Organic semiconductors

1. A compound comprising one or more divalent heteroarylene units of formula I

wherein X 1 , X 2 are independently of each other and on each occurrence identically or differently selected from O or S,

Y is independently of each other and on each occurrence identically or differently selected from O, S or CU 1 U 2 ,

U 1 , U 2 are an electron withdrawing group selected from CN, C(═O)R or C(═O)OR, or U 1 and U 2 together form a carbocyclic, heterocyclic, aromatic or heteroaromatic ring having 4, 6-11, 13-15 ring atoms that is optionally substituted by one or more groups L,

R 1 is independently of each other and on each occurrence identically or differently selected from H or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,

R is independently of each other and on each occurrence identically or differently selected from straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 , —SiR 0 R 00 , —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl or heteroarylalkyl, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,

L is independently of each other and on each occurrence identically or differently selected from F, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,

Y 1 , Y 2 are independently of each other and on each occurrence identically or differently selected from H, F, C1 or CN,

X 0 is halogen,

R 0 , R 00 are independently of each other and on each occurrence identically or differently selected from H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated, with the proviso that, if X 1 , X 2 and Y are O, then the divalent heteroarylene unit of formula I is bonded via the 1- or 4-position of the benzene ring to at least one group that is different from H, wherein the compound is a conjugated polymer comprising one or more repeating units of formula II1 or II2, and optionally one or more repeating units of formula II3:

—(Ar 1 ) a —U—(Ar 2 ) b —(Ar 3 ) c —(Ar 4 ) d —  II1

—(Ar 1 ) a —(Ar 2 ) b —U—(Ar 3 ) c —(Ar 4 ) d —  II2

—(Ar 1 ) a —(Ar 2 ) b —(Ar 3 ) c —(Ar 4 ) d —  II3

wherein U is a unit of formula I,

Ar 1-4 are independently of each other and on each occurrence identically or differently selected from arylene, heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L,

provided that the Ar 1-4 groups are different from the groups of formula I,

a, b, c, d are 0 or 1, wherein in formula II3 a+b+c+d≥1, or wherein the compound is a monomer of formula V1 or V2

R 7 —(Ar 1 ) a —U—(Ar 2 ) b —(Ar 3 ) c —(Ar 4 ) d —R 8   V1

R 7 —(Ar 1 ) a —(Ar 2 ) b —U—(Ar 3 ) c —(Ar 4 ) d —R 8   V2

wherein

R 7 and R 8 are independently of each other selected from the group consisting of H, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, —SiMe 3 , —SiMe 2 F, —SiMeF 2 , —O—SO 2 Z 1 , —B(OZ 2 ) 2 , —CZ 3 ═C(Z 3 ) 2 , —C≡CH, —C≡CSi(Z 1 ) 3 , —ZnX 0 , MgX 0 and —Sn(Z 4 ) 3 , wherein X 0 is halogen, Z 1-4 are selected from the group consisting of C 1-10 alkyl and C 6-12 aryl, each being optionally substituted, and two groups Z 2 may also form a cycloboronate group having 2 to 20 C atoms together with the B- and O-atoms, and wherein at least one of R 7 and R 8 is different from H,

or wherein the compound is selected of formula VI

wherein Ar 21-28 are one of the meanings given for Art, or a unit of formula I, or —CY 1 ═CY 2 —,

R 1t , R 2t are H, F, Cl, Br, —CF 3 , R*, —CF 2 —R*, —O—R*, —S—R*, —SO 2 —R*, —SO 3 —R*, —C(═O)—R*, —C(═S)—R*, —C(═O)—CF 2 —R*, —C(═O)—OR*, —C(═S)—OR*, —O—C(═O)—R*, —O—C(═S)—R*, —C(═O)—SR*, —S—C(═O)—R*, —C(═O)NR*R**, —NR*—C(═O)—R*, —NHR*, —NR*R**, —CR*═CR*R**, —C≡C—R*, —C≡C—SiR*R**R***, —SiR*R**R***, —CH═C(CN)—C(═O)—OR*, —CH═C(CO—OR*) 2 , —CH═C(CO—NR*R**) 2 , —CH═C(CN)(Ar 9 ),

