Luminescent polymers
View Patent ↗A monomer which luminesces in the visible region upon excitation is described of the formula: M n+ (L) n− (CL) x in which n+ is the valency of M, (L) represents one or more anionic ligands with a total valency of n such that at least one of the ligands possesses the formula: Ch-X—Y wherein Ch represents a chelating group which is a ligand fragment comprising the chelate binding sites and the part of the rest of the ligand with which the binding sites are conjugated, Y represents an olefinic group and X represents a spacer comprising a chain of at least 4 carbon and/or hetero atoms, x is 0, 1, or 2, CL represents a neutral co-ligand and M represents a metal atom of group 2, 12, 13, d-block or f-block with the proviso that if Y is part of a styrene or substituted styrene group then M is a f-block or d-block metal.
1. A monomer which luminesces in the visible region upon excitation having the formula:
M n+ (L) n− (CL) x
wherein n+ is the valency of M, (L) represents one or more anionic ligands with a total valency of n− such that at least one of the ligands possesses the formula
Ch-X—Y
wherein Ch represents a chelating group which is a ligand fragment comprising the chelate binding sites and the part of the rest of the ligand with which the binding sites are conjugated, Y represents an olefinic group and X represents a spacer comprising a chain of at least four carbon and/or hetero atoms, x is 0, 1, or 2, CL represents a neutral co-ligand, and M represents a metal atom of group 2, 12, 13, or d-block with the proviso that if Y is part of a styrene or substituted styrene group then M is a d-block metal.
2. A monomer according to claim 1 , wherein Ch is an oxygen or nitrogen donor system.
3. A monomer according to claim 1 , wherein Ch is a carboxylic acid, dicarboxylic acid, hydroxycarboxylic acid, β-diketonate group or hydroxyquinoline group.
4. A monomer according to claim 1 , wherein the spacer comprises 6 to 12 atoms.
5. A monomer according to claim 1 , wherein the spacer comprises carbon atoms and, optionally, oxygen atoms.
6. A monomer according to claim 1 , wherein the spacer comprises a donor or coordinating group.
7. A monomer according to claim 1 , wherein Y is part of an acrylate or substituted acrylate group.
8. A monomer according to claim 7 , wherein Y is part of a methacrylate group.
9. A monomer according to claim 1 , wherein M is selected from the group consisting of europium, samarium, terbium, dysprosium, cerium, yttrium, and gadolinium.
10. A monomer according to claim 9 , wherein (L) represents more than one anionic ligand, and at least one anionic ligand (L) does not possess the formula Ch-X-Y and comprises isoquinoline carboxylic acid, l-naphthoic acid, or 4-tert butylbenzoic acid.
11. A monomer according to claim 1 , wherein M is selected from the group consisting of beryllium, zinc, aluminium, iridium, rhodium, osmium, platinum, and ruthenium.
12. A monomer according to claim 11 , wherein (L) represents more than one anionic ligand, and at least one anionic ligand (L) does not possess the formula Ch-X-Y and comprises 8-hydroxyquinoline.
13. A monomer according to claim 1 , wherein (L) represents more than one anionic ligand and at least one anionic ligand (L) does not possess the formula Ch-X-Y.
14. A monomer according to claim 13 , wherein the anionic ligand (L) which does not possess the formula Ch-X-Y is phenyl pyridine.
15. A monomer according to claim 13 , wherein the anionic ligand (L) which does not possess the formula Ch-X-Y is isoquinoline carboxylic acid, 1-naphthoic acid, or 4-tert butylbenzoic acid.
16. A monomer according to claim 13 , wherein the anionic ligand(L) which does not possess the formula Ch-X-Y is 8-hydroxyquinoline.
17. A monomer according to claim 1 , wherein x is 1 or 2.
18. A monomer according to claim 1 , wherein Ch-X-Y has the formula:
19. A monomer according to claim 1 , wherein Y has the formula:
wherein R 1 and R 2 , which are the same or different, represent a hydrogen atom, or an alkyl radical of 1 to 6 carbon atoms.
20. A process for making a light emitting device comprising:
subjecting a monomer to radical initiation so as to polymerize the monomer to form a polymer, said monomer having the formula:
M + (L) n− (CL) x
wherein n+ is the valency of M, (L) represents one or more anionic ligands with a total valency of n− such that at least one of the ligands possesses the formula
Ch-X—Y
wherein Ch represents a chelating group which is a ligand fragment comprising the chelate binding sites and the part of the rest of the ligand with which the binding sites are conjugated, Y represents an olefinic group and X represents a spacer comprising a chain of at least 4 four carbon and/or hetero atoms, x is 0, 1, or 2, CL represents a neutral co-ligand, and M represents a metal atom of group 2, 12, 13, d-block or f-block with the proviso that if Y is part of a styrene or substituted styrene group then M is a f-block or d-block metal.
21. A process according to claim 20 comprising achieving radical initiation with UV light or visible light, and a photo initiator.
22. A process according to claim 20 , comprising carrying out polymerization in situ where the polymer is desired.
23. A process according to 22 , comprising spincasting a solution of the monomer to form a layer of the light emitting device and then polymerizing the monomer.
24. A process according to claim 23 , comprising polymerizing using a photo mask, and removing unexposed portions using an organic solvent in which the monomer is soluble.
25. A process according to claim 20 , further comprising coating a substrate with a solution containing the monomer prior to subjecting the monomer to radical initiation.
26. A process for making a light emitting device comprising:
subjecting a monomer to actinic radiation so as to polymerize the monomer to form a polymer, said monomer having the formula:
M + (L) n− (CL) x
wherein n+ is the valency of M, (L) represents one or more anionic ligands with a total valency of n− such that at least one of the ligands possesses the formula
Ch-X—Y
wherein Ch represents a chelating group which is a ligand fragment comprising the chelate binding sites and the part of the rest of the ligand with which the binding sites are conjugated, Y represents an olefinic group and X represents a spacer comprising a chain of at least 4 four carbon and/or hetero atoms, x is 0, 1, or 2, CL represents a neutral co-ligand, and M represents a metal atom of group 2, 12, 13, d-block or f-block with the proviso that if Y is part of a styrene or substituted styrene group then M is a f-block or d-block metal.
27. A process according to claim 26 , comprising carrying out polymerization in situ where the polymer is desired.
28. A process according to claim 27 , comprising spincasting a solution of the monomer to form a layer of the light emitting device and then polymerizing the monomer.
29. A process according to claim 28 , comprising polymerizing using a photo mask, and removing unexposed portions using an organic solvent in which the monomer is soluble.
30. A process according to claim 26 , further comprising coating a substrate with a solution containing the monomer prior to subjecting the monomer to actinic radiation.
31. A light emitting device which comprises a layer of a polymer which possesses recurring units of the formula:
M n+ (L) n− (CL) x
wherein M represents a metal atom of group 2, 12, 13,d-block or f-block, n+ is the valency of M, CL represents a neutral co-ligand, x is 0, 1, or 2, and (L) represents one or more anionic ligands with a total valency of n−such that at least one of the ligands possesses the formula:
wherein Ch represents a chelating group which is a ligand fragment comprising the chelate binding sites and the part of the rest of the ligand with which the binding sites are conjugated, X represents a spacer comprising a chain of at least four carbon and/or hetero atoms, R 1 and R 2 , which are the same or different, represent a hydrogen atom, or an alkyl radical of 1 to 6 carbon atoms, and C 1 and C 2 represent first and second carbon atoms.
32. A light emitting device according to claim 31 , comprising a transparent substrate layer, a transparent electrode layer, a light emitting layer, and a back electrode, wherein the light emitting layer comprises said polymer.