Conjugated polymers
The invention relates to novel conjugated polymers containing one or more thieno[3,2-b]thiophene based polycyclic repeating units, to methods for their preparation and educts or intermediates used therein, to polymer blends, mixtures and formulations containing them, to the use of the polymers, polymer blends, mixtures and formulations as organic semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices and organic photodetectors (OPD), and to OE, OPV and OPD devices comprising these polymers, polymer blends, mixtures or formulations.
1. A polymer comprising one or more units of formula I
wherein
R 1 and R 2 independently of each other denote phenyl that is substituted with one or more straight-chain, branched or cyclic alkyl groups with 1 to 30 C atoms that are optionally fluorinated,
Y 1 and Y 2 are independently of each other H, F, Cl or CN, and
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl.
2. A formulation comprising one or more polymers, mixtures or polymer blends according to claim 1 , and one or more organic solvents.
3. The polymer according to claim 1 , characterized in that the units of formula I are selected from formula Ia:
wherein R denotes straight-chain or branched alkyl with 1 to 20 C atoms that is optionally fluorinated.
4. The polymer according to claim 1 , characterized in that it comprises one or more units of formula IIa or IIb
—[(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ]— IIa
—[(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ]— IIb
wherein
U is a unit of formula I as defined in claim 1 ,
Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,
R S is on each occurrence identically or differently F, Br, Cl, —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,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
X 0 is halogen,
a, b, c are on each occurrence identically or differently 0, 1 or 2,
d is on each occurrence identically or differently 0 or an integer from 1 to 10,
wherein the polymer comprises at least one repeating unit of formula IIa or IIb wherein b is at least 1.
5. The polymer according to claim 1 , characterized in that it additionally comprises one or more repeating units selected of formula IIIa or IIIb
—[(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ]— IIIa
-[(A c ) b -(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ]— IIIb
wherein
Ar 1 , Ar 2 , Ar 3 , are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from a unit of formula I, has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,
a, b, c are on each occurrence identically or differently 0, 1 or 2, d is on each occurrence identically or differently 0 or an integer from 1 to 10, and
A c is an aryl or heteroaryl group that is different from U and Ar 1-3 , has 5 to 30 ring atoms, is optionally substituted by one or more groups R S , and is selected from aryl or heteroaryl groups having electron acceptor properties,
R S is on each occurrence identically or differently F, Br, Cl, —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,
wherein the polymer comprises at least one repeating unit of formula IIIa or IIIb wherein b is at least 1.
6. The polymer according to claim 1 , wherein the one or more units of formula I is of formula IV:
wherein
A, B, C independently of each other denote a distinct unit of formula I as defined in claim 1 ,
x is >0 and ≦1,
y is ≧0 and <1,
z is ≧0 and <1,
x+y+z is 1, and
n is an integer >1.
7. The polymer according to claim 1 , characterized in that it is selected from one of the following formulae
*-[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ] n -* IVa
*—[(Ar 1 —U—Ar 2 ) x —(Ar 3 —Ar 3 ) y ] n -* IVb
*-[(Ar 1 —U—Ar 2 ) x —(Ar 3 —Ar 3 —Ar 3 ) y ] n -* IVc
*—[(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] n -* IVd
*—([(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] x —[(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ] y ) n - * IVe
*—[(U—Ar 1 —U) x —(Ar 2 —Ar 3 ) y ] n -* IVf
*—[(U—Ar 1 —U) x —(Ar 2 —Ar 3 —Ar 2 ) y ] n -* IVg
*—[(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) c ] n -* IVh
*—([(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) c ] x —[(Ac c ) b —(Ar 1 ) a -(A c ) b -(Ar 2 ) d ] y ) n -* IVi
*—[(U—Ar 1 ) x —(U—Ar 2 ) y —(U—Ar 3 ) z ] n -* IVk
wherein
U is a unit of formula I,
Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,
a, b, c are on each occurrence identically or differently 0, 1 or 2, d is on each occurrence identically or differently 0 or an integer from 1 to 10,
A c is an aryl or heteroaryl group that is different from U, is optionally substituted by one or more groups R S , and is selected from aryl or heteroaryl groups having electron acceptor properties,
x is >0 and ≦1,
y is ≧0 and <1,
z is ≧0 and <1, and
n is an integer >1,
wherein these polymers can be alternating or random copolymers, and wherein in formula IVd and IVe, in at least one of the repeating units [(Ar 1 ) a —(U) b —(Ar 2 ) c —(Ar 3 ) d ] and in at least one of the repeating units [(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ], b is at least 1 and wherein in formula IVh and IVi, in at least one of the repeating units [(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) d ] and in at least one of the repeating units [(U) b —(Ar 1 ) a —(U) b —(Ar 2 ) d ], b is at least 1.
8. The polymer according to claim 6 , characterized in that it is of formula V
R 5 -chain-R 6 V
wherein “chain” is a polymer chain of formulae IV,
R 5 and R 6 are, independently of each other F, Br, Cl, —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 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, wherein X′ and X″ denote halogen,
R′, R″ and R″ are, independently of each other, H or optionally substituted C 1-40 carbyl or hydrocarbyl, and preferably denote H or alkyl with 1 to 12 C-atoms,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl, and
two of R′, R″ and R′″ may also form a ring together with the hetero atom to which they are attached.
9. The polymer according to claim 4 , wherein one or more of Ar 1 , Ar 2 and Ar 3 denote aryl or heteroaryl selected from the group consisting of the following formulae
wherein R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 independently of each other denote H or F, Br, Cl, —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.
10. The polymer according to claim 5 , wherein A c and/or Ar 3 denotes aryl or heteroaryl selected from the group consisting of the following formulae
wherein R 11 , R 12 , R 13 , R 14 , R 15 and R 16 independently of each other denote H or F, Br, Cl, —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.
