Electrically conducting oligo(pyrazoles)
Inventors
Martin, Brett D. • Trammell, Scott A. • Deschamps, Jeffrey R. • Naciri, Jawad • DePriest, Jeffrey
Assignees
Publication Number
US-10336705-B2
Publication Date
2019-07-02
Expiration Date
2034-05-16
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Abstract
An electrically conducting organic oligomer comprising 4-nitro-1H-pyrazole-3-yl-amine, 4-trifluoromethyl-1H-pyrazol-3-yl-amine, 4-trichloromethyl-1H-pyrazol-3-yl-amine, 4-tribromomethyl-1H-pyrazol-3-yl-amine, 4-ammonium-1H-pyrazol-3-yl-amine, 4-trimethylammonium-1H-pyrazol-3-yl-amine, 4-triethylammonium-1H-pyrazol-3-yl-amine, or 4-tripropylammonium-1H-pyrazol-3-yl-amine. An electrically conducting organic oligomer made from the steps of preparing an acidic aqueous solution with a monomer, preparing the acidic aqueous solution by mixing water with a monomer (3-amino-1H-pyrazole-4-carbonitrile), forming a solution preparing a second aqueous solution, mixing the acidic aqueous solution with the second aqueous solution, and allowing a reaction to proceed at about 40° C.
Core Innovation
This disclosure concerns two novel electrically conducting organic oligomers: oligo(3-amino-1H-pyrazole-4-carbonitrile) (oligo(AP-CN)) and oligo(4-nitro-1H-pyrazole-3-yl-amine) (oligo(AP-NO2)). These oligomers have highly variable redox states and good electron-transporting properties. They are easy to synthesize in a one-step process plus purification and use inexpensive starting materials.
The problem addressed is the need for renewable energy sources and improved materials for polymer solar cells. Conducting polymer photovoltaics face challenges including low photon-to-current conversion efficiencies and short lifetimes compared to silicon-based cells. Most conducting polymers are p-dopable only and stable in positively charged states, limiting efficient electron transport. There is a lack of stable n-dopable conducting polymers which are valuable for electron transport in photovoltaics, organic field effect transistors, and organic light-emitting diodes. Existing synthetic approaches are complex, multi-step, and expensive. The disclosed oligomers aim to provide materials with both n- and p-dopability, high electron conductivity, thermal stability, and easy synthesis from inexpensive precursors.
Claims Coverage
The patent includes one independent claim covering an electrically conducting organic oligomer comprised of specific substituted 1H-pyrazole-3-yl-amine compounds. The main inventive features relate to the chemical composition and structure of the oligomer.
Composition of the electrically conducting organic oligomer
The oligomer comprises at least one of the following substituents at the 4-position of 1H-pyrazole-3-yl-amine: 4-nitro, 4-trifluoromethyl, 4-trichloromethyl, 4-tribromomethyl, 4-ammonium, 4-trimethylammonium, 4-triethylammonium, or 4-tripropylammonium groups.
The independent claim defines the oligomer based on the specific 4-substituted 1H-pyrazole-3-yl-amine structural units that impart electrical conductivity properties, thereby covering oligomers composed of these moieties as the core inventive chemical features.
Stated Advantages
The oligomers have highly variable redox states allowing for quasi-reversible n-dopability and potential p-dopability, supporting efficient electron and hole transport.
They are easy to synthesize in one step with purification using inexpensive starting materials, facilitating commercial scalability and derivative production.
They exhibit high thermal stability with decomposition onset above 350° C., suitable for solar cell applications under harsh conditions.
They achieve significantly higher photocurrent generation compared to gold-coated electrodes and fullerene-coated electrodes, indicating superior electron transport performance.
They are soluble in common polar organic solvents, enabling easy processing for practical device fabrication.
Documented Applications
Use as electron transporters in polymer solar cells to improve photon-to-current conversion efficiencies.
Potential application in organic field effect transistors (OFETs) and organic light emitting diodes (OLEDs) due to their n-dopability.
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