Semiconducting polymers

1. A polymer comprising in said polymer identical or different repeating units of formula I

wherein the asterisks indicate a link to neighboring groups, and the polymer is a conjugated polymer,

X is O, S or NR x ,

R is, on each occurrence identically or differently, H, F, Cl, Br, I, CN, or straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl or heteroaryloxycarbonyl having 4 to 30 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 1 ,

R x is on each occurrence identically or differently straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN,

R 0 and R 00 are independently of each other H or optionally substituted carbyl or hydrocarbyl optionally comprising one or more hetero atoms,

R 1 is on each occurrence identically or differently H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X 0 , —C(═O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or P-Sp-,

P is a polymerizable or crosslinkable group,

Sp is a spacer group or a single bond,

X 0 is halogen.

2. The polymer comprising repeating units which contain a unit of formula I as defined in claim 1 and/or contain one or more aryl or heteroaryl units that are optionally substituted, wherein at least one of the repeating units in the polymer contains at least one unit of formula I as defined in claim 1 .

3. The polymer according to claim 1 , of formula II

—[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ] n —  II

wherein

U is on each occurrence identically or differently a unit of formula I as defined in claim 1 ,

Ar 1 , Ar 2 , Ar a are, on each occurrence identically or differently, and independently of each other, optionally substituted aryl or heteroaryl,

Y 1 and Y 2 are independently of each other H, F, Cl or CN,

x is on each occurrence identically or differently 0, 1 or 2, wherein in at least one repeating unit, i.e. in at least one unit —[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ]—, x is 1,

y is on each occurrence identically or differently 0, 1 or 2,

n is an integer>1.

4. The polymer according to claim 3 , of formula IIa

R 2 —[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ] n —R 3   IIa

wherein U, Ar 1-3 , n, x and y have the meanings of claim 3 , and

R 2 and R 3 have independently of each other one of the meanings of R 1 , or denote H, —CH 2 Cl, —CHO, —CH═CH 2 , —SiR′R″R′″, —SnR′R″R′″, —BR′R″, —B(OR′)(OR″), —B(OH) 2 , or P-Sp, wherein P and Sp are as defined above, and 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 ring together with the hetero atom to which they are attached.

5. The polymer according to claim 2 , wherein the aryl or heteroaryl units are independently of each other 1,4-phenylene, thiophene-2,5-diyl, thiazole-2,5-diyl, selenophene-2,5-diyl, furan-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, thieno[2,3-b]thiophene-2,5-diyl, selenopheno[3,2-b]selenophene-2,5-diyl, selenopheno[2,3-b]selenophene-2,5-diyl, selenopheno[3,2-b]thiophene-2,5-diyl, or selenopheno[2,3-b]thiophene-2,5-diyl, all of which are unsubstituted, or mono- or polysubstituted with R or R 1 as defined in claim 2 .

6. The polymer according to claim 2 , wherein the aryl or heteroaryl units are on each occurrence identically or differently 1,4-phenylene, thiophene-2,5-diyl, selenophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, thieno[2,3-b]thiophene-2,5-diyl, selenopheno[3,2-b]selenophene-2,5-diyl, selenopheno[2,3-b]selenophene-2,5-diyl, selenopheno[3,2-b]thiophene-2,5-diyl, selenopheno[2,3-b]thiophene-2,5-diyl, benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl, 2,2-dithiophene, 2,2-diselenophene, dithieno[3,2-b:2′,3′-d]silole-5,5-diyl, 4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl, carbazole-2,7-diyl, fluorene-2,7-diyl, indaceno[1,2-b:5,6-N]dithiophene-2,7-diyl, benzo[1″,2″:4,5;4″,5″:4′,5′]bis(silolo[3,2-b:3′,2′-b′]thiophene)-2,7-diyl, phenanthro[1,10,9,8-c,d,e,f,g]carbazole-2,7-diyl, benzo[2,1,3]thiadiazole-4,7-diyl, benzo[2,1,3]selenadiazole-4,7-diyl, benzo[2,1,3]oxadiazole-4,7-diyl, 2H-benzotriazole-4,7-diyl, 3,4-difluorothiophene-2,5-diyl, thieno[3,4-b]pyrazine-2,5-diyl, quinoxaline-5,8-diyl, thieno[3,4-b]thiophene-4,6-diyl, thieno[3,4-b]thiophene-6,4-diyl, 3,6-di-thien-2-yl-pyrrolo[3,4-c]pyrrole-1,4-dione, or [1,3]thiazolo[5,4-d][1,3]thiazole-2,5-diyl, all of which are unsubstituted, or mono- or polysubstituted with R or R 1 as defined in claim 2 .