Ar 9 , Ar 10 are aryl or heteroaryl, each having from 4 to 30 ring atoms, optionally containing fused rings and being unsubstituted or substituted with one or more groups L,

R*, R**, R*** are alkyl with 1 to 20 C atoms which is straight-chain, branched or cyclic, and is unsubstituted, or substituted with one or more F or Cl atoms or CN groups, or perfluorinated, and in which one or more C atoms are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —SiR 0 R 00 —, —NR 0 R 00 —, —CHR 0 ═CR 00 — or —C≡C— such that O— and/or S— atoms are not directly linked to each other,

a-h are 0 or 1,

m is 1, 2 or 3,

r is 0, 1, 2, 3 or 4,

with the proviso that if a+b+c+d+e+f+g+h=0 and X 1 , X 2 and Y are O, then at least one of R 1t and R 2t is different from H.

2. The compound according to claim 1 , wherein R 1 and R denote alkyl, alkoxy or thiaalkyl, all of which are straight-chain or branched, have 1 to 25 C atoms, and are optionally fluorinated.

3. The compound according to claim 1 , which comprises one or more repeating units selected from the following formulae:

wherein X has on each occurrence identically or differently one of the meanings of X 1 and X 2 , t is 1, 2, 3 or 4, and R 2 , R 3 and R 4 have independently of each other and on each occurrence identically or differently one of the meanings given of L.

4. The compound according to claim 1 , which is a conjugated polymer of formula III:

* (A) x -(B) y n *  III

wherein

A is a unit of formula I,

B is a unit of formula I, which is different from A,

x is >0 and ≤1,

y is ≥0 and <1,

x+y is 1, and

n is an integer ≥5.

5. The compound according to claim 1 , which is a conjugated polymer selected from the following formulae

wherein

X 1a has one of the meanings given for X 1 ,

X 2a has one of the meanings given for X 1 ,

Y a has one of the meanings given for Y,

R 1a has one of the meanings given for R 1 ,

Ar 2-4 are arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L, provided that the Ar 2-4 groups are different from the groups of formula I,

a, b, c, d are 0 or 1,

x is >0 and ≤1,

y is ≥0 and <1,

x+y is 1,

n is an integer ≥5, and

in formula III3 and III5 at least one of X 1 , X 2 , Y and R 1 is different from its corresponding radical X 1a , X 2a , Y a and R 1a , respectively.

6. The compound according to claim 1 , wherein one or more of Ar 1 , Ar 2 , Ar 3 and Ar 4 denote arylene or heteroarylene selected from the group consisting of the following formulae

wherein R 11 , R 12 , R 13 , R 14 independently of each other denote H, F, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 RO, —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,

X 0 is halogen, and

R 0 , R 00 are independently of each other and on each occurrence identically or differently selected from H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated.

7. The compound according to claim 3 , wherein one or more of Ar 1 , Ar 2 , Ar 3 and Ar 4 denote arylene or heteroarylene selected from the group consisting of the following formulae

wherein R 11 , R 12 , R 13 , R 14 independently of each other denote H, F, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 RO, —SO 2 RO, —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,

X 0 is halogen, and

R 0 , R 00 are independently of each other and on each occurrence identically or differently selected from H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated.

8. The compound according to claim 1 , wherein one or more of Ar 1 , Ar 2 , Ar 3 and Ar 4 denote arylene or heteroarylene selected from the group consisting of the following formulae

wherein R 11 and R 12 independently of each other denote H, F, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,

X 0 is halogen, and

R 0 , R 00 are independently of each other and on each occurrence identically or differently selected from H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated.

9. The compound according to claim 1 , which is a conjugated polymer selected from the following formulae

wherein 0<x≤1, 0≤y<1, 0<z<1, x+y+z=1, X has on each occurrence identically or differently one of the meanings of X 1 and X 2 , t is 1, 2, 3 or 4, n is an integer ≥5, and R 2 , R 3 and R 4 have independently of each other and on each occurrence identically or differently one of the meanings given for L.

