Emissive polymers and devices incorporating these polymers

• US 7,662,309 B2
• Filed: 10/17/2005
• Issued: 02/16/2010
• Est. Priority Date: 05/05/1998
• Status: Expired due to Fees

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Yang, Jye-Shane, Williams, Vance, Miao, Yijun, Levitsky, Igor A., Kim, Jinsang, Swager, Timothy M., Lugmair, Claus G., Deans, Robert
• Primary Examiner(s): Griffin; Walter D
• Assistant Examiner(s): Mui; Christine T
• Application Number:
  US11/252,419
• Publication Number:
  US 20060120917A1
• Time in Patent Office: 1,583 Days
• Field of Search: 422/82, 422/50, 422/81, 422/68.1, 252/582, 252/586, 252/587, 252/588
• US Class Current: 252/301.35
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: C08F 232/00 Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08G 61/00 Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule C08G2/00 - C08G16/00 take precedence
• CPC Class Codes: C08G 61/10 only aromatic carbon atoms, e.g. polyphenylenes
• CPC Class Codes: C08L 101/12 characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity liquid crystal materials or compositions C09K19/00
• CPC Class Codes: C08L 65/00 Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C08L7/00 - C08L57/00, C08L61/00 take precedence; Compositions of derivatives of such polymers
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G01N 2021/7786 Fluorescence
• CPC Class Codes: G01N 21/6428 Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" in vivo A61B5/00; immunoassay G01N33/53
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 21/7703 using reagent-clad optical fibres or optical waveguides using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B
• CPC Class Codes: H10K 10/466 Lateral bottom-gate IGFETs comprising only a single gate
• CPC Class Codes: H10K 10/701 Organic molecular electronic devices
• CPC Class Codes: H10K 30/65 Light-sensitive field-effect devices, e.g. phototransistors
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/151 Copolymers
• CPC Class Codes: H10K 85/154 Ladder-type polymers
• CPC Class Codes: H10K 85/30 : Coordination compounds
• CPC Class Codes: H10K 85/615 : Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
• CPC Class Codes: Y02E 10/549 : Organic PV cells

Abstract

The present invention relates to a class of luminescent and conductive polymer compositions having chromophores, and particularly solid films of these compositions exhibiting increased luminescent lifetimes, quantum yields and amplified emissions. These desirable properties can be provided through polymers having rigid groups designed to prevent polymer reorganization, aggregation or π-stacking upon solidification. These polymers can also display an unusually high stability with respect to solvent and heat exposures. The invention also relates to a sensor and a method for sensing an analyte through the luminescent and conductive properties of these polymers. Analytes can be sensed by activation of a chromophore at a polymer surface. Analytes include aromatics, phosphate ester groups and in particular explosives and chemical warfare agents in a gaseous state. The present invention also relates to devices and methods for amplifying emissions by incorporating a polymer having an energy migration pathway and/or providing the polymer as a block co-polymer or as a multi-layer.

Claims

1. A polymeric composition, comprising:

a conjugated π

-backbone, the π

-backbone comprising a plane of atoms; and

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

,

wherein the polymeric composition comprises a rigid three-dimensional structure such that in a first and a second optical spectrum of the composition, maxima in the first spectrum differ by no more than about 15 nm from corresponding maxima in the second spectrum, the second spectrum being obtained after exposing the composition, characterized by the first spectrum, to an organic solvent that does not dissolve the composition.

2. A polymeric composition as in claim 1, wherein the sum of the first and second heights is at least about 5.0 Å

.

3. A polymeric composition as in claim 1, which, when prepared as a film and exposed to electromagnetic radiation, has a luminescence quantum yield of at least about 0.1 times the quantum yield of the polymeric composition in solution upon exposure to the same conditions of electromagnetic radiation as the film.

4. A polymeric composition as in claim 3, wherein the film has a luminescence quantum yield of at least about 0.15 times the quantum yield of the polymeric composition in solution.

5. A polymeric composition as in claim 3, wherein the film has a luminescence quantum yield of at least about 0.2 times the quantum yield of the polymeric composition in solution.

