Aromatic compounds for organic electroluminescent devices
The invention relates to compounds which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing said compounds.
1 . A compound including at least one structure of the formula (Ia) and/or (Ib):
where the symbols and indices used are as follows:
Z 1 , Z 2 is the same or different at each instance and is N, P, B, Al, P(═O), P(═S), or Ga;
Y 1 , Y 2 , Y 3 is the same or different at each instance and is a bond, N(Ar), N(R), P(Ar), P(R), P(═O)Ar, P(═O)R, P(═S)Ar, P(═S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C═O, C(R) 2 , Si(R) 2 , C═NR, C═NAr, C═C(R) 2 , O, S, Se, S═O, or SO 2 ;
p 2 , p 3 are the same or different and are 0 or 1;
X is N, CR, or C if a Y 1 , Y 2 or Y 3 group binds thereto, with the proviso that not more than two of the X groups in one cycle are N;
R is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R 1 ) 2 , C(═O)N(Ar) 2 , C(═O)N(R 1 ) 2 , C(Ar) 3 , C(R 1 ) 3 , Si(Ar) 3 , Si(R 1 ) 3 , B(Ar) 2 , B(R 1 ) 2 , C(═O)Ar, C(═O)R 1 , P(═O)(Ar) 2 , P(═O)(R 1 ) 2 , P(Ar) 2 , P(R 1 ) 2 , S(═O)Ar, S(═O)R 1 , S(═O) 2 Ar, S(═O) 2 R 1 , OSO 2 Ar, OSO 2 R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R 1 radicals, where one or more non-adjacent CH 2 groups may be replaced by R 1 C═CR 1 , C≡C, Si(R 1 ) 2 , C═O, C═S, C═Se, C═NR 1 , —C(═O)O—, —C(═O)NR 1 —, NR 1 , P(═O)(R 1 ), —O—, —S—, SO or SO 2 , or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R 1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R 1 radicals; at the same time, two R radicals may also together form a ring system;
Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R 1 radicals; at the same time, it is possible for two Ar radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R 1 ), C(R 1 ) 2 , Si(R 1 ) 2 , C═O, C═NR 1 , C═C(R 1 ) 2 , O, S, S═O, SO 2 , N(R 1 ), P(R 1 ) and P(═O)R 1 ;
R 1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO 2 , N(Ar′) 2 , N(R 2 ) 2 , C(═O)Ar′, C(═O)R 2 , P(═O)(Ar′) 2 , P(Ar′) 2 , B(Ar′) 2 , B(R 2 ) 2 , C(Ar′) 3 , C(R 2 ) 3 , Si(Ar′) 3 , Si(R 2 ) 3 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 radicals, where one or more non-adjacent CH 2 groups may be replaced by —R 2 C═CR 2 —, —C≡C—, Si(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , —C(═O)O—, —C(═O)NR 2 —, NR 2 , P(═O)(R 2 ), —O—, —S—, SO or SO 2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R 2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R 2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R 2 radicals, or a combination of these systems; at the same time, two or more, preferably adjacent R 1 radicals together may form a ring system; at the same time, one or more R 1 radicals may form a ring system with a further part of the compound;
Ar′ is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R 2 radicals; at the same time, it is possible for two Ar′ radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R 2 ), C(R 2 ) 2 , Si(R 2 ) 2 , C═O, C═NR 2 , C═C(R 2 ) 2 , O, S, S═O, SO 2 , N(R 2 ), P(R 2 ) and P(═O)R 2 ;
R 2 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; or two or more substituents R 2 together may form a ring system; and
wherein at least two R radicals form a fused ring together with the further groups to which the two R radicals bind, where the two R radicals form at least one structure of the formulae (RA-1) to (RA-12);
where R 1 has the definition set out above, the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R radicals bind, and the further symbols have the following definition,
Y 4 is the same or different at each instance and is C(R 1 ) 2 , (R 1 ) 2 C—C(R 1 ) 2 , (R 1 )C═C(R 1 ), NR 1 , NAr, O or S;
R a is the same or different at each instance and is F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more R 2 radicals, where one or more non-adjacent CH 2 groups may be replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , —O(═O)O—, —C(═O)NR 2 —, NR 2 , P(═O)(R 1 ), —O—, —S—, SO or SO 2 , or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R 2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R 2 radicals; or two R a radicals together may form a ring system;
s is 0, 1, 2, 3, 4, 5 or 6;
t is 0, 1, 2, 3, 4, 5, 6, 7 or 8;
v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.
2 . A compound as claimed in claim 1 , comprising at least one structure of the formulae (IIa), (IIb), (IIc) and (IId):
where p 2 , p 3 , Y 1 , Y 2 , Y 3 , X, Z 1 , Z 2 and R have the definitions given in claim 1 , the index n is 0, 1, 2 or 3, the index j is 0, 1 or 2, and the index k is 0 or 1, where the sum total of the indices k, j and n is 0, 1, 2, 3, 4, 5 or 6.
