A photo- and electrochemically-active porphyrin-fullerene dyad electropolymer.
Identifieur interne : 001B37 ( Main/Exploration ); précédent : 001B36; suivant : 001B38A photo- and electrochemically-active porphyrin-fullerene dyad electropolymer.
Auteurs : RBID : pubmed:20358126English descriptors
- KwdEn :
- MESH :
- chemical , chemical synthesis : Polymers.
- chemical , chemistry : Fullerenes, Polymers, Porphyrins.
- Absorption, Electric Conductivity, Electrochemistry, Electron Transport, Mass Spectrometry, Permeability, Photochemical Processes, Spectroscopy, Fourier Transform Infrared, Time Factors.
Abstract
A hole- and electron-conducting polymer has been prepared by electropolymerization of a porphyrin-fullerene monomer. The porphyrin units are linked by aminophenyl groups to form a linear chain in which the porphyrin is an integral part of the polymer backbone. The absorption spectrum of a film formed on indium-tin-oxide-coated glass resembles that of a model porphyrin-fullerene dyad, but with significant peak broadening. The film demonstrates a first oxidation potential of 0.75 V vs. SCE, corresponding to oxidation of the porphyrin polymer, and a first reduction potential of -0.63 V vs. SCE, corresponding to fullerene reduction. Time-resolved fluorescence studies show that the porphyrin first excited singlet state is strongly quenched by photoinduced electron transfer to fullerene. Transient absorption investigations reveal that excitation generates mobile charge carriers that recombine by both geminate and nongeminate pathways over a large range of time scales. Similar studies on a related polymer that lacks the fullerene component show complex, laser-intensity-dependent photoinduced electron transfer behavior. The properties of the porphyrin-fullerene electropolymer suggest that it may be useful in organic photovoltaic applications, wherein light absorption leads to charge separation within picoseconds in a "molecular heterojunction" with no requirement for exciton migration.
DOI: 10.1039/c0pp00013b
PubMed: 20358126
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The porphyrin units are linked by aminophenyl groups to form a linear chain in which the porphyrin is an integral part of the polymer backbone. The absorption spectrum of a film formed on indium-tin-oxide-coated glass resembles that of a model porphyrin-fullerene dyad, but with significant peak broadening. The film demonstrates a first oxidation potential of 0.75 V vs. SCE, corresponding to oxidation of the porphyrin polymer, and a first reduction potential of -0.63 V vs. SCE, corresponding to fullerene reduction. Time-resolved fluorescence studies show that the porphyrin first excited singlet state is strongly quenched by photoinduced electron transfer to fullerene. Transient absorption investigations reveal that excitation generates mobile charge carriers that recombine by both geminate and nongeminate pathways over a large range of time scales. Similar studies on a related polymer that lacks the fullerene component show complex, laser-intensity-dependent photoinduced electron transfer behavior. The properties of the porphyrin-fullerene electropolymer suggest that it may be useful in organic photovoltaic applications, wherein light absorption leads to charge separation within picoseconds in a "molecular heterojunction" with no requirement for exciton migration.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="MEDLINE"><PMID Version="1">20358126</PMID><DateCreated><Year>2010</Year><Month>06</Month><Day>30</Day></DateCreated><DateCompleted><Year>2010</Year><Month>11</Month><Day>01</Day></DateCompleted><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1474-9092</ISSN><JournalIssue CitedMedium="Internet"><Volume>9</Volume><Issue>7</Issue><PubDate><Year>2010</Year><Month>Jul</Month><Day>30</Day></PubDate></JournalIssue><Title>Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology</Title><ISOAbbreviation>Photochem. Photobiol. Sci.</ISOAbbreviation></Journal><ArticleTitle>A photo- and electrochemically-active porphyrin-fullerene dyad electropolymer.