Materials for organic electroluminescent devices
The present invention relates to a process to produce compounds of the formula (1) which are suitable for use in electronic devices, as well as to intermediate compounds of formula (Int-1) and compounds of formula (1-1) and (1-2) obtained via the process. These compounds are particularly suitable for use organic electroluminescent devices. The present invention also relate to electronic devices, which comprise these compounds.
1. A compound of formula (Int-1),
where the following applies to the symbols used:
V is CR or N, with the proviso that there are maximum three N per 6-membered-ring, or two adjacent groups V (V—V or V═V) stand for a group of the formula (V-1) or (V-2),
in which the dashed bonds indicate the linking to the spirobifluorene skeleton;
E is a divalent bridge selected from N(R 0 ), B(R 0 ), O, C(R 0 ) 2 , Si(R 0 ) 2 , C═NR 0 , C═C(R 0 ) 2 , S, S═O, SO 2 , P(R 0 ) and P(═O)R 0 ;
X 2 is Cl, Br, I, trifluoromethanesulfonate (CF 3 SO 3 —), tosylate (CH 3 C 6 H 4 SO 3 —) or mesylate (CH 3 SO 3 —);
Ar L is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 1 ;
R 0 , R, R 2 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, CHO, CN, C(═O)Ar 3 , P(═O)(Ar 3 ) 2 , S(═O)Ar 3 , S(═O) 2 Ar 3 , N(Ar 3 ) 2 , Si(R 3 ) 3 , B(OR 3 ) 2 , OSO 2 R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 3 , where one or more non-adjacent CH 2 groups may be replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , Ge(R 3 ) 2 , Sn(R 3 ) 2 , C═O, C═S, C═Se, P(═O)(R 3 ), SO, SO 2 , O, S or CONR 3 and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 3 , and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 3 , where two adjacent substituents R 0 , two adjacent substituents R or two adjacent substituents R 2 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 3 ;
R 1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CHO, CN, C(═O)Ar 3 , P(═O)(Ar 3 ) 2 , S(═O)Ar 3 , S(═O)Ar 3 , Si(R 3 ) 3 , B(OR 3 ) 2 , OSO 2 R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 3 , where one or more non-adjacent CH 2 groups may be replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , Ge(R 3 ) 2 , Sn(R 3 ) 2 , C═O, C═S, C═Se, P(═O)(R 3 ), SO, SO 2 , O, S or CONR 3 and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 3 , and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 3 , where two adjacent substituents R 1 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 3 ;
R 3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CHO, CN, C(═O)Ar 3 , P(═O)(Ar 3 ) 2 , S(═O)Ar 3 , S(═O)Ar 3 , Si(R 4 ) 3 , B(OR 4 ) 2 , OSO 2 R 4 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 4 , where one or more non-adjacent CH 2 groups may be replaced by R 4 C═CR 4 , C≡C, Si(R 4 ) 2 , Ge(R 4 ) 2 , Sn(R 4 ) 2 , C═O, C═S, C═Se, P(═O)(R 4 ), SO, SO2, O, S or CONR4 and where one or more H atoms may be replaced by D, F, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R4, and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R4, where two adjacent substituents R3 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 4 ;
R 4 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where one or more non-adjacent CH 2 groups may be replaced by SO, SO 2 , O, S and where one or more H atoms may be replaced by D or F, and aromatic or heteroaromatic ring system having 5 to 24 C atoms;
Ar 3 is selected, identically or differently on each occurrence, from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R 4 ;
n is 1, 2, or 3;
X 2 is Cl, Br, I, trifluoromethanesulfonate (CF 3 SO 3 —), tosylate (CH 3 C 6 H 4 SO 3 —) or mesylate (CH 3 SO 3 —);
X 3 is Cl, Br, I or —B(OR B ) 2 ; with the proviso that one of the group X 1 or X 3 must stand for —B(OR B ) 2 but not both groups stand for —B(OR B ) 2 at the same time.
2. The compound according to claim 1 , characterized in that X 2 is Br, Cl or I.
3. The compound according to claim 1 , selected from formulae (Int-2) to (Int-9),
where the symbols have the same meaning as defined in claim 1 .
4. The compound according to claim 1 , selected from the compounds of formulae (Int-2-1) to (Int-2-8),
where the symbols have the same meaning as in claim 1 .
5. The compound according to claim 1 , selected from the compounds of formulae (Int-2-1-1) to (Int-2-8-1),
where X 2 has the same meaning as in claim 1 .
6. A compound of formula (1-1) or (1-2),
where the symbols V, R 1 have the same meaning as in claim 1 ,
Ar 1 , Ar 2 are, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 ; Ar 1 and Ar 2 here may be connected via a single bond or a divalent bridge selected from —N(R 2 )—, —O—, —S—, —C(R 2 ) 2 —, —C(R 2 ) 2 —C(R 2 ) 2 —, —Si(R 2 ) 2 — and —B(R 2 )—; and
where m is 0, 1, 2, 3 or 4.
7. The compound according to claim 6 , selected from the compounds of formulae (1-1-1) and (1-2-1),
8. The compound according to claim 6 , selected from the compounds of formula (1-1-1a) and (1-2-1a),
9. The compound according to claim 6 , wherein Ar 1 and Ar 2 are selected, identically or differently on each occurrence from the groups of the following formulae (A-1) to (A-48),
where the dashed bonds indicate the bonds to the nitrogen atom,
where the groups of formulae (A-1) to (A-48) may further be substituted at each free position by a group R 2 as defined in claim 1 ,
where the group R 0 , in formulae (A-31) to (A-34), (A-41), (A-42) and (A-44), is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, Si(R 3 ) 3 , a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which may be substituted by one or more radicals R 3 , an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which may be substituted by one or more radicals R 3 , where two adjacent substituents R 0 may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 3 .
10. Electronic device comprising at least one compound according to claim 6 , selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.
11. Electronic device according to claim 10 , which is an organic electroluminescent device, characterised in that the at least one compound is employed as hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer or as matrix material for fluorescent or phosphorescent emitters.
12. A formulation comprising at least one compound according to claim 6 and at least one solvent.
13. A mixture comprising at least one compound according to claim 6 and at least one further compound.