{"@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/1360848658147687040.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1021/jacs.8b13593"}},{"identifier":{"@type":"URI","@value":"https://pubs.acs.org/doi/pdf/10.1021/jacs.8b13593"}},{"identifier":{"@type":"PMID","@value":"30721045"}},{"identifier":{"@type":"HANDLE","@value":"10261/200873"}}],"resourceType":"学術雑誌論文(journal article)","dc:title":[{"@value":"Postsynthetic Covalent and Coordination Functionalization of Rhodium(II)-Based Metal–Organic Polyhedra"}],"description":[{"notation":[{"@value":"Metal-organic polyhedra (MOP) are ultrasmall (typically 1-4 nm) porous coordination cages made from the self-assembly of metal ions and organic linkers and are amenable to the chemical functionalization of its periphery; however, it has been challenging to implement postsynthetic functionalization due to their chemical instability. Herein, we report the use of coordination chemistries and covalent chemistries to postsynthetically functionalize the external surface of ≈2.5 nm stable Rh(II)-based cuboctahedra through their Rh-Rh paddlewheel units or organic linkers, respectively. We demonstrate that 12 N-donor ligands, including amino acids, can be coordinated on the periphery of Rh-MOPs. We used this reactivity to introduce new functionalities (e.g., chirality) to the MOPs and to tune their hydrophilic/hydrophobic characteristics, which allowed us to modulate their solubility in diverse solvents such as dichloromethane and water. We also demonstrate that all 24 organic linkers can be postsynthetically functionalized with esters via covalent chemistry. In addition, we anticipate that these two types of postsynthetic reactions can be combined to yield doubly functionalized Rh-MOPs, in which a total of 36 new functional molecules can be incorporated on their surfaces. Likewise, these chemistries could be synergistically combined to enable covalent functionalization of MOPs through new linkages such as ethers. We believe that both reported postsynthetic pathways can potentially be used to engineer Rh-MOPs as scaffolds for applications in delivery, sorption, and catalysis."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1380848658147687043","@type":"Researcher","foaf:name":[{"@value":"Arnau Carné-Sánchez"}],"jpcoar:affiliationName":[{"@value":"Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1380848658147687042","@type":"Researcher","foaf:name":[{"@value":"Jorge Albalad"}],"jpcoar:affiliationName":[{"@value":"Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1380848658147687044","@type":"Researcher","foaf:name":[{"@value":"Thais Grancha"}],"jpcoar:affiliationName":[{"@value":"Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1380848658147687041","@type":"Researcher","foaf:name":[{"@value":"Inhar Imaz"}],"jpcoar:affiliationName":[{"@value":"Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1380848658147687045","@type":"Researcher","foaf:name":[{"@value":"Judith Juanhuix"}],"jpcoar:affiliationName":[{"@value":"ALBA Synchrotron, Cerdanyola del Vallès, 08290 Barcelona, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1380848658147687040","@type":"Researcher","foaf:name":[{"@value":"Patrick Larpent"}],"jpcoar:affiliationName":[{"@value":"Institute for Integrated Cell-Material Science (WPI-iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1420282801202959616","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"90452276"},{"@type":"NRID","@value":"1000090452276"},{"@type":"ORCID","@value":"0000-0003-3849-8038"},{"@type":"NRID","@value":"9000404090499"},{"@type":"NRID","@value":"9000283394959"},{"@type":"NRID","@value":"9000258600795"},{"@type":"NRID","@value":"9000397946248"},{"@type":"NRID","@value":"9000022503431"},{"@type":"NRID","@value":"9000397707850"},{"@type":"NRID","@value":"9000282394525"},{"@type":"NRID","@value":"9000404629369"},{"@type":"NRID","@value":"9000279889750"},{"@type":"NRID","@value":"9000323291372"},{"@type":"NRID","@value":"9000240539255"},{"@type":"NRID","@value":"9000399010695"},{"@type":"NRID","@value":"9000259862949"},{"@type":"NRID","@value":"9000391866648"},{"@type":"NRID","@value":"9000345247115"},{"@type":"NRID","@value":"9000257984218"},{"@type":"NRID","@value":"9000261046641"},{"@type":"NRID","@value":"9000004528233"},{"@type":"NRID","@value":"9000288837355"},{"@type":"NRID","@value":"9000237871341"},{"@type":"NRID","@value":"9000347362059"},{"@type":"NRID","@value":"9000257734683"},{"@type":"NRID","@value":"9000107393792"},{"@type":"NRID","@value":"9000024813870"},{"@type":"NRID","@value":"9000018149804"},{"@type":"NRID","@value":"9000019108947"},{"@type":"RESEARCHMAP","@value":"https://researchmap.jp/shuheifurukawa"}],"foaf:name":[{"@value":"Shuhei