Fluorescent, semi-conductive polymers, and devices comprising them

• US 20050196775A1
• Filed: 12/06/2004
• Published: 09/08/2005
• Est. Priority Date: 12/04/2003
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Swager, Timothy M., Kim, Youngmi
• Granted Patent: US 7,700,366 B2
• Time in Patent Office: Days
• US Class Current: 435/6.14
• CPC Class Codes: C08G 61/02 Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• CPC Class Codes: C08G 61/06 prepared by ring-opening of carbocyclic compounds
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1425 Non-condensed systems
• CPC Class Codes: G01N 33/582 with fluorescent label
• CPC Class Codes: H05B 33/14 characterised by the chemical or physical composition or the arrangement of the electroluminescent material , or by the simultaneous addition of the electroluminescent material in or onto the light source
• 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 85/114 Poly-phenylenevinylene; Derivatives thereof
• CPC Class Codes: Y02E 10/549 Organic PV cells

Abstract

The present invention relates to fluorescent, semiconductive polymers comprising electron withdrawing groups bonded to the polymer. The invention also relates to a method of detecting analytes comprising contacting the analyte with the fluorescent, semiconductive polymers of the present invention. The invention also relates to light emitting devices, photovoltaic devices, and sensors comprising the fluorescent, semiconductive polymers of the present invention.

Claims

1. A fluorescent, semiconductive polymer comprising a conjugated backbone and electron withdrawing groups bonded to the polymer.

2. The fluorescent, semiconductive polymer of claim 1, wherein the polymer is soluble in an organic solvent.

3. The fluorescent, semiconductive polymer of claim 1, wherein the electron withdrawing groups are not bonded directly to the conjugated backbone.

4. The fluorescent, semiconductive polymer of claim 1, wherein the electron withdrawing groups are not bonded directly to the conjugated backbone and the fluorescent, semiconductive polymer comprises a hyperconjugated 3-D structure.

5. The fluorescent, semiconductive polymer of claim 1, wherein the electron withdrawing groups are directly bonded to the conjugated backbone.

6. The fluorescent, semiconductive polymer of claim 1, wherein the polymer comprises a moiety where the electron withdrawing group is not bonded directly to the conjugated backbone, and a moiety where the electron withdrawing group is bonded directly to the conjugated backbone.

7. The fluorescent, semiconductive polymer of claim 1, wherein the electron withdrawing groups are selected from the group consisting of esters, perhalogenated alkyls, perhalogenated aryls, nitriles, or electron deficient heteroaryls.

8. The fluorescent, semiconductive polymer of claim 6, wherein the electron withdrawing groups are perfluorinated alkyls.

9. The fluorescent, semiconductive polymer of claim 7, wherein the perfluorinated alkyls are perfluorinated C₁-C₁₂ alkyls.

10. The fluorescent, semiconductive polymer of claim 8, wherein the perfluorinated alkyls are selected from the group consisting of —

CF₃, —

C₄F₉, —

C₈F₁₇, —

C₁₀F₂₁, or mixtures thereof.

11. The fluorescent, semiconductive polymer of claim 1, wherein the fluorescent, semiconductive polymer represented by formula Ia, Ib, Ic or Id:

12. The fluorescent, semiconductive polymer of claim 11, wherein R is an ester or a perhalogenated alkyl group.

13. The fluorescent, semiconductive polymer of claim 11, wherein R is an ester.

14. The fluorescent, semiconductive polymer of claim 11, wherein R is —

CO₂CH₃ or —

CO₂C(CH₃)₃.

15. The fluorescent, semiconductive polymer of claim 11, wherein R is a perfluorinated alkyl group.

16. The fluorescent, semiconductive polymer of claim 11, wherein R is a perfluorinated C_1-12 alkyl group.

17. The fluorescent, semiconductive polymer of claim 11, wherein R₁ is —

CF₃, —

C₄F₉, C₈F₁₇, or —

C₁₀F₂₁.

18. The fluorescent, semiconductive polymer of claim 11, wherein R₁ is —

CF₃.

19. The fluorescent, semiconductive polymer of claim 11, wherein R₁ is —

C₄F₉.

20. The fluorescent, semiconductive polymer of claim 11, wherein R₁ is —

C₈F₁₇.

21. The fluorescent, semiconductive polymer of claim 11, wherein R₁ is —

C₁₀F₂₁.

22. The fluorescent, semiconductive polymer of claim 11, wherein at least one set of two R groups taken together form an electron deficient heteroaryl group.