11. A mixture or polymer 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.
12. The mixture or polymer blend according to claim 11 , characterized in that it further comprises one or more n-type organic semiconductor compounds.
13. The mixture or polymer blend according to claim 12 , characterized in that the n-type organic semiconductor compound is a fullerene or substituted fullerene.
14. A formulation comprising one or more polymers, mixtures or polymer blends according to claim 1 , and one or more solvents.
15. A charge transport, semiconducting, electrically conducting, photoconducting or light emitting material in an optical, electrooptical, electronic, electroluminescent or photoluminescent device, or in a component of such a device, or in an assembly comprising such a device or component, which comprises a polymer according to claim 1 .
16. A charge transport, semiconducting, electrically conducting, photoconducting or light emitting material comprising a polymer, according to claim 1 .
17. An optical, electrooptical, electronic, electroluminescent or photoluminescent device, or a component thereof, or an assembly comprising it, which comprises a charge transport, semiconducting, electrically conducting, photoconducting or light emitting material, and comprises a polymer according to claim 1 .
18. A device, a component thereof, or an assembly comprising it according to claim 17 , wherein the device is selected from organic field effect transistors (OFET), thin film transistors (TFT), organic light emitting diodes (OLED), organic light emitting transistors (OLET), organic photovoltaic devices (OPV), organic photodetectors (OPD), organic solar cells, laser diodes, Schottky diodes, and photoconductors, the component is selected from charge injection layers, charge transport layers, interlayers, planarising layers, antistatic films, polymer electrolyte membranes (PEM), conducting substrates, conducting patterns, and the assembly 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.
19. The device according to claim 18 , which is an OFET, bulk heterojunction (BHJ) OPV device or inverted BHJ OPV device.
20. A monomer of formula VIa or VIb
R 7 —(Ar 1 ) a —U—(Ar 2 ) c —R 8 VIa
R 7 —U—(Ar 1 ) a —U—R 8 VIb
wherein a and c are on each occurrence identically or differently 0, 1 or 2, U is a unit of formula I as defined in claim 1 ,
Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, has 5 to 30 ring atoms and is optionally substituted, preferably by one or more groups R S ,
R S is on each occurrence identically or differently F, Br, Cl, —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,
R 7 and R 8 are selected from the group consisting of 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, —C≡CSi(Z 1 ) 3 , —ZnX 0 and —Sn(Z 4 ) 3 , wherein X 0 is halogen, preferably Cl, Br or I, and
Z 1-4 are selected from the group consisting of alkyl and aryl, each being optionally substituted, and two groups Z 2 may also together form a cyclic group.
21. The monomer according to claim 20 , which is selected from the following formulae
R 7 —Ar 1 —U—Ar 2 —R 8 VI1
R 7 —U—R 8 VI2
R 7 —Ar 1 —U—R 8 VI3
R 7 —U—Ar 2 —R 8 VI4
R 7 —U—Ar 1 —U—R 8 VI5
wherein U, Ar 1 , Ar 2 , R 7 and R 8 are as defined in claim 20 .
22. A process of preparing a polymer according to claim 1 , by coupling one or more monomers
R 7 —(Ar 1 ) a —U—(Ar 2 ) c —R 8 VIa
R 7 —U—(Ar 1 ) a —U—R 8 VIb
wherein a and c are on each occurrence identically or differently 0, 1 or 2,
U is a unit of formula I as defined in claim 1 ,
Ar 1 , Ar 2 , Ar 3 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, has 5 to 30 ring atoms and is optionally substituted by one or more groups R S ,
R S is on each occurrence identically or differently F, Br, Cl, —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, and
R 7 and R 8 are selected from Cl, Br, I, —B(OZ 2 ) 2 and —Sn(Z 4 ) 3 ,
with each other and/or with one or more monomers selected from the following formulae
R 7 —(Ar 1 ) a -A c -(Ar 2 ) c —R 8 VIII
R 7 —Ar 1 —R 8 IX
R 7 —Ar 3 —R 8 X
wherein Ar 3 is on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is different from U, has 5 to 30 ring atoms and is optionally substituted by one or more groups R S , A c is an aryl or heteroaryl group that is different from U, and R 7 and R 8 are selected from Cl, Br, I, —B(OZ 2 ) 2 and —Sn(Z 4 ) 3 ,
in an aryl-aryl coupling reaction.
23. The polymer according to claim 4 , characterized in that it additionally comprises one or more repeating units selected of formula IIIa or IIIb
—[(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ]— IIIa
-[(A c ) b -(Ar 1 ) a -(A c ) b -(Ar 2 ) c —(Ar 3 ) d ]— IIIb
wherein Ar 1 , Ar 2 , Ar 3 , a, b, c and d are as defined in claim 4 , and A c is an aryl or heteroaryl group that is different from U and Ar 1-3 , has 5 to 30 ring atoms, is optionally substituted by one or more groups R S as defined in claim 4 , and is selected from aryl or heteroaryl groups having electron acceptor properties, wherein the polymer comprises at least one repeating unit of formula IIIa or IIIb wherein b is at least 1.
24. The polymer according to claim 23 , wherein (U) b is of formula IV:
wherein
A, B, C independently of each other denote a distinct unit of formula I, Ia, Ia1, IIa, IIb, IIIa, or IIIb,
x is >0 and ≦1,
y is ≧0 and <1,
z is >0 and <1,
x+y+z is 1, and
n is an integer >1.
25. The polymer according to claim 1 , wherein in formula I, R 0 and R 00 are independently of each other H or alkyl with 1 to 12 C-atoms.