Furukawa"}],"jpcoar:affiliationName":[{"@value":"Institute for Integrated Cell-Material Science (WPI-iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan"},{"@value":"Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1380848658147687046","@type":"Researcher","foaf:name":[{"@value":"Daniel Maspoch"}],"jpcoar:affiliationName":[{"@value":"Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain"},{"@value":"ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain"}]}],"contributor":[{"@id":"https://cir.nii.ac.jp/crid/1892835442916179978","@type":"Researcher","foaf:name":[{"@value":"Agencia Estatal de Investigación (España)"}]},{"@id":"https://cir.nii.ac.jp/crid/1892835442916179972","@type":"Researcher","foaf:name":[{"@value":"Ministerio de Economía y Competitividad (España)"}]},{"@id":"https://cir.nii.ac.jp/crid/1892835442916179981","@type":"Researcher","foaf:name":[{"@value":"Generalitat de Catalunya"}]},{"@id":"https://cir.nii.ac.jp/crid/1892835442916179968","@type":"Researcher","foaf:name":[{"@value":"European Research Council"}]},{"@id":"https://cir.nii.ac.jp/crid/1892835442916179975","@type":"Researcher","foaf:name":[{"@value":"European Commission"}]},{"@id":"https://cir.nii.ac.jp/crid/1892835442916179974","@type":"Researcher","foaf:name":[{"@value":"Ministerio de Ciencia, Innovación y Universidades (España)"}]},{"@id":"https://cir.nii.ac.jp/crid/1892835442916179979","@type":"Researcher","foaf:name":[{"@value":"Ministry of Education, Culture, Sports, Science and Technology (Japan)"}]},{"@id":"https://cir.nii.ac.jp/crid/1891992116170453760","@type":"Researcher","foaf:name":[{"@value":"Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]"}]},{"@id":"https://cir.nii.ac.jp/crid/1892835442916179982","@type":"Researcher","foaf:name":[{"@value":"Japan Society for the Promotion of Science"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"00027863"},{"@type":"EISSN","@value":"15205126"}],"prism:publicationName":[{"@value":"Journal of the American Chemical Society"}],"dc:publisher":[{"@value":"American Chemical Society (ACS)"}],"prism:publicationDate":"2019-02-05","prism:volume":"141","prism:number":"9","prism:startingPage":"4094","prism:endingPage":"4102"},"reviewed":"false","dc:rights":["https://doi.org/10.15223/policy-029","https://doi.org/10.15223/policy-037","https://doi.org/10.15223/policy-045"],"url":[{"@id":"https://pubs.acs.org/doi/pdf/10.1021/jacs.8b13593"}],"createdAt":"2019-02-05","modifiedAt":"2023-04-13","foaf:topic":[{"@id":"https://cir.nii.ac.jp/all?q=Chemical%20instability","dc:title":"Chemical instability"},{"@id":"https://cir.nii.ac.jp/all?q=Metal-organic%20polyhedron","dc:title":"Metal-organic polyhedron"},{"@id":"https://cir.nii.ac.jp/all?q=Co-ordination%20chemistries","dc:title":"Co-ordination chemistries"},{"@id":"https://cir.nii.ac.jp/all?q=Functional%20molecules","dc:title":"Functional molecules"},{"@id":"https://cir.nii.ac.jp/all?q=Covalent%20chemistry","dc:title":"Covalent chemistry"},{"@id":"https://cir.nii.ac.jp/all?q=Hydrophilic/hydrophobic","dc:title":"Hydrophilic/hydrophobic"},{"@id":"https://cir.nii.ac.jp/all?q=Covalent%20functionalizations","dc:title":"Covalent functionalizations"},{"@id":"https://cir.nii.ac.jp/all?q=Chemical%20functionalization","dc:title":"Chemical functionalization"}],"project":[{"@id":"https://cir.nii.ac.jp/crid/1040000781958691840","@type":"Project","projectIdentifier":[{"@type":"KAKEN","@value":"17H05367"},{"@type":"JGN","@value":"JP17H05367"},{"@type":"URI","@value":"https://kaken.nii.ac.jp/grant/KAKENHI-PUBLICLY-17H05367/"}],"notation":[{"@language":"ja","@value":"対称性破壊型配位集積化による多孔性ゲルの創製"}]},{"@id":"https://cir.nii.ac.jp/crid/1040000781992976768","@type":"Project","projectIdentifier":[{"@type":"KAKEN","@value":"18H01995"},{"@type":"JGN","@value":"JP18H01995"},{"@type":"URI","@value":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18H01995/"}],"notation":[{"@language":"ja","@value":"金属錯体多面体を用いた外場応答型人工イオンチャネルの創製"},{"@language":"en","@value":"Stimuli-Responsive Synthetic Ion Channels Based on Metal-Organic Polyhedra"}]}],"relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050001338453522560","@type":"Article","resourceType":"学術雑誌論文(journal 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