The present invention relates to new semiconductive oligomers and polymers, a process for their manufacture and their use in thin film electronic and optical devices, such as organic light emitting diodes (OLED) and photovoltaic devices, eg. solar cells and photodetectors.
1. An oligomer or polymer comprising an optionally substituted first repeat unit of formula (Ir):
wherein R 1 , R 2 , R 3 and R 4 , which may be the same or different, are independently selected from hydrogen or a substituent and two or more of R 1 , R 2 , R 3 and R 4 may be linked to form a ring and the oligomer or polymer comprises a second repeat unit.
2. An oligomer or polymer according to claim 1 wherein each R 1 , R 2 , R 3 and R 4 is independently selected from the group consisting of optionally substituted alkyl, alkoxy, aryl, or heteroaryl.
3. An oligomer or polymer according to claim 1 , wherein at least one of R 1 , R 2 , R 3 and R 4 is optionally substituted phenyl or optionally substituted C 1-20 alkyl.
4. An oligomer or polymer according to claim 3 wherein at least one R 1 , R 2 , R 3 and R 4 is different from at least one other R 1 , R 2 , R 3 and R 4 .
5. An oligomer or polymer according to claim 1 , wherein the second repeat unit is selected from optionally substituted aryl, heteroaryl and triarylamine repeat units.
6. An optionally substituted monomer of formula (Im):
wherein R 1 , R 2 , R 3 and R 4 , which may be the same or different, are independently selected from hydrogen or a substituent and two or more of R 1 , R 2 , R 3 and R 4 may be linked to form a ring; and
each P represents a polymerisable group.
7. A monomer according to claim 6 wherein each P represents a leaving group capable of participating in a polycondensation mediated by a metal of variable oxidation state.
8. A monomer according to claim 7 wherein each P is independently selected from halogen; a moiety of formula —O—SO 2 —Z wherein Z is selected from the group consisting of optionally substituted alkyl and aryl; or a reactive boron group selected from a boronic acid, a boronic ester or a borane.
9. A process for preparing an oligomer or polymer comprising the step of oligomerising or polymerising a monomer according to claim 6 .
10. A process for preparing an oligomer or polymer according to claim 9 wherein each P is independently a halogen or a moiety of formula —O—SO 2 —Z, and the monomer of formula (Im) is oligomerised or polymerised in the presence of a nickel complex catalyst.
11. A process for preparing a polymer according to claim 9 wherein the monomer of formula (Im) is oligomerised or polymerised with a second aromatic monomer in the presence of a palladium complex catalyst and a base and
a. each P is the same or different and comprises a reactive boronic group and the second monomer comprises two reactive groups independently selected from halogen and a moiety of formula —O—SO 2 —Z, or
b. each P independently comprises a halogen or a moiety of formula —O—SO 2 —Z and the second monomer comprises two reactive boron groups which are the same or different.
12. A process for preparing an ohgomer or polymer according to claim 9 , wherein one P is a reactive boron group and the other P is a halogen or a moiety of formula —O—SO 2 —Z.
13. An optical device comprising an oligomer or polymer according to claim 1 .
14. An optical device according to claim 13 wherein the oligomer or polymer is located between a first electrode for injection of charge carriers of a first type and a second electrode for injection of charge carriers of a second type.
15. A switching device comprising an oligomer or polymer according to claim 1 .
16. A field effect transistor comprising an insulator having a first side and a second side; a gate electrode located on the first side of the insulator; an oligomer or polymer according to claim 1 located on the second side of the insulator; and a drain electrode and a source electrode located on the oligomer or polymer.
17. An integrated circuit comprising a field effect transistor according to claim 16 .
18. A polymer comprising an optionally substituted first repeat unit of formula (Ir):
wherein R 1 , R 2 , R 3 and R 4 , which may be the same or different, are independently selected from hydrogen or a substituent and two or more of R 1 , R 2 , R 3 and R 4 may be linked to form a ring and the oligomer or polymer comprises a second repeat unit.