Emissive polymers and devices incorporating these polymers

• US 20070081921A1
• Filed: 09/29/2006
• Published: 04/12/2007
• Est. Priority Date: 05/05/1998
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Swager, Timothy, Amara, John
• Granted Patent: US 8,198,096 B2
• Time in Patent Office: Days
• US Class Current: 422/82.50
• 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: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1425 Non-condensed systems
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: Y10T 436/14 Heterocyclic carbon compound [i.e. , O, S, N, Se, Te, as only ring hetero atom]
• CPC Class Codes: Y10T 436/145555 Hetero-N

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 such as heterocycles, 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 sensor, comprising:

a luminescent polymer comprising a hydrogen-bond donor,

wherein the hydrogen-bond donor is capable of interacting with an analyte to form a complex between the hydrogen-bond donor and the analyte, the complex being capable of interacting with the luminescent polymer and causing the luminescent polymer to signal the presence of the analyte,

wherein, in the absence of the hydrogen-bond donor, the analyte is less capable of interacting with the luminescent polymer.

2. A sensor as in claim 1, wherein the hydrogen-bond donor is capable of forming a hydrogen bond with the analyte to form the complex.

3. A sensor as in claim 1, wherein the complex is a charge transfer complex.

4. A sensor as in claim 1, wherein the hydrogen-bond donor is covalently bonded to the luminescent polymer.

5. A sensor as in claim 1, wherein the hydrogen-bond donor is chiral.

6. A sensor as in claim 1, wherein the luminescent polymer comprises a hydrogen-bond donor.

7. A sensor as in claim 6, wherein the hydrogen-bond donor is a group comprising an electron-withdrawing group.

8. A sensor as in claim 7, wherein the electron-withdrawing group comprises fluorine, nitro, acyl, cyano, or sulfonate.

9. A sensor as in claim 6, wherein the hydrogen-bond donor is a hexafluoroisopropanol group.

10. A sensor as in claim 1, wherein the analyte comprises a heterocycle comprising nitrogen.

11. A sensor as in claim 1, wherein the analyte is 2,4-dinitrotoluene, 4-aminopyridine, N,N′

-dimethylamino-pyridine, pyridine, or 2,4-dichloro-pyrimidine.

12. A sensor as in claim 1, wherein the luminescent polymer is a polyarylene, polyarylene vinylene, polyarylene ethynylene, ladder polymer, or substituted derivative thereof.

13. A method as in claim 1, wherein the luminescent polymer has the structure,

14. A sensor as in claim 1, wherein the luminescent polymer has the structure,

15. A sensor as in claim 14, wherein at least one of R²⁷ and R²⁸ comprises the structure,

16. A sensor as in claim 14, wherein at least one of R²⁷ and R²⁸ has the structure,

17. A sensor as in claim 1, further comprising a source of energy applicable to the luminescent polymer to cause emission of radiation;

and

an emission detector positionable to detect the emission.

18. A method for determination of an analyte, comprising:

providing a luminescent polymer comprising a hydrogen-bond donor;

exposing the luminescent polymer to a sample suspected of containing an analyte, wherein the analyte, if present, interacts with the hydrogen-bond donor to cause a change in the luminescence of the polymer; and

determining the change in the luminescence of the polymer, thereby determining the analyte,

wherein, in the absence of the hydrogen-bond donor, the analyte produces a lower degree of change in the luminescence of the polymer.

19. A method as in claim 18, wherein the interacting comprises forming a complex between the hydrogen-bond donor and the analyte.

20. A method as in claim 18, wherein the hydrogen-bond donor forms a hydrogen bond with the analyte to form the complex.

21. A method as in claim 19, wherein the complex is a charge transfer complex.

22. A method as in claim 18, wherein the hydrogen-bond donor is covalently bonded to the luminescent polymer.

23. A method as in claim 18, wherein the hydrogen-bond donor is chiral.

24. A method as in claim 18, wherein the luminescent polymer comprises a hydrogen-bond donor.

25. A method as in claim 18, wherein the analyte has a reduction potential which is made less negative upon its interaction with the hydrogen-bond donor.

26. A method as in claim 18, wherein the hydrogen-bond donor is a group comprising an electron-withdrawing group.

27. A method as in claim 26, wherein the electron-withdrawing group comprises fluorine, nitro, acyl, cyano, or sulfonate.

28. A method as in claim 18, wherein the hydrogen-bond donor is a hexafluoroisopropanol group.

29. A method as in claim 18, wherein the analyte comprises a heterocycle comprising nitrogen.

30. A method as in claim 18, wherein the hydrogen-bond donor is covalently bonded to the luminescent polymer.

31. A method as in claim 18, wherein the change comprises a decrease in luminescence intensity.

32. A method as in claim 18, wherein the change comprises an increase in luminescence intensity.

33. A method as in claim 18, wherein the change comprises a change in the wavelength of the luminescence.

34. A method as in claim 18, wherein the change is caused by a photoinduced charge transfer reaction between the luminescent polymer and the complex.

35. A method as in claim 18, wherein the luminescent polymer comprises a first monomer and a second monomer, wherein the first monomer is non-planar with respect to the second monomer.