Multifunctional π-expanded macrocyclic oligothiophene 6-mers and related macrocyclic oligomers.
Identifieur interne : 001A89 ( PubMed/Curation ); précédent : 001A88; suivant : 001A90Multifunctional π-expanded macrocyclic oligothiophene 6-mers and related macrocyclic oligomers.
Auteurs : Masahiko Iyoda [Japon] ; Keita Tanaka ; Hideyuki Shimizu ; Masashi Hasegawa ; Tohru Nishinaga ; Tomohiko Nishiuchi ; Yoshihito Kunugi ; Takayuki Ishida ; Hiroyuki Otani ; Hiroyasu Sato ; Koji Inukai ; Kazukuni Tahara ; Yoshito TobeSource :
- Journal of the American Chemical Society [ 1520-5126 ] ; 2014.
Abstract
Multifunctional π-expanded macrocyclic oligothiophene 6-mer 1, as well as 9- (2) and 12-mers (3), was synthesized using a McMurry coupling reaction as the key step. The 6-mer 1 was converted to cyclo[6](2,5-thienylene-ethynylene) (4) by using a bromination-dehydrobromination procedure. From X-ray analysis, the crystal structures of nonplanar 1 and round-shaped 2 and 4 were elucidated. STM showed that 4 formed a self-assembled monolayer at the liquid/solid interface to produce a hexagonal porous network. Chemical oxidation of 1, 2, and 4 with 1 and 2 equiv of Fe(ClO4)3 produced 1(•+) and 1(2+), 2(•+) and 2(2+), and 4(•+) and 4(2+), respectively. Although oligothiophene radical cations containing β,β-disubstituted thiophenes usually do not form π-dimers, 4(•+) clearly formed a π-dimer owing to its planar, round shape. As for the dications of 1, 2, and 4, 1(2+), which has 34π-electrons, exhibited a large diatropic ring current effect, whereas 34π dication 4(2+) only showed a medium diatropic ring current effect. In contrast to 1(2+) and 4(2+), 52π dication 2(2+) had biradical cationic character instead of Hückel-type cyclic conjugation. Interestingly, 6-mer 1 showed polymorphism and unusual melting point behavior due to the number of stable conformations in the solid state. Single crystals of 1 melted at 176 °C, whereas an amorphous film of 1 crystallized in the temperature range of 80-83 °C to form a lamellarly stacked microcrystalline film, which melted at 139 °C. The polymorphism of 1 was applied to either fluorescence switching or switching of field effect transistor (FET) activity and electrical conductivity.
DOI: 10.1021/ja4101744
PubMed: 24428352
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Shimizu</name></author><author><name sortKey="Hasegawa, Masashi" sort="Hasegawa, Masashi" uniqKey="Hasegawa M" first="Masashi" last="Hasegawa">Masashi Hasegawa</name></author><author><name sortKey="Nishinaga, Tohru" sort="Nishinaga, Tohru" uniqKey="Nishinaga T" first="Tohru" last="Nishinaga">Tohru Nishinaga</name></author><author><name sortKey="Nishiuchi, Tomohiko" sort="Nishiuchi, Tomohiko" uniqKey="Nishiuchi T" first="Tomohiko" last="Nishiuchi">Tomohiko Nishiuchi</name></author><author><name sortKey="Kunugi, Yoshihito" sort="Kunugi, Yoshihito" uniqKey="Kunugi Y" first="Yoshihito" last="Kunugi">Yoshihito Kunugi</name></author><author><name sortKey="Ishida, Takayuki" sort="Ishida, Takayuki" uniqKey="Ishida T" first="Takayuki" last="Ishida">Takayuki Ishida</name></author><author><name sortKey="Otani, Hiroyuki" sort="Otani, Hiroyuki" uniqKey="Otani H" first="Hiroyuki" last="Otani">Hiroyuki Otani</name></author><author><name sortKey="Sato, Hiroyasu" sort="Sato, Hiroyasu" uniqKey="Sato H" first="Hiroyasu" last="Sato">Hiroyasu Sato</name></author><author><name sortKey="Inukai, Koji" sort="Inukai, Koji" uniqKey="Inukai K" first="Koji" last="Inukai">Koji Inukai</name></author><author><name sortKey="Tahara, Kazukuni" sort="Tahara, Kazukuni" uniqKey="Tahara K" first="Kazukuni" last="Tahara">Kazukuni Tahara</name></author><author><name sortKey="Tobe, Yoshito" sort="Tobe, Yoshito" uniqKey="Tobe Y" first="Yoshito" last="Tobe">Yoshito Tobe</name></author></titleStmt><publicationStmt><idno type="wicri:source">PubMed</idno><date when="2014">2014</date><idno type="RBID">pubmed:24428352</idno><idno type="pmid">24428352</idno><idno type="doi">10.1021/ja4101744</idno><idno type="wicri:Area/PubMed/Corpus">001A89</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Corpus" wicri:corpus="PubMed">001A89</idno><idno type="wicri:Area/PubMed/Curation">001A89</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Curation">001A89</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en">Multifunctional π-expanded macrocyclic oligothiophene 6-mers and related macrocyclic oligomers.