Compounds and polymers which contain substituted indenofluorene derivatives as structural unit, process for the preparation thereof, and the use thereof as electronic devices and mixtures and solutions
The present invention relates to polymers which contain substituted indenofluorene derivatives as structural unit, to substituted indenofluorene derivatives, to a process for the preparation of the polymers according to the invention, to mixtures and solutions which comprise the polymers according to the invention, and to the use of the polymers according to the invention in electronic devices, in particular in organic electroluminescent devices, so-called OLEDs (OLED=organic light emitting diode).
1. A polymer for use as a matrix material in electroluminescent device which consists essentially of a structural unit of the formula (I):
where the symbols and indices used have the following meanings:
the dashed lines represent, independently of one another, a bond to a further structural unit of the polymer;
L 1 and L 2 represent, independently of one another, or a unit selected from the group consisting of a C 1-10 -alkylene group, C 2-10 -alkenylene group, C 2-10 -alkynylene group and Si 1-10 -silylene group, where one or more CH 2 units is optionally replaced by NR, O or S and one or more SiH 2 units is optionally replaced by O;
W represents a tetravalent unit selected from the group consisting of C, Si, Ge and a structural element of the following formulae (II) and (III):
where
D is, identically or differently on each occurrence, a unit selected from the group consisting of CR 2 , O, S and NR,
E and J are each, independently of one another, units selected from the group consisting of CR and N,
n is 1, 2 or 3, and
m is 0, 1 or 2; where
R is a radical selected from the group consisting of H, F and C 1-6 -alkyl;
with the proviso that only one representative from E, D and J is different from CR or CR 2 ;
where, in the case where the tetravalent unit W is a unit of the formula (II) or (III), C 1 and C 3 are bonded to different atoms of the unit W;
U, V and V′ represent, independently of one another, a single covalent bond or a divalent unit selected from the group consisting of CR 1 R 2 , C═O, NR 1 , O, SiR 1 R 2 , P═O, S and GeR 1 R 2 ;
where
R 1 and R 2 are selected, independently of one another, from the group consisting of H, F, a C 1-40 -alkyl group, a C 2-40 -alkenyl group, a C 2-40 -alkynyl group, an optionally substituted C 6-40 -aryl group and an optionally substituted 5- to 25-membered heteroaryl group;
C 1 to C 8 each represent a C atom;
Ar 1 and Ar 2 each represent, independently of one another, a 5- to 25-membered, optionally substituted aromatic or heteroaromatic ring system;
Ar 3 , Ar 4 and Ar 5 represent, independently of one another, an optionally substituted C 6-40 -aryl group or an optionally substituted 5- to 25-membered heteroaryl group, where C atoms C 1 and C 2 are part of Ar 3 , C atoms C 3 to C 6 are part of Ar 4 and C atoms C 7 and C 8 are part of Ar 5 .
2. The polymer according to claim 1 , wherein U, V and V′ represent, independently of one another, a single covalent bond or CR 1 R 2 .
3. A process for the preparation of the polymer according to claim 1 , which comprises preparing the polymer by SUZUKI, YAMAMOTO, STILLE or HARTWIG-BUCHWALD polymerization.
4. A mixture comprising the polymer according to claim 1 with a low-molecular-weight substance which is a triplet emitter.
5. A solution comprising the mixture according to claim 4 in one or more solvents.
6. A solution comprising the polymer according to claim 1 in one or more solvents.
7. A polymer for use as a matrix material in electroluminescent device which consists essentially of a structural unit of the formula (I):
where the symbols and indices used have the following meanings:
the dashed lines represent, independently of one another, a bond to a further structural unit of the polymer;
L 1 and L 2 represent, independently of one another, a single covalent bond or a unit selected from the group consisting of a C 1-10 -alkylene group, C 2-10 -alkenylene group, C 2-10 -alkynylene group and Si 1-10 -silylene group, where one or more CH 2 units is optionally replaced by NR, O or S and one or more SiH 2 units is optionally replaced by O;
W represents a tetravalent unit selected from the group consisting of C, Si, Ge— and a structural element of the following formulae (II) and (III):
where
D is, identically or differently on each occurrence, a unit selected from the group consisting of CR 2 , O, S and NR,
E and J are each, independently of one another, units selected from the group consisting of CR and N,
n is 1, 2 or 3, and
m is 0, 1 or 2; where
R is a radical selected from the group consisting of H, F and C 1-6 -alkyl;
with the proviso that only one representative from E, D and J is different from CR or CR 2 ;
where, in the case where the tetravalent unit W is a unit of the formula (II) or (III), C 1 and C 3 are bonded to different atoms of the unit W;
U, V and V′ represent, independently of one another, a divalent unit selected from the group consisting of CR 1 R 2 , C═O, NR 1 , O, SiR 1 R 2 , P═O, S and GeR 1 R 2 ;
where
R 1 and R 2 are selected, independently of one another, from the group consisting of H, F, a C 1-40 -alkyl group, a C 2-40 -alkenyl group, a C 2-40 -alkynyl group, an optionally substituted C 6-40 -aryl group and an optionally substituted 5- to 25-membered heteroaryl group;
C 1 to C 8 each represent a C atom;
Ar 1 and Ar 2 each represent, independently of one another, a 5- to 25-membered, optionally substituted aromatic or heteroaromatic ring system;
Ar 3 , Ar 4 and Ar 5 represent, independently of one another, an optionally substituted C 6-40 -aryl group or an optionally substituted 5- to 25-membered heteroaryl group, where C atoms C 1 and C 2 are part of Ar 3 , C atoms C 3 to C 6 are part of Ar 4 and C atoms C 7 and C 8 are part of Ar 5 .
