{"@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/1363670320061365760.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/anie.201806281"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201806281"}},{"identifier":{"@type":"URI","@value":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201806281"}}],"dc:title":[{"@value":"Molecular Engineering of Free‐Base Porphyrins as Ligands—The N−H⋅⋅⋅X Binding Motif in Tetrapyrroles"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>The core N−H units of planar porphyrins are often inaccessible to forming hydrogen‐bonding complexes with acceptor molecules. This is due to the fact that the amine moieties are “shielded” by the macrocyclic system, impeding the formation of intermolecular H‐bonds. However, methods exist to modulate the tetrapyrrole conformations and to reshape the vector of N−H orientation outwards, thus increasing their availability and reactivity. Strategies include the use of porpho(di)methenes and phlorins (calixphyrins), as well as saddle‐distorted porphyrins. The former form cavities due to interruption of the aromatic system. The latter are highly basic systems and capable of binding anions and neutral molecules via N−H⋅⋅⋅X‐type H‐bonds. This Review discusses the role of porphyrin(oid) ligands in various coordination‐type complexes, means to access the core for hydrogen bonding, the concept of conformational control, and emerging applications, such as organocatalysis and sensors.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1383670320061365761","@type":"Researcher","foaf:name":[{"@value":"Marc Kielmann"}],"jpcoar:affiliationName":[{"@value":"School of Chemistry SFI Tetrapyrrole Laboratory Trinity Biomedical Sciences Institute Trinity College Dublin The University of Dublin  152–160 Pearse Street Dublin 2 Ireland"}]},{"@id":"https://cir.nii.ac.jp/crid/1383670320061365760","@type":"Researcher","foaf:name":[{"@value":"Mathias O. Senge"}],"jpcoar:affiliationName":[{"@value":"School of Chemistry SFI Tetrapyrrole Laboratory Trinity Biomedical Sciences Institute Trinity College Dublin The University of Dublin  152–160 Pearse Street Dublin 2 Ireland"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"14337851"},{"@type":"EISSN","@value":"15213773"}],"prism:publicationName":[{"@value":"Angewandte Chemie International Edition"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2018-11-05","prism:volume":"58","prism:number":"2","prism:startingPage":"418","prism:endingPage":"441"},"reviewed":"false","dc:rights":["http://creativecommons.org/licenses/by-nc/4.0/"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201806281"},{"@id":"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201806281"}],"createdAt":"2018-08-03","modifiedAt":"2023-09-14","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050290106068272768","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Efficient Near-Infrared Light-Driven Hydrogen Evolution Catalyzed by a Saddle-Distorted Porphyrin as a Photocatalyst"}]},{"@id":"https://cir.nii.ac.jp/crid/1050571581044983296","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"A Mechanistic Dichotomy in Two-Electron Reduction of Dioxygen  Catalyzed by N,N’-Dimethylated Porphyrin Isomers"},{"@value":"A Mechanistic Dichotomy in Two‐Electron Reduction of Dioxygen Catalyzed by <i>N</i>,<i>N</i>’‐Dimethylated Porphyrin Isomers"}]},{"@id":"https://cir.nii.ac.jp/crid/1360016870541838080","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Nonplanar porphyrins: synthesis, properties, and unique functionalities"}]},{"@id":"https://cir.nii.ac.jp/crid/1360025431108368000","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Steric factors controlling regioselective and efficient <i>N</i>-methylation of β-tetrabromoporphyrins"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285708112291712","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"A Diprotonated Porphyrin as an Electron Mediator in Photoinduced Electron Transfer in Hydrogen-Bonded Supramolecular Assemblies"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285708194309504","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Dioxygen/Hydrogen Peroxide Interconversion Using Redox Couples of Saddle-Distorted Porphyrins and Isophlorins"}]},{"@id":"https://cir.nii.ac.jp/crid/1360294643840468992","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Hydrogen Bond Engineering Visualized by Picometer-Level Distortion of Planar Porphyrin Isomers"}]},{"@id":"https://cir.nii.ac.jp/crid/1360585256673728512","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Molecular Engineering of β-Substituted Oxoporphyrinogens for Hydrogen-Bond Donor Catalysis"}]},{"@id":"https://cir.nii.ac.jp/crid/1360588380594601984","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Efficient Near‐Infrared‐Light‐Driven H<sub>2</sub> Production with Salts of a Diprotonated Saddle‐Distorted Porphyrin as Photosensitizers"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/anie.201806281"},{"@type":"CROSSREF","@value":"10.1039/d5ob00212e_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"},{"@type":"CROSSREF","@value":"10.1021/acsaem.0c00206_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"},{"@type":"CROSSREF","@value":"10.1021/acs.jpclett.1c03020_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"},{"@type":"CROSSREF","@value":"10.1002/chem.202000942_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"},{"@type":"CROSSREF","@value":"10.1002/cptc.202500009_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"},{"@type":"CROSSREF","@value":"10.1039/d2cs00391k_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"},{"@type":"CROSSREF","@value":"10.1021/jacs.9b01038_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"},{"@type":"CROSSREF","@value":"10.1021/acs.jpcc.9b02449_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"},{"@type":"CROSSREF","@value":"10.1002/ejoc.201901706_references_DOI_1cVHjJRrgEpq4ZaCwxneNaJqVsb"}]}