alkyl, or Ci-Ci₈alkyl which is interrupted by O, R¹⁰ , R¹⁰ , R¹⁶ and R¹⁶ are independently of each other hydrogen, Ci-Ci₈alkyl, a group L¹-X¹, wherein L¹-X¹ is as defined in claim 1 ;

R³, R^3', R⁴, R^4', R⁷ and R^7' are independently of each other a group -(C(=O))_X-L¹-X¹, wherein -(C(=O))_X-L¹-X¹ is a group of formula -C(=0)A⁵, -P(=O)A⁴A^4', -SiA⁶A⁷A⁸, -

, or wherein

A¹, A^1', A³ and A³ are independently of each other

or A¹ and A^1', or A³ and A^3' together with the nitrogen atom to which they are bonded form a heteroaromatic ring, or ring system,

, A⁴ , A⁶, A⁷ and A⁸ are independently of each other a group

R¹¹⁶, R^116', R¹¹⁷ and R^117' are independently of each other H, CrCi₈alkyl, C_rCi₈alkyl which is interrupted by O,

R¹²³ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or d-Ci₈alkoxy; d-

Ci₈alkyl, Ci-Ci₈alkyl which is interrupted by -O-; ml can be the same or different at each occurence and is 0, or 1 , and

R⁴¹ is Ci-Ci₈alkyl, Ci-Ci₈alkyl which is interrupted by O, or phenyl, which is optionally

substituted by

The compound of the formula (II) according to any of claims 1 to 7, which is a

compound of formula

wherein

Y is O, SO₂, NR¹⁶³, or S, wherein R¹⁶³ is C_rC₄alkyl, C(=O)-R¹⁷⁰, or (C(=O)-BU-R¹⁷⁰, R¹⁷⁰ is C₆-Ci₈aryl; C₆-Ci₈aryl, which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d- Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

BU is

, or , wherein ml is 0,1 , or 2, and R⁴¹ is a Ci-C₂5alkyl group, or a Ci-C₂5alkoxy group,

R and R are independently of each other H,

, or a group L -X , R and R are independently of each other H, or a group L -X , wherein L 1 -X v1 , r R-)216 and R ->217 are as defined in claim 8 and R and R are as defined in claim 1

10. The compound according to claim 8, or 9:

1 1. An electronic device, comprising a compound according to any of claims 1 to 10.

12. The electronic device according to claim 1 1 , which is an electroluminescent device comprising a cathode, an anode, and therebetween a light emitting layer containing a host material and a phosphorescent light-emitting material, wherein the host material is a compound according to any of claims 1 to 9.

13. Use of the compounds according to any of claims 1 to 1 1 for electrophotographic photoreceptors, photoelectric converters, solar cells, image sensors, dye lasers and electroluminescent devices.

14. A compound of formula

), wherein X, X', Y, Y', R¹, R^1>, R¹¹, R^11>, R², R^2', R³, R^3', R⁴, R^4', R⁵, R^5', R⁶, R^6', R⁷, R^7', R⁸, R^8', R⁹, R^9', R¹², R^12', R¹³, R^13', R¹⁴, R^14', R¹⁵, R^15', R¹⁰, R^10', R¹⁶ and R^16' are as defined in claim 2, and wherein at least one of the substituents R², R^2', R³, R^3', R⁴, R^4', R⁵, R^5', R⁶, R^6', R⁷, R^7', R⁸, R^8', R⁹, R^9', R¹², R^12', R¹³, R^13', R¹⁴, R^14', R¹⁵, and R^15' is a group of formula 0-SO₂-CF₃.

A process for the preparation of compounds of the formula Va, Vb, Via, Vila, or Villa

and/or

X, X', Y, Y', R¹, R^1', R¹⁰, R^10', R¹⁶ and R^16' are as defined in claim 1 , and R³, R^3', R⁴, R^4', R¹³, R^{14 '}, R⁷ and R⁷ are a group of formula -0-SO₂-CF₃ by reacting compounds of the formula Va, Via, and Vila, wherein R³, R^3', R⁴, R^4', R¹³, R^14', R⁷ and R^7' are OH, with a

group of formula