8. A process for the preparation of the polymer according to claim 7 , which comprises preparing the polymer by SUZUKI, YAMAMOTO, STILLE or HARTWIG-BUCHWALD polymerization.
9. A mixture comprising the polymer according to claim 7 with a low-molecular-weight substance which is a triplet emitter.
10. A solution comprising the mixture according to claim 9 in one or more solvents.
11. A solution comprising the polymer according to claim 7 in one or more solvents.
12. The polymer according to claim 7 , wherein U, V and V′ represent, independently of one another, a single covalent bond or CR 1 R 2 .
13. An electronic device having at least one emitting layer which comprises
a polymer which consists essentially of a structural unit of the formula (I):
where the symbols and indices used have the following meanings:
the dashed lines represent, independently of one another, a bond to a further structural unit of the polymer;
L 1 and L 2 represent a single covalent bond
W represents a tetravalent unit selected from the group consisting of C,
U, V and V′ represent, independently of one another, a single covalent bond or a divalent unit selected from the group consisting of CR 1 R 2 , C═O, NR 1 , O, SiR 1 R 2 , P═O, S and GeR 1 R 2 ;
where
R 1 and R 2 are selected, independently of one another, from the group consisting of H, F, a C 1-40 -alkyl group, a C 2-40 -alkenyl group, a C 2-40 -alkynyl group, an optionally substituted C 6-40 -aryl group and an optionally substituted 5- to 25-membered heteroaryl group;
C 1 to C 8 each represent a C atom;
Ar 1 and Ar 2 each represent, independently of one another, a 5- to 25-membered, optionally substituted aromatic or heteroaromatic ring system;
Ar 3 , Ar 4 and Ar 5 represent, independently of one another, an optionally substituted C 6-40 -aryl group or an optionally substituted 5- to 25-membered heteroaryl group, where C atoms C 1 and C 2 are part of Ar 3 , C atoms C 3 to C 6 are part of Ar 4 and C atoms C 7 and C 8 are part of Ar 5 ,
as a host material for green triplet materials and one triplet emitter.
14. The electronic device as claimed in claim 13 , wherein one representative from U and V represents a single covalent bond and the other represents the unit CR 1 R 2 .
15. The electronic device as claimed in claim 13 , wherein the structural unit is a structural unit of the formulae (Va) and/or (Vb):
wherein the dashed lines represent, independently of one another, a bond to a further structural unit of the polymer;
X and Y have the same meanings as R 1 and R 2 .
16. The electronic device as claimed in claim 13 , wherein the polymer is a partially conjugated polymer, where the conjugation is interrupted by the structural unit of the formula (I).
17. The electronic device as claimed in claim 13 , wherein, besides the structural unit of the formula (I), the polymer also contains at least one further structural unit.
18. An organic electroluminescent device having at least one emitting layer which comprises
a polymer which consists essentially of a structural unit of the formula (I):
where the symbols and indices used have the following meanings:
the dashed lines represent, independently of one another, a bond to a further structural unit of the polymer;
L 1 and L 2 represent a single covalent bond
W represents a tetravalent unit selected from the group consisting of C,
U, V and V′ represent, independently of one another, a single covalent bond or a divalent unit selected from the group consisting of CR 1 R 2 , C═O, NR 1 , O, SiR 1 R 2 , P═O, S and GeR 1 R 2 ;
where
R 1 and R 2 are selected, independently of one another, from the group consisting of H, F, a C 1-40 -alkyl group, a C 2-40 -alkenyl group, a C 2-40 -alkynyl group, an optionally substituted C 6-40 -aryl group and an optionally substituted 5- to 25-membered heteroaryl group;
C 1 to C 8 each represent a C atom;
Ar 1 and Ar 2 each represent, independently of one another, a 5- to 25-membered, optionally substituted aromatic or heteroaromatic ring system;
Ar 3 , Ar 4 and Ar 5 represent, independently of one another, an optionally substituted C 6-40 -aryl group or an optionally substituted 5- to 25-membered heteroaryl group, where C atoms C 1 and C 2 are part of Ar 3 , C atoms C 3 to C 6 are part of Ar 4 and C atoms C 7 and C 8 are part of Ar 5 ,
as a host material for green triplet materials and one triplet emitter.
19. The organic electronic device according to claim 18 , wherein the device is an organic or polymeric organic electroluminescent device (OLED, PLED), an organic integrated circuit (O-IC), an organic field-effect transistor (OFET), an organic thin-film transistor (OTFT), an organic solar cell (O-SC), an organic laser diode (O-laser), an organic photovoltaic (OPV) element or device or an organic photoreceptor (OPC).
20. The organic electronic device according to claim 19 , wherein the device is a polymeric organic electroluminescent device (PLED).
21. The organic electroluminescent device according to claim 18 , wherein one representative from U and V represents a single covalent bond and the other represents the unit CR 1 R 2 .
22. The organic electroluminescent device according to claim 18 , wherein the structural unit is a structural unit of the formulae (Va) and/or (Vb):
wherein the dashed lines represent, independently of one another, a bond to a further structural unit of the polymer;
X and Y have the same meanings as R 1 and R 2 .
23. The organic electroluminescent device according to claim 18 , wherein the polymer is a partially conjugated polymer, where the conjugation is interrupted by the structural unit of the formula (I).
24. The organic electroluminescent device according to claim 18 , besides the structural unit of the formula (I), the polymer also contains at least one further structural unit.