</ArticleTitle><Pagination><MedlinePgn>890-900</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1039/c0pp00013b</ELocationID><Abstract><AbstractText>A hole- and electron-conducting polymer has been prepared by electropolymerization of a porphyrin-fullerene monomer. The porphyrin units are linked by aminophenyl groups to form a linear chain in which the porphyrin is an integral part of the polymer backbone. The absorption spectrum of a film formed on indium-tin-oxide-coated glass resembles that of a model porphyrin-fullerene dyad, but with significant peak broadening. The film demonstrates a first oxidation potential of 0.75 V vs. SCE, corresponding to oxidation of the porphyrin polymer, and a first reduction potential of -0.63 V vs. SCE, corresponding to fullerene reduction. Time-resolved fluorescence studies show that the porphyrin first excited singlet state is strongly quenched by photoinduced electron transfer to fullerene. Transient absorption investigations reveal that excitation generates mobile charge carriers that recombine by both geminate and nongeminate pathways over a large range of time scales. Similar studies on a related polymer that lacks the fullerene component show complex, laser-intensity-dependent photoinduced electron transfer behavior. The properties of the porphyrin-fullerene electropolymer suggest that it may be useful in organic photovoltaic applications, wherein light absorption leads to charge separation within picoseconds in a "molecular heterojunction" with no requirement for exciton migration.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Gervaldo</LastName><ForeName>Miguel</ForeName><Initials>M</Initials><Affiliation>Departamento de Química, Universidad Nacional de Río Cuarto, Agencia Postal 3 (5800), Río Cuarto, Argentina.</Affiliation></Author><Author ValidYN="Y"><LastName>Liddell</LastName><ForeName>Paul A</ForeName><Initials>PA</Initials></Author><Author ValidYN="Y"><LastName>Kodis</LastName><ForeName>Gerdenis</ForeName><Initials>G</Initials></Author><Author ValidYN="Y"><LastName>Brennan</LastName><ForeName>Bradley J</ForeName><Initials>BJ</Initials></Author><Author ValidYN="Y"><LastName>Johnson</LastName><ForeName>Christopher R</ForeName><Initials>CR</Initials></Author><Author ValidYN="Y"><LastName>Bridgewater</LastName><ForeName>James W</ForeName><Initials>JW</Initials></Author><Author ValidYN="Y"><LastName>Moore</LastName><ForeName>Ana L</ForeName><Initials>AL</Initials></Author><Author ValidYN="Y"><LastName>Moore</LastName><ForeName>Thomas A</ForeName><Initials>TA</Initials></Author><Author ValidYN="Y"><LastName>Gust</LastName><ForeName>Devens</ForeName><Initials>D</Initials></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType>Journal Article</PublicationType><PublicationType>Research Support, U.S. Gov't, Non-P.H.S.</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2010</Year><Month>04</Month><Day>01</Day></ArticleDate></Article><MedlineJournalInfo><Country>England</Country><MedlineTA>Photochem Photobiol Sci</MedlineTA><NlmUniqueID>101124451</NlmUniqueID><ISSNLinking>1474-905X</ISSNLinking></MedlineJournalInfo><ChemicalList><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Fullerenes</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Polymers</NameOfSubstance></Chemical><Chemical><RegistryNumber>0</RegistryNumber><NameOfSubstance>Porphyrins</NameOfSubstance></Chemical></ChemicalList><CitationSubset>IM</CitationSubset><MeshHeadingList><MeshHeading><DescriptorName MajorTopicYN="N">Absorption</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Electric Conductivity</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Electrochemistry</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Electron Transport</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Fullerenes</DescriptorName><QualifierName MajorTopicYN="Y">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Mass Spectrometry</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Permeability</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="Y">Photochemical Processes</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Polymers</DescriptorName><QualifierName MajorTopicYN="N">chemical synthesis</QualifierName><QualifierName MajorTopicYN="Y">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Porphyrins</DescriptorName><QualifierName MajorTopicYN="Y">chemistry</QualifierName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Spectroscopy, Fourier Transform Infrared</DescriptorName></MeshHeading><MeshHeading><DescriptorName MajorTopicYN="N">Time Factors</DescriptorName></MeshHeading></MeshHeadingList></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="aheadofprint"><Year>2010</Year><Month>4</Month><Day>1</Day></PubMedPubDate><PubMedPubDate PubStatus="epublish"><Year>2010</Year><Month>7</Month><Day>30</Day></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2010</Year><Month>4</Month><Day>2</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2010</Year><Month>4</Month><Day>2</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2010</Year><Month>11</Month><Day>3</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="doi">10.1039/c0pp00013b</ArticleId><ArticleId IdType="pubmed">20358126</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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