Mono-, oligo- and polythieno[2,3-b]thiophenes
The invention relates to novel mono-, oligo and poly[2,3-b]-thienothiophenes, their use as semiconductors or charge transport materials, in optical, electro-optical or electronic devices like for example liquid crystal displays, optical films, organic field effect transistors (FET or OFET) for thin film transistor liquid crystal displays and integrated circuit devices such as RFID tags, electroluminescent devices in flat panel displays, and in photovoltaic and sensor devices, and to a field effect transistor, light emitting device or ID tag comprising the novel polymers.
1. A monomer, oligomer or polymer of formula I
-[(A) a —(B) b —(C) c —(D) d ] n — I
wherein
A and C are, independently of each other in each case, a group of formula II
R 1 and R 2 are, independently of each other, H, halogen, or a straight chain, branched or cyclic alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or poly-substituted by F, Cl, Br, I, OH or CN, in which one or more non-adjacent CH 2 groups are optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, or are optionally substituted aryl or heteroaryl, P—Sp—or P—Sp*—,
P is a polymerisable or reactive group,
P* is a group that can be converted to or substituted by a polymerisable or reactive group P,
Sp is a spacer group or a single bond,
R 0 and R 00 are, independently of each other, H, aryl or alkyl with 1 to 12 C-atoms,
B and D are, independently of each other in each case, —CX 1 ═CX 2 —, —C≡C— or an arylene or heteroarylene group that is optionally substituted with one or more R 1 groups,
X 1 and X 2 are, independently of each other, H, F, Cl or CN,
a, b, c, d are, independently of each other, 0 or an integer of 1 to 10, with a+b+c+d>0, and wherein in at least one recurring unit [(A) a —(B) b —(C) c —(D) d ] at least one of a and c is 1 and at least one of b and d is 1, and
n is an integer ≧1,
wherein the recurring units [(A) a —(B) b —(C) c —(D) d ] are identical or different, and
with the proviso that if a is 1, then —(B) b —(C) c —(D) d — is different from —CH═CH—Ar—CH═CH—, with Ar being 2,5-thiophene, 1,4-phenylene or 2,5-dimethoxy-1,4-phenylene, or the compounds comprise at least one group P—Sp—or P*—Sp—.
2. A monomer, oligomer or polymer according to claim 1 , wherein the monomer, oligomer or polymer of formula I is of formula I1
R 3 —[(A) a —(B) b —(C) c —(D) d ] n —R 4 I1
wherein A, B, C, D, a, b, c and d are defined as in claim 1 , and R 3 and R 4 are, independently of each other, H, halogen, Sn(R 0 ) 3 , CH 2 Cl, COH, CH═CH 2 , SiR 0 R 00 R 000 , optionally substituted aryl or heteroaryl, P—Sp—or P*—Sp—, wherein P, P*, Sp, R 0 and R 00 are defined as in claim 1 , and R 000 has one of the meanings of R 0 .
3. An oligomer or polymer according to claim 1 , having a degree of polymerisation of 10 to 5000.
4. A monomer according to claim 2 , wherein n is 1 and one or both of R 3 and R 4 are P—Sp—or P*—Sp—.
5. A monomer, oligomer or polymer according to claim 1 , wherein R 1 and R 2 are, independently of each other, C 1 –C 20 -alkyl that is optionally substituted with one or more fluorine atoms, C 1 –C 20 -alkoxy, C 1 –C 20 -alkenyl, C 1 –C 20 -alkynyl, C 1 –C 20 -thioether, C 1 –C 20 -silyl, C 1 –C 20 -ester, C 1 –C 20 -amino, C 1 –C 20 -fluoroalkyl or optionally substituted aryl or heteroaryl.
6. A monomer, oligomer or polymer according to claim 1 , wherein
B and/or D are, independently of each other, 1,4-phenylene, fluorinated 1,4-phenylene, 2,5-pyridine, 2,5-pyrimidine, p,p′-biphenyl, naphthalene-2,6-diyl, thiophene-2,5-diyl, fluorinated or alkylated thiophene-2,5-diyl, fluorinated benzo[1,2-b:4,5-b′]dithiophene, 2,5-thiazole, 2,5-thiadiazole, 2,5-oxazole or 2,5-oxadiazole, all of which are unsubstituted, mono- or polysubstituted with L,
wherein
L is F, Cl, Br, or an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, or is C 1 –C 20 -alkenyl, C 1 –C 20 -alkynyl, C 1 –C 20 -thioalkyl, C 1 –C 20 -silyl, C 1 –C 20 -ester, C 1 –C 20 -amino, or C 1 –C 20 -fluoroalkyl.
7. A monomer, oligomer or polymer according to claim 1 , wherein B and/or D are, independently of each other, thiophene-2,5-diyl or 2.2-dithiophene, that are optionally substituted by one or more groups having the meaning of R 1 in claim 1 , or a group of formula III
wherein R 5 and R 6 have one of the meanings of R 1 .
8. A monomer, oligomer or polymer according to claim 1 , which is selected from the following formulae
wherein R 1 , R 2 and n are defined as in claim 1 and R 5 and R 6 have one of the meanings of R 1 .
9. A monomer according to claim 1 , which is selected from the following formulae
wherein R 1 , R 2 and Sp are defined as in claim 1 , P′ is defined as P or P* in claim 1 , and R′ is H, halogen, Sn(R 0 ) 3 , CH 2 Cl, COH, CH═CH 2 SiR 0 R 00 R 000 , optionally substituted aryl or heterbaryl, P—Sp—or P*—Sp—, wherein P, P*, Sp, R 0 and R 00 are defined as in claim 1 , and R 000 having one of the meanings of R 0 .
