Emissive sensors and devices incorporating these sensors

• US 8,367,001 B2
• Filed: 11/15/2010
• Issued: 02/05/2013
• Est. Priority Date: 05/05/1998
• Status: Expired due to Fees

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Swager, Timothy M., Zhang, Shi-Wei
• Primary Examiner(s): Warden, Jill
• Assistant Examiner(s): COLE, MONIQUE T
• Application Number:
  US12/946,685
• Publication Number:
  US 20110142717A1
• Time in Patent Office: 813 Days
• Field of Search: 436/127, 436/106, 436/104, 422/98, 422/68.1, 422/82.01, 422/82.07, 422/82.08, 546/348
• US Class Current: 422/82.05
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1092 containing sulfur as the only heteroatom
• CPC Class Codes: C09K 2211/1408 Carbocyclic compounds
• CPC Class Codes: C09K 2211/1425 Non-condensed systems
• 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 85/615 Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
• CPC Class Codes: H10K 85/649 Aromatic compounds comprising a hetero atom
• CPC Class Codes: H10K 85/657 Polycyclic condensed heteroaromatic hydrocarbons
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y10T 436/163333 Organic [e.g., chemical warfare agents, insecticides, etc.]
• CPC Class Codes: Y10T 436/17 Nitrogen containing
• CPC Class Codes: Y10T 436/20 Oxygen containing

Abstract

The present invention generally relates to luminescent and/or optically absorbing compositions and/or precursors to those compositions, including solid films incorporating these compositions/precursors, exhibiting increased luminescent lifetimes, quantum yields, enhanced stabilities and/or amplified emissions. The present invention also relates to sensors and methods for sensing analytes through luminescent and/or optically absorbing properties of these compositions and/or precursors. Examples of analytes detectable by the invention include electrophiles, alkylating agents, thionyl halides, and phosphate ester groups including phosphoryl halides, cyanides and thioates such as those found in certain chemical warfare agents. The present invention additionally relates to devices and methods for amplifying emissions, such as those produced using the above-described compositions and/or precursors, by incorporating the composition and/or precursor within a polymer having an energy migration pathway. In some cases, the compositions and/or precursors thereof include a compound capable of undergoing a cyclization reaction.

Claims

1. A sensor, comprising:

a substrate comprising a compound having a structure;

2. The sensor of claim 1, wherein at least a portion of the compound is able to undergo an intramolecular cyclization reaction upon reaction of the compound with an electrophile to form a cyclized product, wherein the electrophile comprises a phosphate ester.

3. The sensor of claim 2, wherein the electrophile comprises an electrophilic phosphorous, sulfur, or arsenic atom.

4. The sensor of claim 3, wherein the electrophilic phosphorous, sulfur, or arsenic atom is bonded to more than one electron-withdrawing moiety.

5. The sensor of claim 2, wherein the electrophile comprises an electrophilic carbon that is multiply-bonded another electrophilic atom.

6. The sensor of claim 2, wherein the electrophile is a chemical warfare agent.

7. The sensor of claim 1, wherein at least a portion of the compound undergoes an intramolecular cyclization reaction upon reaction with an electrophile to form a cyclized product, the intramolecular cyclization reaction comprising an intramolecular nucleophilic substitution reaction.

8. The sensor of claim 7, wherein the cyclized product has a greater emissivity than the compound.

9. The sensor of claim 1, wherein the compound has the following structure,

10. The sensor of claim 2, wherein the electrophile is sarin, phosgene, soman, tabun, thionyl chloride,

19. The sensor of claim 1, wherein two R groups are joined together to form an aromatic group selected from the group consisting of a benzene ring, a pyridine ring, a naphthalene ring, an anthracene ring, a pyridine ring, a quinoline ring, a thiophene ring, a furan ring, a quinolizine ring, and an iptycene moiety.

11. A method, comprising:

reacting a compound with an electrophile to produce a product having greater emissivity than the compound, wherein the product comprises at least a portion of the compound that has been cyclized upon reaction with the electrophile,

wherein the compound has the following structure,

13. The method of claim 11, wherein the electrophile is sarin, phosgene, soman, tabun, thionyl chloride,

14. The method of claim 11, wherein two R groups are joined together to form an aromatic group selected from the group consisting of a benzene ring, a pyridine ring, a naphthalene ring, an anthracene ring, a pyridine ring, a quinoline ring, a thiophene ring, a furan ring, a quinolizine ring, and an iptycene moiety.

15. The method of claim 11, wherein the compound has the following structure,

12. A method, comprising:

cyclizing at least a portion of a compound by reacting the compound with an electrophile, the compound having a structure;

16. The method of claim 12, wherein the electrophile is sarin, phosgene, soman, tabun, thionyl chloride,

17. The method of claim 12, wherein two R groups are joined together to form an aromatic group selected from the group consisting of a benzene ring, a pyridine ring, a naphthalene ring, an anthracene ring, a pyridine ring, a quinoline ring, a thiophene ring, a furan ring, a quinolizine ring, and an iptycene moiety.

18. The method of claim 12, wherein the compound has the following structure,