23. The fluorescent, semiconductive polymer of claim 11, wherein R₁ is H.

24. The fluorescent, semiconductive polymer of claim 11, wherein A is a fused benzene ring.

25. The fluorescent, semiconductive polymer of claim 11, wherein n is greater than about 10, 100, or 1000.

26. The fluorescent, semiconductive polymer of claim 11, wherein R is —

CO₂Me, R₁ is H, A is a fused benzene ring, and n is greater than about 10, 100, or 1000.

27. The fluorescent, semiconductive polymer of claim 11, wherein R is —

CF₃, R₁ is H, A is a fused benzene ring, and n is greater than about 10, 100, or 1000.

28. The fluorescent, semiconductive polymer of claim 1, wherein the fluorescent, semiconductive polymer comprises formula II:

29. The fluorescent, semiconductive polymer of claim 28, wherein B is a double bond.

30. The fluorescent, semiconductive polymer of claim 28, wherein B is a triple bond.

31. The fluorescent, semiconductive polymer of claim 28, wherein B is aryl.

32. The fluorescent, semiconductive polymer of claim 28, wherein R is a perhalogenated alkyl.

33. The fluorescent, semiconductive polymer of claim 28, wherein R is a perfluorinated alkyl.

34. The fluorescent, semiconductive polymer of claim 28, wherein R is an ester.

35. The fluorescent, semiconductive polymer of claim 28, wherein R is —

CO₂CH₃ or —

CO₂C(CH₃)₃.

36. The fluorescent, semiconductive polymer of claim 28, wherein R is —

CF₃, —

C₄F₉, —

C₈F₁₇, or —

C₁₀F₂₁.

37. The fluorescent, semiconductive polymer of claim 28, wherein R is —

CF₃.

38. The fluorescent, semiconductive polymer of claim 28, wherein R is —

C₄F₉.

39. The fluorescent, semiconductive polymer of claim 28, wherein R is —

C₈F₁₇.

40. The fluorescent, semiconductive polymer of claim 28, wherein R is —

C₁₀F₂₁.

41. The fluorescent, semiconductive polymer of claim 28, wherein at least one R¹ is a perfluorinated C_1-12 alkyl.

42. The fluorescent, semiconductive polymer of claim 28, wherein two R¹ are perfluorinated C_1-12 alkyls.

43. The fluorescent, semiconductive polymer of claim 28, wherein at least one R¹ is a C_1-12 alkoxy group.

44. The fluorescent, semiconductive polymer of claim 28, wherein two R¹ are C_1-12 alkoxy groups.

45. The fluorescent, semiconductive polymer of claim 28, wherein a is 2.

46. The fluorescent, semiconductive polymer of claim 28, wherein m and n are greater than about 10, 100, or 1000.

47. The fluorescent, semiconductive polymer of claim 28, wherein two sets of adjacent R¹ each form a monocyclic ring.

48. The fluorescent, semiconductive polymer of claim 28, wherein two sets of adjacent R¹ each form a bicyclic ring.

49. The fluorescent, semiconductive polymer of claim 28, wherein two sets of adjacent R¹ each form a tricyclic ring.

50. The fluorescent, semiconductive polymer of claim 28, wherein two sets of adjacent R¹ each form a tetracyclic ring.

51. The fluorescent, semiconductive polymer of claim 28, wherein two sets of adjacent R¹ each form either a monocyclic, bicyclic, tricyclic, or tetracyclic structure wherein at least one structure comprises an electron deficient heteroaryl ring.

52. The fluorescent, semiconductive polymer of claim 28, wherein two sets of R¹ are each independently selected from the group consisting of

53. A method of detecting an analyte, comprising:

a) contacting an analyte with a fluorescent, semiconductive polymer of claim 1, 11, or 28, thereby aggregating the fluorescent, semiconductive polymes and thereby optionally forming an emissive exciplex;

wherein the maximum emission wavelength of said exciplex is not the same as the maximum emission wavelength of the fluorescent, semiconductive polymer; and

b) detecting the partial or complete quenching of the fluorescence of the fluorescent, semiconductive polymer or the emission of the exciplex or both.

54. The method of claim 53, wherein said analyte is a molecule comprising an electron donating moiety.

55. The method of claim 53, wherein said contact results in the partial or complete quenching of the fluorescence of the fluorescent, semiconductive polymer.

56. The method of claim 53, wherein the maximum emission wavelength of the fluorescent, semiconductive polymer and the maximum emission wavelength of the exciplex are separated by at least about 150 nm.

