Heterocyclic spiro compounds

1. A compound of formula (I):

wherein

X is O, S, or C(R 1 ) 2 ;

Ar is on each occurrence, identically or differently, an aryl group having 6 to 40 C atoms or a heteroaryl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 1 ;

R 1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, C(═O)Ar 1 , P(═O)(Ar 1 ) 2 , S(═O)Ar 1 , S(═O) 2 Ar 1 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , and wherein one or more non-adjacent CH 2 groups are optionally replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, P(═O)(R 2 ), SO, SO 2 , O, S, or CONR 2 , and wherein one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN, or NO 2 , an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems; and wherein two or more adjacent substituents R 1 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another;

R 2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, C(═O)Ar 1 , P(═O)(Ar 1 ) 2 , S(═O)Ar 1 , S(═O) 2 Ar 1 , CN, NO 2 , Si(R 3 ) 3 , B(OR 3 ) 2 , OSO 2 R 3 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 3 , wherein one or more non-adjacent CH 2 groups are optionally replaced by 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 wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO 2 , or a combination of these systems; and wherein two or more adjacent substituents R 2 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another;

Ar 1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 ; wherein two radicals Ar 1 bonded to the same phosphorus atom are also optionally linked to one another by a single bond or a bridge selected from the group consisting of B(R 3 ), C(R 3 ) 2 , Si(R 3 ) 2 , C═O, C═NR 3 , C═C(R 3 ) 2 , O, S, S═O, SO 2 , N(R 3 ), P(R 3 ), and P(═O)R 3 ;

R 3 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein one or more H atoms of the hydrocarbon radical are optionally replaced by F; and wherein two or more adjacent substituents R 3 optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another;

n is on each occurrence, identically or differently, 0, 1, 2, 3, or 4;

m is on each occurrence, identically or differently, 0, 1, 2, or 3;

o is on each occurrence, identically or differently, 0, 1, or 2;

p, q, r, and u

are on each occurrence, identically or differently, 0 or 1;

s and t

are, on each occurrence, 0;

E is an electron-transporting group, which is optionally substituted by one or more radicals R 1 ;

R a is, independently, H, D, or F;

R b is, independently, H, D, or F;

with the proviso that

the compound of formula (I) contains only one electron-transporting group E;

the sum of all indices m, s and, t is less than 7;

the sum of all indices n, q and, u is less than 9; and

the sum of the indices r and o is less than 3.

2. The compound of claim 1 , wherein p is 0, so that E is bonded directly to the benzofuran or spiro group.

3. The compound of claim 1 , wherein at least one radical containing the electron-transporting group E is bonded in position 1, 3, 4, 5, 6, or 8 of the spirobifluorene skeleton.

4. The compound of claim 1 , wherein the electron-transporting group E is a heteroaryl group having 5 to 60 aromatic ring atoms.

5. The compound of claim 4 , wherein the electron-transporting group E comprises at least one structure selected from the group consisting of triazines, pyrimidines, pyrazines, imidazoles, benzimidazoles, and pyridines.

6. The compound of claim 4 , wherein the electron-transporting group E comprises at least one structure selected from the group consisting of formulae (E-1) through (E-10):

wherein

the dashed bond marks the bonding position,

Q′ is on each occurrence, identically or differently, CR 1 or N, and

Q″ is NR 1 , O, or S, and

wherein at least one Q′ is N and/or at least one Q″ is NR 1 .

7. The compound of claim 4 , wherein the electron-transporting group E comprises at least one structure selected from the group consisting of formulae (E-11) through (E-19):

wherein the dashed bond marks the bonding position.

8. The compound of claim 6 , wherein at least one of the radicals R 1 in the structures of formulae (E-1) through (E-10) is Ar.

9. The compound of claim 7 , wherein at least one of the radicals R 1 in the structures of formulae (E-11) through (E-19) is Ar.

10. The compound of claim 1 , wherein the compound comprises a compound of formulae (II), (Ill), (IV), (V), (VI), and/or (VII):

11. An oligomer, polymer, or dendrimer comprising one or more compounds of claim 1 , wherein one or more bonds are present from the compound to the oligomer, polymer, or dendrimer.

12. A composition comprising at least one compound of claim 1 and at least one organofunctional material.

13. A composition comprising at least one oligomer, polymer, or dendrimer of claim 11 and at least one organofunctional material.

14. A formulation comprising at least one compound of claim 1 and at least one solvent.

15. A formulation comprising an oligomer, polymer, or dendrimer of claim 11 and at least one solvent.

16. A formulation comprising at least one composition of claim 12 and at least one solvent.

17. A formulation comprising at least one composition of claim 13 and at least one solvent.

18. A process for preparing a compound of claim 1 , comprising preparing the spirobifluorene skeleton, followed by introducing a radical containing an electron-transporting group via a coupling reaction.

19. A process for preparing an oligomer, polymer, or dendrimer of claim 11 , comprising preparing the spirobifluorene skeleton, followed by introducing a radical containing an electron-transporting group via a coupling reaction.

20. An electronic device comprising at least one compound of claim 1 .

21. The electronic device of claim 20 , wherein the electronic device is 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, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells and organic laser diodes.