3 . A compound as claimed in claim 1 , selected from the compounds of the formulae (IIIa), (IIIb), (IIIc) and (IIId):
where Y 1 , Y2, Y 3 , X, Z 1 , Z 2 and R have the definitions given in claim 1 , the index l is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, and the index n is 0, 1, 2 or 3, where the sum total of the indices l, m and n is 2, 3, 4, 5, 6, 7 or 8, preference being given to structures of the formulae (IIIa) and (IIIb).
4 . A compound as claimed in claim 1 , wherein, if Z 1 is N and Y 1 is N(Ar), compounds are excluded in which the Ar group of the N(Ar) radical represented by Y 1 , together with four R radicals derived from X groups of the ring systems to which the Y 1 radical binds, forms an aromatic ring system where any two of the four X groups are adjacent.
5 . A compound as claimed in claim 1 , wherein Z 1 is selected from N and P and the Y 1 group is P(═O)Ar, P(═O)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C═O, S═O or SO 2 , or
that Z 1 is selected from N and P and the Z 2 group is B, Al, P(═O), P(═S) or Ga, or
that Z 2 is selected from N and P and at least one of the Y 2 , Y 3 groups is P(═O)Ar, P(═O)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C═O, S═O or SO 2 .
6 . A compound as claimed in claim 1 , wherein Z 1 is selected from B, Al, P(═O), P(═S) and Ga and the Y 1 group is N(Ar), N(R), P(Ar), P(R), O, S or Se, or
that Z 1 is selected from B, Al, P(═O), P(═S) and Ga, and the Z 2 , Y 3 group is N or P, or
that Z 2 is selected from B, Al, P(═O), P(═S) and Ga, and at least one of the Y 2 , Y 3 groups is N(Ar), N(R), P(Ar), P(R), O, S or Se.
7 . A compound as claimed in claim 1 , that Z 1 and/or Z 2 is/are B.
8 . A compound as claimed in claim 1 , that Z 1 and/or Z 2 is/are N.
9 . A compound as claimed in claim 1 , that at least two R radicals form a fused ring together with the further groups to which the two R radicals bind, where the two R radicals form of the structures of the formulae (RA-1a) to (RA-4f):
where the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbols R1, R2, Ra and the indices s and t have the definition set out above, especially in claim 1 .
10 . A compound as claimed in claim 1 , that at least two R radicals form a fused ring together with the further groups to which the two R radicals bind, where the two R radicals form of the structures of the formula (RB):
where R 1 has the definition set out in claim 1 , the index m is 0, 1, 2, 3 or 4, and Y 5 is C(R 1 ) 2 , NR 1 , NAr, BR 1 , BAr, O or S.
11 . A compound as claimed in claim 1 , comprising at least one structure of the formulae (IVa) to (IVr), where the compounds have at least one fused ring:
where Y 1 , Y 2 , Y 3 , X, Z 1 , Z 2 and R have the definitions given in claim 1 , the symbol o represents the sites of attachment, the index l is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, the index n is 0, 1, 2 or 3, the index j is 0, 1 or 2, and the index k is 0 or 1, where the sum total of the indices k, j, l, m and n is 0, 1, 2, 3, 4, 5 or 6.
12 . A compound as claimed in claim 1 , wherein the compounds have at least two fused rings, wherein at least one fused ring is formed by structures of the formulae (RA-1) to (RA-12) and a further ring is formed by structures of the formulae (RA-1) to (RA-12) or (RB), comprising at least one structure of the formulae (Va) to (Vs):
where Y 1 , Y 2 , Y 3 , X, Z 1 , Z 2 and R have the definitions given in claim 1 , the symbol o represents the sites of attachment of at least one structure of the formulae (RA-1) to (RA-12) or a structure of the formula (RB), the index l is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, the index n is 0, 1, 2 or 3, the index j is 0, 1 or 2, and the index k is 0 or 1, where the sum total of the indices k, j, l, m and n is 0, 1, 2, 3 or 4.
13 . An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1 , wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.
14 . A formulation comprising at least one compound as claimed in claim 1 and at least one further compound, where the further compound is preferably selected from one or more solvents.
15 . A composition comprising at least one compound as claimed in claim 1 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.
16 . A process for preparing a compound as claimed in claim 1 , wherein a base skeleton having a Z 1 group or a precursor of the Z 1 group is synthesized, and then a ring closure reaction is conducted by means of a nucleophilic aromatic substitution reaction or a coupling reaction.
17 . A method comprising incorporating the compound as claimed in claim 1 in an electronic device.
18 . An electronic device comprising at least one compound as claimed in claim 1 , wherein the electronic device is an electroluminescent device.