10. A polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline.
11. An anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material according to claim 10 that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or crosslinked to fix the oriented state.
12. A side chain liquid crystal polymer obtained by
I) polymerisation of one or more
a) monomer or oligomer according to claim 1 or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
or
II) grafting to a polymer backbone in a polymeranaloguous reaction, optionally with one or more mesogenic or non-mesogenic comonomers that are not of claim 1 , one or more
a) monomer or oligomer according to claim 1 , or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline.
13. A semiconductor or charge transport material in an optical, electrooptical or electronic device, a field effect transistor (FET), an integrated circuitry, a thin film transistor (TFT) for flat panel display applications, or a radio frequency identification (RFID) tag, or a semiconducting component for organic light emitting diode (OLED) applications, a charge transport or electroluminescent layer in an electroluminescent display or backlight of a liquid crystal display (LCD), comprising
a monomer, oligomer or polymer of claim 1 ,
a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
an anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material described above that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or
crosslinked to fix the oriented state, or
a side chain liquid crystal polymer obtained by
I) polymerisation of one or more
a) monomer or oligomer according to claim 1 or
b) a polymerisable liquid crystal material comprising one, or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
or
II) grafting to a polymer backbone in a polymeranaloguous reaction, optionally with one or more mesogenic or non-mesogenic comonomers that are not of claim 1 , one or more
a) monomer or oligomer according to claim 1 , or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of-the polymerisable compounds is mesogenic or liquid crystalline.
14. An electroluminescent material, a photovoltaic or sensor device, an electrode material in a battery, a photoconductor, an electrophotographic device, an electrophotographic recording or an alignment layer in a LCD or OLED device comprising
a monomer, oligomer or polymer of claim 1 ,
a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
an anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material described above that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or crosslinked to fix the oriented state, or
a side chain liquid crystal polymer obtained by
I) polymerisation of one or more
a) monomer or oligomer according to claim 1 or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
or
II) grafting to a polymer backbone in a polymeranaloguous reaction, optionally with one or more-mesogenic or non-mesogenic comonomers that are not of claim 1 , one or more
a) monomer or oligomer according to claim 1 , or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more pblymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline.
15. An optical, electrooptical or electronic device, FET, integrated circuit (IC), TFT, OLED or alignment layer comprising
a monomer, oligomer or polymer of claim 1 ,
a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable-compounds is mesogenic or liquid crystalline,
an anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material described above that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or crosslinked to fix the oriented state, or
a side chain liquid crystal polymer obtained by
I) polymerisation of one or more
a) monomer or oligomer according to claim 1 or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
or
II) grafting to a polymer backbone in a polymeranaloguous reaction, optionally with one or more mesogenic or non-mesogenic comonomers that are not of claim 1 , one or more
a) monomer or oligomer according to claim 1 , or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline.
16. A TFT or TFT array for a flat panel display, radio frequency identification (RFID) tag, electroluminescent display or backlight, comprising
a monomer, oligomer or polymer of claim 1 ,
a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
an anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material described above that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or crosslinked to fix the oriented state, or
a side chain liquid crystal polymer obtained by
I) polymerisation of one or more
a) monomer or oligomer according to claim 1 or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
or
II) grafting to a polymer backbone in a polymeranaloguous reaction, optionally-with one or more mesogenic or non-mesogenic comonomers that are not of claim 1 , one or more
a) monomer or oligomer according to claim 1 , or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline.
17. A security marking or device comprising a FET or an RFID tag a monomer, oligomer or polymer of claim 1 ,
a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
an anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material described above that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or
crosslinked to fix the oriented state, or
a side chain liquid crystal polymer obtained by
I) polymerisation of one or more
a) monomer or oligomer according to claim 1 or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
or
II) grafting to a polymer backbone in a polymeranaloguous reaction, optionally with one or more mesogenic or non-mesogenic comonomers that are not of claim 1 , one or more
a) monomer or oligomer according to claim 1 , or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline.
18. A conducting ionic material that is an oxidatively or reductively doped
monomer, oligomer or polymer of claim 1 ,
a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
an anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material described above that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or
crosslinked to fix the oriented state, or
a side chain liquid crystal polymer obtained by
I) polymerisation of one or more
a) monomer or oligomer according to claim 1 or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
or
II) grafting to a polymer backbone in a polymeranaloguous reaction, optionally with one or more mesogenic or non-mesogenic comonomers that are not of claim 1 , one or more
a) monomer or oligomer according to claim 1 , or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline.
19. A charge injection layer, planarising layer, antistatic film or conducting substrate or pattern for electronic applications or flat panel display, comprising
a monomer, oligomer or polymer of claim 1 ,
a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
an anisotropic polymer film with charge transport properties obtainable from a polymerisable liquid crystal material described above that is aligned in its liquid crystal phase into macroscopically uniform orientation and polymerised or crosslinked to fix the oriented state, or
a side chain liquid crystal polymer obtained by
I) polymerisation of one or more
a) monomer or oligomer according to claim 1 or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one polymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline,
or
II) grafting to a polymer backbone in a polymeranaloguous reaction, optionally with one or more mesogenic or non-mesogenic comonomers that are not of claim 1 , one or more
a) monomer or oligomer according to claim 1 , or
b) a polymerisable liquid crystal material comprising one or more monomer, oligomer or polymer according to claim 1 comprising at least one pblymerisable group, and optionally comprising one or more polymerisable compounds not of claim 1 , wherein at least one of the polymerisable compounds is mesogenic or liquid crystalline.
20. A monomer, oligomer or polymer according to claim 6 , wherein L is C 1 –C 20 -alkyl or C 1 –C 20 -fluoroalkyl.