7. The polymer according to claim 6 , wherein R is primary alkyl or alkoxy with 1 to 30 C atoms, secondary alkyl or alkoxy with 3 to 30 C atoms, or tertiary alkyl or alkoxy with 4 to 30 C atoms, wherein in all these groups one or more H atoms are optionally replaced by F, or R is aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms.

8. A mixture or blend comprising one or more polymers according to claim 1 and one or more compounds or polymers having semiconducting, charge transport, hole/electron transport, hole/electron blocking, electrically conducting, photoconducting or light emitting properties.

9. A formulation comprising one or more polymers, according to claim 1 , and one or more solvents.

10. A charge transport, semiconducting, electrically conducting, photoconducting or light emitting material in optical, electrooptical, electronic, electroluminescent or photoluminescent components or devices which comprises a polymer according to claim 1 .

11. An optical, electrooptical or electronic component or device comprising one or more polymers, according to claim 1 .

12. A component or device according to claim 11 , which is an organic field effect transistor (OFET), a thin film transistor (TFT), an integrated circuit (IC), a logic circuit, a capacitor, a radio frequency identification (RFID) tag, an organic light emitting diode (OLED), an organic light emitting transistor (OLET), a flat panel display, a backlight of display, an organic photovoltaic device (OPV), a solar cell, a laser diode, a photoconductor, a photodetector, an electrophotographic device, an electrophotographic recording device, an organic memory device, a sensor device, a charge injection layer, a charge transport layer or an interlayer in a polymer light emitting diode (PLEDs), a Schottky diode, a planarizing layer, an antistatic film, a polymer electrolyte membrane (PEM), a conducting substrate, a conducting pattern, an electrode material in a battery, an alignment layer, a biosensor, a biochip, a security marking, a security device, or a component or device for detecting and discriminating DNA sequences.

13. The component or device according to claim 11 , which is an OFET or a bulk heterojunction OPV device.

14. A monomer of formula Ia

R 2 —U—R 3   Ia

wherein U is a unit of formula

I

wherein the asterisks indicate a link to neighboring groups,

X is O, S or NR x ,

R is, on each occurrence identically or differently, H, F, Cl, Br, I, CN, or straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl or heteroaryloxycarbonyl having 4 to 30 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 1 ,

R x is on each occurrence identically or differently straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN,

R 0 and R 00 are independently of each other H or optionally substituted carbyl or hydrocarbyl optionally comprising one or more hetero atoms,

R 1 is on each occurrence identically or differently H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X 0 , —C(═O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or P-Sp-,

P is a polymerizable or crosslinkable group,

Sp is a spacer group or a single bond,

X 0 is halogen, and

R 2 and R 3 are, independently of each other, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, —SiMe 2 F, —SiMeF 2 , —O—SO 2 Z 1 , —B(OZ 2 ) 2 , —CZ 3 ═C(Z 3 ) 2 , —C≡CH or —Sn(Z 4 ) 3 , wherein Z 1-4 are alkyl or aryl, each being optionally substituted, and two groups Z 2 may also form a cyclic group.

15. A process of preparing a polymer according to claim 1 , by coupling:

one or more monomers of formula Ia

R 2 —U—R 3   Ia

wherein U is a unit of formula I

wherein the asterisks indicate a link to neighboring groups,

X is O, S or NR x ,

R is, on each occurrence identically or differently, H, F, Cl, Br, I, CN, or straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or denote aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl or heteroaryloxycarbonyl having 4 to 30 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 1 ,

R x is on each occurrence identically or differently straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN,

R 0 and R 00 are independently of each other H or optionally substituted carbyl or hydrocarbyl optionally comprising one or more hetero atoms,

R 1 is on each occurrence identically or differently H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X 0 , —C(═O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or P-Sp-,

P is a polymerizable or crosslinkable group,

Sp is a spacer group or a single bond,

X 0 is halogen, and

R 2 and R 3 are, independently of each other, Cl, Br, I, O-tosylate, O-triflate, O-mesylate, O-nonaflate, —SiMe 2 F, —SiMeF 2 , —O—SO 2 Z 1 , —B(OZ 2 ) 2 , —CZ 3 ═C(Z 3 ) 2 , —C≡CH or —Sn(Z 4 ) 3 , wherein Z 1-4 are alkyl or aryl, each being optionally substituted, and two groups Z 2 may also form a cyclic group,

and/or one or more monomers of the formula

R 2 —Ar 3 —R 3

wherein R 2 and R 3 are as defined above and Ar 3 is, on each occurrence identically or differently, optionally substituted aryl or heteroaryl,

in an aryl-aryl coupling reaction.

16. The formulation according to claim 9 , wherein the solvent is an organic solvent.