{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1362825894103668096.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/anie.201913552"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201913552"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201913552"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.201913552"}}],"dc:title":[{"@value":"Anti‐Aromatic versus Induced Paratropicity: Synthesis and Interrogation of a Dihydro‐diazatrioxa[9]circulene with a Proton Placed Directly above the Central Ring"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>We present a high‐yielding intramolecular oxidative coupling within a diazadioxa[10]helicene to give a dihydro‐diazatrioxa[9]circulene. This is the first [<jats:italic>n</jats:italic>]circulene containing more than eight <jats:italic>ortho</jats:italic>‐annulated rings (<jats:italic>n</jats:italic>>8). The single‐crystal X‐ray structure reveals a tight columnar packing, with a proton from a pendant naphthalene moiety centred directly above the central nine‐membered ring. This distinct environment induces a significant magnetic deshielding effect on that particular proton as determined by <jats:sup>1</jats:sup>H NMR spectroscopy. The origin of the deshielding effect was investigated computationally in terms of the NICS values. It is established that the deshielding effect originates from an induced paratropic ring current from the seven aromatic rings of the [9]circulene structure, and is not due to the nine‐membered ring being antiaromatic. UV/Vis spectroscopy reveals more efficient conjugation in the prepared diazatrioxa[9]circulene compared to the parent helical azaoxa[10]helicenes, and DFT calculations, including energy levels, confirm the experimental observations.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1382825894103668100","@type":"Researcher","foaf:name":[{"@value":"Stephan K. Pedersen"}],"jpcoar:affiliationName":[{"@value":"University of Copenhagen Department of Chemistry  Universitetsparken 5 2100 Copenhagen Ø Denmark"}]},{"@id":"https://cir.nii.ac.jp/crid/1382825894103668102","@type":"Researcher","foaf:name":[{"@value":"Kristina Eriksen"}],"jpcoar:affiliationName":[{"@value":"University of Copenhagen Department of Chemistry  Universitetsparken 5 2100 Copenhagen Ø Denmark"}]},{"@id":"https://cir.nii.ac.jp/crid/1382825894103668099","@type":"Researcher","foaf:name":[{"@value":"Nataliya N. Karaush‐Karmazin"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Nanomaterials Science Bohdan Khmelnytsky National University  18031 Cherkasy Ukraine"}]},{"@id":"https://cir.nii.ac.jp/crid/1382825894103668096","@type":"Researcher","foaf:name":[{"@value":"Boris Minaev"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Nanomaterials Science Bohdan Khmelnytsky National University  18031 Cherkasy Ukraine"}]},{"@id":"https://cir.nii.ac.jp/crid/1382825894103668097","@type":"Researcher","foaf:name":[{"@value":"Hans Ågren"}],"jpcoar:affiliationName":[{"@value":"Division of Theoretical Chemistry and Biology School of Engineering Sciences in Chemistry, Biotechnology and Health KTH Royal Institute of Technology  10691 Stockholm Sweden"},{"@value":"College of Chemistry and Chemical Engineering Henan University  Kaifeng, Henan 475004 P. R. China"}]},{"@id":"https://cir.nii.ac.jp/crid/1382825894103668101","@type":"Researcher","foaf:name":[{"@value":"Gleb V. Baryshnikov"}],"jpcoar:affiliationName":[{"@value":"Division of Theoretical Chemistry and Biology School of Engineering Sciences in Chemistry, Biotechnology and Health KTH Royal Institute of Technology  10691 Stockholm Sweden"}]},{"@id":"https://cir.nii.ac.jp/crid/1382825894103668098","@type":"Researcher","foaf:name":[{"@value":"Michael Pittelkow"}],"jpcoar:affiliationName":[{"@value":"University of Copenhagen Department of Chemistry  Universitetsparken 5 2100 Copenhagen Ø Denmark"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"14337851"},{"@type":"EISSN","@value":"15213773"}],"prism:publicationName":[{"@value":"Angewandte Chemie International Edition"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2020-02-20","prism:volume":"59","prism:number":"13","prism:startingPage":"5144","prism:endingPage":"5150"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201913552"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201913552"},{"@id":"https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.201913552"}],"createdAt":"2020-01-21","modifiedAt":"2023-09-07","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050024953984429056","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Synthesis of terminus-decorated aza[9]helicenes: control of interlayer interaction"}]},{"@id":"https://cir.nii.ac.jp/crid/1050294872220241664","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Fold‐in Synthesis of a Pentabenzopentaaza[10]circulene"}]},{"@id":"https://cir.nii.ac.jp/crid/1360009142816272128","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Highly Stable Radical Cations of <i>N</i>,<i>N’</i>‐Diarylated Tetrabenzotetraaza[8]circulene"}]},{"@id":"https://cir.nii.ac.jp/crid/1360009142888657024","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Synthesis and Characterization of Peralkylated Pyrrole-Fused Azacoronene"}]},{"@id":"https://cir.nii.ac.jp/crid/1360013168800853120","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Synthesis, Properties, and Packing Structures of Wing-Shaped N-Doped Nanographene in Various Oxidation States"}]},{"@id":"https://cir.nii.ac.jp/crid/1360017279864257280","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Theoretical study on the structures, electronic properties, and aromaticity of thia[4]circulenes"}]},{"@id":"https://cir.nii.ac.jp/crid/1360857593690150400","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Facile Synthesis of Azahelicenes and Diaza[8]circulenes through the Intramolecular Scholl Reaction"}]},{"@id":"https://cir.nii.ac.jp/crid/1390867056396941056","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"ja","@value":"ピロールのNHサイトの特性を活かしたアザヘリセン類の合成"},{"@language":"en","@value":"Synthesis of Azahelicene Derivatives by Utilizing Functionalities of Pyrrolic NH Sites"},{"@language":"ja-Kana","@value":"ピロール ノ NH サイト ノ トクセイ オ イカシタ アザヘリセンルイ ノ ゴウセイ"}]},{"@id":"https://cir.nii.ac.jp/crid/2051433317038775040","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Synthesis of novel heteronanographenes via fold-in approach"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/anie.201913552"},{"@type":"CROSSREF","@value":"10.1002/chem.202001934_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"},{"@type":"CROSSREF","@value":"10.1021/acs.joc.0c03042_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"},{"@type":"CROSSREF","@value":"10.1021/acs.orglett.1c03669_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"},{"@type":"CROSSREF","@value":"10.1039/d2nj04359a_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"},{"@type":"CROSSREF","@value":"10.1246/bcsj.20220030_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"},{"@type":"CROSSREF","@value":"10.1093/chemle/upae159_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"},{"@type":"CROSSREF","@value":"10.1002/anie.202116789_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"},{"@type":"CROSSREF","@value":"10.1002/chem.202102269_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"},{"@type":"CROSSREF","@value":"10.5059/yukigoseikyokaishi.83.413_references_DOI_SPlOnpLpX6FbifiEl2ngoH4wveO"}]}