57. The method of claim 53, wherein the maximum emission wavelength of the fluorescent, semiconductive polymer and the maximum emission wavelength of the exciplex are separated by at least about 200 nm.

58. The method of claim 53, wherein the maximum emission wavelength of the fluorescent, semiconductive polymer and the maximum emission wavelength of the exciplex are separated by at least about 250 nm.

59. The method of claim 53, wherein the maximum emission wavelength of the fluorescent, semiconductive polymer and the maximum emission wavelength of the exciplex are separated by at least about 300 nm.

60. The method of claim 53, the fluorescent, semiconductive polymer having a first emission spectrum and the exciplex having a second emission spectrum, wherein the first emission spectrum and the second emission spectrum overlap by less than about 10%.

61. The method of claim 60, wherein the overlap is less than about 5%.

62. The method of claim 53, the fluorescent, semiconductive polymer having a first emission lifetime, the exciplex having a second emission lifetime, wherein the first emission lifetime is at least about 100 times greater than the second emission lifetime.

63. The method of claim 53, wherein the fluorescent, semiconductive polymer has a maximum emission wavelength less than about 700 nanometers.

64. The method of claim 53, wherein the exciplex has a maximum emission wavelength greater than about 700 nanometers.

65. The method of claim 53, wherein the analyte is a biological molecule.

66. The method of claim 65, wherein the biological molecule is a protein.

67. The method of claim 65, wherein the biological molecule is a peptide.

68. The method of claim 65, wherein the biological molecule is a mono- or oligonucleotide.

69. The method of claim 65, wherein the biological molecule is an RNA.

70. The method of claim 65, wherein the biological molecule is a DNA.

71. The method of claim 65, wherein the biological molecule is detected when it complexes with another peptide molecule, small molecule, RNA, or DNA.

72. A light emitting device comprising the fluorescent, semiconductive polymer of claim 1, 11, or 28 and a source of electrical current comprising an electrode capable of supplying the fluorescent, semiconductive polymer with electrons.

73. The light emitting device of claim 72, wherein the fluorescent, semiconductive polymer comprises perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-carbon bonds are formed.

74. The light emitting device of claim 72, wherein the fluorescent, semiconductive polymer comprises perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-fluoride complexes are formed.

75. The light emitting device of claim 72, wherein the fluorescent, semiconductive polymer comprises a nitrogen containing electron deficient heteroaryl, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-nitrogen bonds are formed.

76. The light emitting device of claim 72, wherein the fluorescent, semiconductive polymer comprises a nitrogen containing electron deficient heteroaryl and perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-nitrogen bonds are formed.

77. The light emitting device of claim 72, wherein the fluorescent, semiconductive polymer comprises a nitrogen containing electron deficient heteroaryl and perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, new metal-carbon bonds are formed.

78. The light emitting device of claim 72, wherein the fluorescent, semiconductive polymer comprises a nitrogen containing electron deficient heteroaryl and perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, new metal-fluoride complexes are formed.

79. A sensor comprising the fluorescent, semiconductive polymer of claim 1, 11, or 28 and a detector capable of detecting a decrease in fluorescence or an increase in fluorescence or both.

80. The sensor of claim 79, wherein the sensor is a biosensor.

81. A photovoltaic device comprising the fluorescent, semiconductive polymer of claim 1, 11, or 28 and a source of electrical current comprising an electrode, wherein the photovoltaic cell is capable of displaying a current or voltage in response to the presence of photons that can be absorbed by the polymer.

82. The photovoltaic device of claim 81, wherein the fluorescent, semiconductive polymer comprises perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-carbon bonds are formed.

83. The photovoltaic device of claim 81, wherein the fluorescent, semiconductive polymer comprises perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-fluoride complexes are formed.

84. The photovoltaic device of claim 81, wherein the fluorescent, semiconductive polymer comprises a nitrogen containing electron deficient heteroaryl, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-nitrogen bonds are formed.

85. The photovoltaic device of claim 81, wherein the fluorescent, semiconductive polymer comprises a nitrogen containing electron deficient heteroaryl and perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-nitrogen bonds are formed.

86. The photovoltaic device of claim 81, wherein the fluorescent, semiconductive polymer comprises a nitrogen containing electron deficient heteroaryl and perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-carbon bonds are formed.

87. The photovoltaic device of claim 81, wherein the fluorescent, semiconductive polymer comprises a nitrogen containing electron deficient heteroaryl and perfluorinated alkyls and/or perfluorinated aryls, wherein at the interface between the electrode and the fluorescent, semiconductive polymer, metal-fluoride complexes are formed.