</title><author><name sortKey="Iyoda, Masahiko" sort="Iyoda, Masahiko" uniqKey="Iyoda M" first="Masahiko" last="Iyoda">Masahiko Iyoda</name><affiliation wicri:level="1"><nlm:affiliation>Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University , Hachioji, Tokyo 192-0397, Japan.</nlm:affiliation><country xml:lang="fr">Japon</country><wicri:regionArea>Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University , Hachioji, Tokyo 192-0397</wicri:regionArea></affiliation></author><author><name sortKey="Tanaka, Keita" sort="Tanaka, Keita" uniqKey="Tanaka K" first="Keita" last="Tanaka">Keita Tanaka</name></author><author><name sortKey="Shimizu, Hideyuki" sort="Shimizu, Hideyuki" uniqKey="Shimizu H" first="Hideyuki" last="Shimizu">Hideyuki Shimizu</name></author><author><name sortKey="Hasegawa, Masashi" sort="Hasegawa, Masashi" uniqKey="Hasegawa M" first="Masashi" last="Hasegawa">Masashi Hasegawa</name></author><author><name sortKey="Nishinaga, Tohru" sort="Nishinaga, Tohru" uniqKey="Nishinaga T" first="Tohru" last="Nishinaga">Tohru Nishinaga</name></author><author><name sortKey="Nishiuchi, Tomohiko" sort="Nishiuchi, Tomohiko" uniqKey="Nishiuchi T" first="Tomohiko" last="Nishiuchi">Tomohiko Nishiuchi</name></author><author><name sortKey="Kunugi, Yoshihito" sort="Kunugi, Yoshihito" uniqKey="Kunugi Y" first="Yoshihito" last="Kunugi">Yoshihito Kunugi</name></author><author><name sortKey="Ishida, Takayuki" sort="Ishida, Takayuki" uniqKey="Ishida T" first="Takayuki" last="Ishida">Takayuki Ishida</name></author><author><name sortKey="Otani, Hiroyuki" sort="Otani, Hiroyuki" uniqKey="Otani H" first="Hiroyuki" last="Otani">Hiroyuki Otani</name></author><author><name sortKey="Sato, Hiroyasu" sort="Sato, Hiroyasu" uniqKey="Sato H" first="Hiroyasu" last="Sato">Hiroyasu Sato</name></author><author><name sortKey="Inukai, Koji" sort="Inukai, Koji" uniqKey="Inukai K" first="Koji" last="Inukai">Koji Inukai</name></author><author><name sortKey="Tahara, Kazukuni" sort="Tahara, Kazukuni" uniqKey="Tahara K" first="Kazukuni" last="Tahara">Kazukuni Tahara</name></author><author><name sortKey="Tobe, Yoshito" sort="Tobe, Yoshito" uniqKey="Tobe Y" first="Yoshito" last="Tobe">Yoshito Tobe</name></author></analytic><series><title level="j">Journal of the American Chemical Society</title><idno type="eISSN">1520-5126</idno><imprint><date when="2014" type="published">2014</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Multifunctional π-expanded macrocyclic oligothiophene 6-mer 1, as well as 9- (2) and 12-mers (3), was synthesized using a McMurry coupling reaction as the key step. The 6-mer 1 was converted to cyclo[6](2,5-thienylene-ethynylene) (4) by using a bromination-dehydrobromination procedure. From X-ray analysis, the crystal structures of nonplanar 1 and round-shaped 2 and 4 were elucidated. STM showed that 4 formed a self-assembled monolayer at the liquid/solid interface to produce a hexagonal porous network. Chemical oxidation of 1, 2, and 4 with 1 and 2 equiv of Fe(ClO4)3 produced 1(•+) and 1(2+), 2(•+) and 2(2+), and 4(•+) and 4(2+), respectively. Although oligothiophene radical cations containing β,β-disubstituted thiophenes usually do not form π-dimers, 4(•+) clearly formed a π-dimer owing to its planar, round shape. As for the dications of 1, 2, and 4, 1(2+), which has 34π-electrons, exhibited a large diatropic ring current effect, whereas 34π dication 4(2+) only showed a medium diatropic ring current effect. In contrast to 1(2+) and 4(2+), 52π dication 2(2+) had biradical cationic character instead of Hückel-type cyclic conjugation. Interestingly, 6-mer 1 showed polymorphism and unusual melting point behavior due to the number of stable conformations in the solid state. Single crystals of 1 melted at 176 °C, whereas an amorphous film of 1 crystallized in the temperature range of 80-83 °C to form a lamellarly stacked microcrystalline film, which melted at 139 °C. The polymorphism of 1 was applied to either fluorescence switching or switching of field effect transistor (FET) activity and electrical conductivity. </div></front></TEI><pubmed><MedlineCitation Status="PubMed-not-MEDLINE" Owner="NLM"><PMID Version="1">24428352</PMID><DateCompleted><Year>2014</Year><Month>10</Month><Day>09</Day></DateCompleted><DateRevised><Year>2014</Year><Month>02</Month><Day>12</Day></DateRevised><Article PubModel="Print-Electronic"><Journal><ISSN IssnType="Electronic">1520-5126</ISSN><JournalIssue CitedMedium="Internet"><Volume>136</Volume><Issue>6</Issue><PubDate><Year>2014</Year><Month>Feb</Month><Day>12</Day></PubDate></JournalIssue><Title>Journal of the American Chemical Society</Title><ISOAbbreviation>J. Am. Chem. Soc.