10. The compound according to claim 1 , which is a conjugated polymer of formula IV

R 5 -chain-R 6   IV

wherein “chain” denotes a polymer chain selected from formulae III:

* (A) x -(B) y n *  III

wherein

A is a unit of formula I,

B is a unit of formula I, which is different from A,

x is >0 and ≤1,

y is ≥0 and <1,

x+y is 1, and

n is an integer ≥5, and

R 5 and R 6 have independently of each other one of the meanings of R 1 or L, or denote, independently of each other, H, F, Br, Cl, I, —CH 2 Cl, —CHO, —CR′═CR″ 2 , —SiR′R″R′″, —SiR′X′X″, —SiR′R″X′, —SnR′R″R′″, —BR′R″, —B(OR′)(OR″), —B(OH) 2 , —O—SO 2 —R′, —C≡CH, —C≡C—SiR′ 3 , —ZnX′ or an endcap group, X′ and X″ denote halogen, R′, R″ and R′″ have independently of each other one of the meanings of R 0 , and two of R′, R″ and R′″ may also form a cyclosilyl, cyclostannyl, cycloborane or cycloboronate group with 2 to 20 C atoms together with the respective hetero atom to which they are attached.

11. The compound of claim 1 , which is selected from the following formulae

R 7 —Ar 1 —U—Ar 2 —R 8   V1a

R 7 —U—R 8   V1b

R 7 —Ar 1 —U—R 8   V1c

R 7 —U—Ar 2 —R 8   V1d.

12. The compound of claim 1 , which is selected of formula V3

R 7 —U*—R 8   V3

wherein U* is a unit selected from formulae R1-R11:

wherein

R 1 is independently of each other and on each occurrence identically or differently selected from H or straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more CH 2 groups are optionally replaced by —O—, —S—, —C(═O)—, —C(═S)—, —C(═O)—O—, —O—C(═O)—, —NR 0 —, —SiR 0 R 00 —, —CF 2 —, —CR 0 ═CR 00 —, —CY 1 ═CY 2 — or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and in which one or more CH 2 or CH 3 groups are optionally replaced by a cationic or anionic group, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the aforementioned cyclic groups has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, and is unsubstituted or substituted by one or more identical or different groups L,

X is O or S,

Y is O, S or CU 1 U 2 ,

U 1 , U 2 are an electron withdrawing group selected from CN, C(═O)R or C(═O)OR, or U 1 and U 2 together form a carbocyclic, heterocyclic, aromatic or heteroaromatic ring having 4 to 15 ring atoms that is optionally substituted by one or more groups L,

L is independently of each other and on each occurrence identically or differently selected from F, Cl, —CN, —NC, —NCO, —NCS, —OCN, —SCN, R 0 , OR 0 , SR 0 , —C(═O)X 0 , —C(═O)R 0 , —C(═O)—OR 0 , —O—C(═O)—R 0 , —NH 2 , —NHR 0 , —NR 0 R 00 , —C(═O)NHR 0 , —C(═O)NR 0 R 00 , —SO 3 R 0 , —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 20 C atoms that is optionally substituted and optionally comprises one or more hetero atoms,

X 0 is halogen,

R 0 , R 00 are independently of each other and on each occurrence identically or differently selected from H or straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated,

t is 1, 2, 3 or 4,

R 2 , R 3 and R 4 have independently of each other and on each occurrence identically or differently one of the meanings given of L.

13. The compound according to claim 1 , wherein:

a) one or more of Ar 1 , Ar 2 , Ar 3 and Ar 4 denote arylene or heteroarylene from the group consisting of the following formulae

wherein R 11 , R 12 , R 13 , R 14 independently of each other denote H or have one of the meanings of L, and/or

b) one or more of Ar 1 , Ar 2 , Ar 3 and Ar 4 denote arylene or heteroarylene selected from the group consisting of the formulae

wherein R 11 , R 12 , R 13 , R 14 independently of each other denote H or have one of the meanings of L, and

c) one or more of Ar 1 , Ar 2 , Ar 3 and Ar 4 denote arylene or heteroarylene selected from the group consisting of the formulae

wherein R 11 and R 12 independently of each other denote H or have one of the meanings of L.