6. A polymeric composition as in claim 3, wherein the film has a luminescence quantum yield of at least about 0.3 times the quantum yield of the polymeric composition in solution.

7. A polymeric composition as in claim 3, wherein the film has a luminescence quantum yield of at least about 0.4 times the quantum yield of the polymeric composition in solution.

8. A polymeric composition as in claim 3, wherein the film has a luminescence quantum yield of at least about 0.5 times the quantum yield of the polymeric composition in solution.

9. A polymeric composition as in claim 1, wherein the maxima in the first spectrum differ by no more than about 10 nm from corresponding maxima in the second spectrum.

10. A polymeric composition as in claim 1, wherein the maxima in the first spectrum differ by no more than about 5 nm from corresponding maxima in the second spectrum.

11. A polymeric composition as in claim 1, wherein the maxima in the second spectrum have an intensity change of less than about 10% relative to the maxima in the first spectrum.

12. A polymeric composition as in claim 11, wherein the intensity change is less than about 15%.

13. A polymeric composition as in claim 1, comprising a rigid three-dimensional structure such that in a first and second optical spectra of the composition, maxima in the first spectrum differ by no more than 15 nm from corresponding maxima in the second spectrum, the second spectrum being obtained after heating the composition to a temperature of no more than 150°

C.

14. A polymeric composition as in claim 13, wherein the maxima in the first spectrum differ by no more than about 10 nm from corresponding maxima in the second spectrum.

15. A polymeric composition as in claim 13, wherein the maxima in the first spectrum differ by no more than about 5 nm from corresponding maxima in the second spectrum.

16. A polymeric composition as in claim 13, wherein the maxima in the second spectrum have an intensity change of less than about 10% relative to the maxima in the first spectrum.

17. A polymeric composition as in claim 16, wherein the intensity change is less than about 15%.

18. A polymeric composition as in claim 1, wherein the backbone is free from π

-stacking.

19. A polymeric composition as in claim 1, wherein the π

-backbone comprises the structure;

20. A polymeric composition as in claim 19, wherein E_a is attached to the π

-backbone and the polymeric composition comprises the structure;

21. A polymeric composition as in claim 20, wherein G and H may be the same or different, and each is selected from the group consisting of:

22. A polymeric composition as in claim 21, wherein A is selected from the group consisting of:

23. A polymeric composition as in claim 21, wherein at least one of G, H, I and J comprises a naphthalene group, the naphthalene group being a component of an exciplex structure.

24. A polymeric composition as in claim 20, wherein the composition is essentially rigid with respect to structural rearrangement under conditions selected from the group consisting of heating the composition to a temperature of less than about 150°

C. and exposing the composition to an organic solvent that does not dissolve the composition.

25. A polymeric composition as in claim 20, which, when prepared as a film and exposed to electromagnetic radiation, has a luminescence quantum yield of at least about 0.1 times the quantum yield of the polymeric composition in solution upon exposure to the same conditions of electromagnetic radiation as the film.

27. A polymeric composition as in claim 19 comprising the structure:

28. A polymeric composition as in claim 19, comprising the structure:

29. A polymeric composition as in claim 19, which, when prepared as a film and exposed to electromagnetic radiation, has a luminescence quantum yield of at least about 0.1 times the quantum yield of the polymeric composition in solution upon exposure to the same conditions of electromagnetic radiation as the film.

26. A polymeric composition, comprising:

a conjugated π

- backbone, the π

-backbone comprising a plane of atoms; and

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

,

wherein the π

-backbone comprises the structure;

30. A polymeric composition, comprising:

a conjugated π

-backbone, the π

-backbone comprising a plane of atoms; and

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

,

wherein the π

-backbone comprises the structure;

31. A polymeric composition as in claim 30, wherein the maxima in the second spectrum have an intensity of less than about 10% than the maxima in the first spectrum.

32. A polymeric composition, comprising:

a conjugated π

-backbone, the π

-backbone comprising a plane of atoms; and

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

,

wherein the π

-backbone comprises the structure;

33. A polymeric composition as in claim 32, wherein the maxima in the second spectrum have an intensity of less than about 10% than the maxima in the first spectrum.