</ISOAbbreviation></Journal><ArticleTitle>Multifunctional π-expanded macrocyclic oligothiophene 6-mers and related macrocyclic oligomers.</ArticleTitle><Pagination><MedlinePgn>2389-96</MedlinePgn></Pagination><ELocationID EIdType="doi" ValidYN="Y">10.1021/ja4101744</ELocationID><Abstract><AbstractText>Multifunctional π-expanded macrocyclic oligothiophene 6-mer 1, as well as 9- (2) and 12-mers (3), was synthesized using a McMurry coupling reaction as the key step. The 6-mer 1 was converted to cyclo[6](2,5-thienylene-ethynylene) (4) by using a bromination-dehydrobromination procedure. From X-ray analysis, the crystal structures of nonplanar 1 and round-shaped 2 and 4 were elucidated. STM showed that 4 formed a self-assembled monolayer at the liquid/solid interface to produce a hexagonal porous network. Chemical oxidation of 1, 2, and 4 with 1 and 2 equiv of Fe(ClO4)3 produced 1(•+) and 1(2+), 2(•+) and 2(2+), and 4(•+) and 4(2+), respectively. Although oligothiophene radical cations containing β,β-disubstituted thiophenes usually do not form π-dimers, 4(•+) clearly formed a π-dimer owing to its planar, round shape. As for the dications of 1, 2, and 4, 1(2+), which has 34π-electrons, exhibited a large diatropic ring current effect, whereas 34π dication 4(2+) only showed a medium diatropic ring current effect. In contrast to 1(2+) and 4(2+), 52π dication 2(2+) had biradical cationic character instead of Hückel-type cyclic conjugation. Interestingly, 6-mer 1 showed polymorphism and unusual melting point behavior due to the number of stable conformations in the solid state. Single crystals of 1 melted at 176 °C, whereas an amorphous film of 1 crystallized in the temperature range of 80-83 °C to form a lamellarly stacked microcrystalline film, which melted at 139 °C. The polymorphism of 1 was applied to either fluorescence switching or switching of field effect transistor (FET) activity and electrical conductivity. </AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Iyoda</LastName><ForeName>Masahiko</ForeName><Initials>M</Initials><AffiliationInfo><Affiliation>Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University , Hachioji, Tokyo 192-0397, Japan.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Tanaka</LastName><ForeName>Keita</ForeName><Initials>K</Initials></Author><Author ValidYN="Y"><LastName>Shimizu</LastName><ForeName>Hideyuki</ForeName><Initials>H</Initials></Author><Author ValidYN="Y"><LastName>Hasegawa</LastName><ForeName>Masashi</ForeName><Initials>M</Initials></Author><Author ValidYN="Y"><LastName>Nishinaga</LastName><ForeName>Tohru</ForeName><Initials>T</Initials></Author><Author ValidYN="Y"><LastName>Nishiuchi</LastName><ForeName>Tomohiko</ForeName><Initials>T</Initials></Author><Author ValidYN="Y"><LastName>Kunugi</LastName><ForeName>Yoshihito</ForeName><Initials>Y</Initials></Author><Author ValidYN="Y"><LastName>Ishida</LastName><ForeName>Takayuki</ForeName><Initials>T</Initials></Author><Author ValidYN="Y"><LastName>Otani</LastName><ForeName>Hiroyuki</ForeName><Initials>H</Initials></Author><Author ValidYN="Y"><LastName>Sato</LastName><ForeName>Hiroyasu</ForeName><Initials>H</Initials></Author><Author ValidYN="Y"><LastName>Inukai</LastName><ForeName>Koji</ForeName><Initials>K</Initials></Author><Author ValidYN="Y"><LastName>Tahara</LastName><ForeName>Kazukuni</ForeName><Initials>K</Initials></Author><Author ValidYN="Y"><LastName>Tobe</LastName><ForeName>Yoshito</ForeName><Initials>Y</Initials></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList><ArticleDate DateType="Electronic"><Year>2014</Year><Month>01</Month><Day>31</Day></ArticleDate></Article><MedlineJournalInfo><Country>United States</Country><MedlineTA>J Am Chem Soc</MedlineTA><NlmUniqueID>7503056</NlmUniqueID><ISSNLinking>0002-7863</ISSNLinking></MedlineJournalInfo></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="entrez"><Year>2014</Year><Month>1</Month><Day>17</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="pubmed"><Year>2014</Year><Month>1</Month><Day>17</Day><Hour>6</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2014</Year><Month>1</Month><Day>17</Day><Hour>6</Hour><Minute>1</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="pubmed">24428352</ArticleId><ArticleId IdType="doi">10.1021/ja4101744</ArticleId></ArticleIdList></PubmedData></pubmed></record>Pour manipuler ce document sous Unix (Dilib)
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