14. The compound of claim 1 , wherein Ar 21-28 are selected from the following groups

a) the group consisting of the formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D44, D106, D111, D140 and D140:

wherein R 11 , R 12 , R 13 , R 14 independently of each other denote H or have one of the meanings of L,

b) the group consisting of the formulae A1, A6, A7, A15, A16, A20, A74, A88, A92 and A98

wherein R 11 , R 12 , R 13 , R 14 independently of each other denote H or have one of the meanings of L, and

c) the group consisting of the formulae Sp1, Sp6 and Sp10:

wherein R 11 and R 12 independently of each other denote H or have one of the meanings of L.

15. The compound of claim 1 , which is selected of formula VI1

R 1t —U*—R 2t   VI1

wherein U* is a unit selected from formulae R 1 -R 11 :

wherein X has on each occurrence identically or differently one of the meanings of X 1 and X 2 , t is 1, 2, 3 or 4, and R 2 , R 3 and R 4 have independently of each other and on each occurrence identically or differently one of the meanings given for L.

16. A mixture comprising one or more compounds according to claim 1 and one or more additional compounds having one or more of semiconducting, charge transport, hole or electron transport, hole or electron blocking, electrically conducting, photoconducting or light emitting properties.

17. A mixture comprising one or more compounds according to claim 1 , and one or more n-type organic semiconductors.

18. The mixture of claim 17 , wherein the n-type organic semiconductors are selected from fullerenes or substituted fullerenes.

19. A formulation comprising one or more compounds according to claim 1 and further comprising one or more organic solvents.

20. A semiconducting, charge transport, electrically conducting, photoconducting or light emitting material comprising a compound according to claim 1 .

21. An optical, electrooptical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising such a device or component, which comprises the compound according to claim 1 .

22. The optical, electrooptical, electronic, electroluminescent or photoluminescent device of claim 21 , which is selected from organic thin film transistors (OTFT), organic thin film transistors (OTFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, dye-sensitized solar cells (DSSC), perovskite-based solar cells, laser diodes, Schottky diodes, photoconductors and photodetectors.

23. The component of claim 21 , which is selected from charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates and conducting patterns.

24. The assembly of claim 21 , which is selected from integrated circuits (IC), radio frequency identification (RFID) tags or security markings or security devices containing them, flat panel displays or backlights thereof, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors and biochips.

25. A bulk heterojunction comprising a mixture according to claim 16 .

26. A bulk heterojunction (BHJ) OPV device or inverted BHJ OPV device, comprising a bulk heterojunction of claim 25 .

27. The compound according to claim 1 , wherein the conjugated polymer is prepared by coupling one or more monomers selected from the monomers of formula V1 or V2:

R 7 —(Ar 1 ) a —U—(Ar 2 ) b —(Ar 3 ) c —(Ar 4 ) d —R 8   V1

R 7 —(Ar 1 ) a —(Ar 2 ) b —U—(Ar 3 ) c —(Ar 4 ) d —R 8   V2

wherein

U is a unit of formula I as defined,

Ar 1-4 arylene or heteroarylene that has 5 to 20 ring atoms, is mono- or polycyclic, does optionally contain fused rings, is unsubstituted or substituted by one or more identical or different groups L, provided that the Ar 1-4 groups are different from groups of the formula I, a, b, c, d are 0 or 1, and

R 7 and R 8 are independently of each other selected from the group consisting of H, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, —SiMe 3 , —SiMe 2 F, —SiMeF 2 , —O—SO 2 Z 1 , —B(OZ 2 ) 2 , —CZ 3 ═C(Z 3 ) 2 , —C≡CH, —C≡CSi(Z 1 ) 3 , —ZnX 0 , Mg—X 0 and —Sn(Z 4 ) 3 , wherein X 0 is halogen, Z 1-4 are selected from the group consisting of C1-10 alkyl and C6-12 aryl, each being optionally substituted, and two groups Z 2 may also form a cycloboronate group having 2 to 20 C atoms together with the B- and O-atoms, and wherein at least one of R 7 and R 8 is different from H;

with each other and/or with one or more monomers of formulae MI-MIV:

R 7 —Ar 1 —R 8   MI

R 7 —Ar 2 —R 8   MII

R 7 —Ar a —R 8   MIII

R 7 —Ar 4 —R 8   MIV

in an aryl-aryl coupling reaction.