34. A polymeric composition, comprising:

a conjugated π

-backbone, the π

-backbone comprising a plane of atoms; and

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

,

wherein the π

-backbone comprises the structure;

35. A polymeric composition, comprising:

a conjugated π

-backbone, the π

-backbone comprising a plane of atoms; and

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

,

wherein the polymeric composition comprises a rigid three-dimensional structure such that in a first and second optical spectra of the composition, maxima in the first spectrum differ by no more than 15 nm from corresponding maxima in the second spectrum, the second spectrum being obtained after heating the composition to a temperature of no more than 150°

C.

36. A polymeric composition as in claim 35, wherein the sum of the first and second heights is at least about 5.0 Å

.

37. A polymeric composition as in claim 35, wherein the maxima in the first spectrum differ by no more than about 10 nm from corresponding maxima in the second spectrum.

38. A polymeric composition as in claim 35, wherein the maxima in the first spectrum differ by no more than about 5 nm from corresponding maxima in the second spectrum.

39. A polymeric composition as in claim 35, wherein the maxima in the second spectrum have an intensity change of less than about 10% relative to the maxima in the first spectrum.

40. A polymeric composition as in claim 39, wherein the intensity change is less than about 15%.

41. A polymeric composition, comprising:

a conjugated π

-backbone, the π

-backbone comprising a plane of atoms; and

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

,

wherein the backbone is free from π

-stacking.

42. A polymeric composition as in claim 41, wherein the sum of the first and second heights is at least about 5.0 Å

.

43. A polymeric composition as in claim 41, which, when prepared as a film and exposed to electromagnetic radiation, has a luminescence quantum yield of at least about 0.1 times the quantum yield of the polymeric composition in solution upon exposure to the same conditions of electromagnetic radiation as the film.

44. A polymeric composition as in claim 43, wherein the film has a luminescence quantum yield of at least about 0.15 times the quantum yield of the polymeric composition in solution.

45. A polymeric composition as in claim 43, wherein the film has a luminescence quantum yield of at least about 0.2 times the quantum yield of the polymeric composition in solution.

46. A polymeric composition as in claim 43, wherein the film has a luminescence quantum yield of at least about 0.3 times the quantum yield of the polymeric composition in solution.

47. A polymeric composition as in claim 43, wherein the film has a luminescence quantum yield of at least about 0.4 times the quantum yield of the polymeric composition in solution.

48. A polymeric composition as in claim 43, wherein the film has a luminescence quantum yield of at least about 0.5 times the quantum yield of the polymeric composition in solution.

49. A polymeric composition as in claim 41, wherein the maxima in the first spectrum differ by no more than about 10 nm from corresponding maxima in the second spectrum.

50. A polymeric composition as in claim 41, wherein the maxima in the first spectrum differ by no more than about 5 nm from corresponding maxima in the second spectrum.

51. A polymeric composition as in claim 41, wherein the maxima in the second spectrum have an intensity change of less than about 10% relative to the maxima in the first spectrum.

52. A polymeric composition as in claim 51, wherein the intensity change is less than about 15%.

53. A polymeric composition, comprising:

a conjugated π

-backbone, the π

-backbone comprising a plane of atoms; and

a first group and a second group attached to the π

-backbone, the first group having a first fixed height above the plane and the second group having a second fixed height below the plane wherein a sum of the first and second heights is at least about 4.5 Å

,

wherein the π

-backbone comprises the structure;

54. A polymeric composition as in claim 53, wherein G and H may be the same or different, and each is selected from the group consisting of:

55. A polymeric composition as in claim 54, wherein A is selected from the group consisting of:

56. A polymeric composition as in claim 54, wherein at least one of G, H, I and J comprises a naphthalene group, the naphthalene group being a component of an exciplex structure.

57. A polymeric composition as in claim 53, wherein the composition is essentially rigid with respect to structural rearrangement under conditions selected from the group consisting of heating the composition to a temperature of less than about 150°

C. and exposing the composition to an organic solvent that does not dissolve the composition.

58. A polymeric composition as in claim 53, comprising the structure:

59. A polymeric composition as in claim 53, comprising the structure: