{"@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/1360004233236435328.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1021/jp5123163"}},{"identifier":{"@type":"URI","@value":"https://pubs.acs.org/doi/pdf/10.1021/jp5123163"}},{"identifier":{"@type":"PMID","@value":"25615010"}}],"resourceType":"学術雑誌論文(journal article)","dc:title":[{"@value":"Near-Infrared Photoelectrochemical Conversion via Photoinduced Charge Separation in Supramolecular Complexes of Anionic Phthalocyanines with Li<sup>+</sup>@C<sub>60</sub>"}],"description":[{"notation":[{"@value":"Two phthalocyanines possessing carboxylate groups ((TBA)4H2Pc·1 and (TBA)4H2Pc·2) form 1:2 supramolecular complexes with lithium cation-encapsulated C60 (Li(+)@C60) [H2Pc·1(4-)/(Li(+)@C60)2 and H2Pc·2(4-)/(Li(+)@C60)2] in a polar mixed solvent. From the UV-vis spectral changes, the binding constants (K) were estimated as ca. 10(12) M(-2). Upon the photoexcitation of constructed supramolecular complexes, photoinduced electron transfer occurred to form the charge-separated (CS) state. The lifetime of the CS state was determined to be 1.2 ms for H2Pc·2(4-)/(Li(+)@C60)2, which is the longest CS lifetime among the porphyrinoid/fullerene supramolecular complexes. H2Pc·1(4-)/(Li(+)@C60)2 also afforded the long-lived CS state of 1.0 ms. The spin state of the long-lived CS states was determined to be a triplet, as indicated by the EPR signal at g = 4. The reorganization energy (λ) and the electronic coupling term were determined to be λ = 1.70 eV, V = 0.15 cm(-1) from the temperature dependence of the rate constant for the charge recombination of the CS state of H2Pc·1(4-)/(Li(+)@C60)2. The energy of the CS state (0.49 eV) is much smaller than the reorganization energy, indicating that the back-electron-transfer process is located in the Marcus normal region. The small electronic coupling term results from the spin-forbidden back electron transfer due to the triplet CS state. Supramolecular complexes of anionic zinc phthalocyanines with Li(+)@C60 were also prepared and investigated. The ZnPc·4(4-)/Li(+)@C60 supramolecular nanoclusters were assembled on the optically transparent electrode (OTE) of nanostructured SnO2 (OTE/SnO2) to construct the dye-sensitized solar cell. The IPCE (incident photon-to-photocurrent efficiency) values of OTE/SnO2/(ZnPc·4(4-)/Li(+)@C60)n were much higher than the sum of the two IPCE values of the individual systems OTE/SnO2/(Li(+)@C60)n and OTE/SnO2/(ZnPc·4(4-))n, covering the near-infrared region."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1380004233236435205","@type":"Researcher","foaf:name":[{"@value":"Yuki Kawashima"}],"jpcoar:affiliationName":[{"@value":"Department\rof Material and Life Science, Graduate School of Engineering, Osaka University, and ALCA, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1420001326227216000","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"00379140"},{"@type":"NRID","@value":"1000000379140"},{"@type":"ORCID","@value":"0000-0001-8328-9249"},{"@type":"NRID","@value":"9000400184100"},{"@type":"NRID","@value":"9000256029590"},{"@type":"NRID","@value":"9000258597681"},{"@type":"NRID","@value":"9000002084209"},{"@type":"NRID","@value":"9000256431879"},{"@type":"NRID","@value":"9000258596843"},{"@type":"NRID","@value":"9000258601924"},{"@type":"NRID","@value":"9000257715697"},{"@type":"NRID","@value":"9000257738029"},{"@type":"NRID","@value":"9000398616226"},{"@type":"NRID","@value":"9000283740253"},{"@type":"NRID","@value":"9000256024962"},{"@type":"NRID","@value":"9000258602156"},{"@type":"NRID","@value":"9000258595148"},{"@type":"NRID","@value":"9000258599321"},{"@type":"NRID","@value":"9000404681479"},{"@type":"NRID","@value":"9000283741747"},{"@type":"NRID","@value":"9000258596536"},{"@type":"NRID","@value":"9000258600469"},{"@type":"NRID","@value":"9000258596999"},{"@type":"NRID","@value":"9000413523205"},{"@type":"NRID","@value":"9000403827931"},{"@type":"NRID","@value":"9000283741457"},{"@type":"NRID","@value":"9000283741736"},{"@type":"NRID","@value":"9000283741121"},{"@type":"NRID","@value":"9000411581114"},{"@type":"NRID","@value":"9000257726469"},{"@type":"NRID","@value":"9000363175202"},{"@type":"NRID","@value":"9000255829345"},{"@type":"NRID","@value":"9000258594412"},{"@type":"NRID","@value":"9000258596539"},{"@type":"NRID","@value":"9000258597685"},{"@type":"NRID","@value":"9000257715435"},{"@type":"NRID","@value":"9000395382547"},{"@type":"NRID","@value":"9000398955723"},{"@type":"NRID","@value":"9000002736995"},{"@type":"NRID","@value":"9000258600190"},{"@type":"NRID","@value":"9000258597677"},{"@type":"NRID","@value":"9000258597005"},{"@type":"NRID","@value":"9000283122874"},{"@type":"NRID","@value":"9000257727757"},{"@type":"NRID","@value":"9000016384450"},{"@type":"NRID","@value":"9000256024005"},{"@type":"NRID","@value":"9000258601405"},{"@type":"NRID","@value":"9000258598684"},{"@type":"NRID","@value":"9000258597012"},{"@type":"NRID","@value":"9000413525719"},{"@type":"NRID","@value":"9000283741552"},{"@type":"NRID","@value":"9000402020406"},{"@type":"NRID","@value":"9000022804724"},{"@type":"NRID","@value":"9000361707204"},{"@type":"NRID","@value":"9000283740256"},{"@type":"NRID","@value":"9000255702833"},{"@type":"NRID","@value":"9000258598973"},{"@type":"NRID","@value":"9000283124333"},{"@type":"NRID","@value":"9000283122628"},{"@type":"NRID","@value":"9000402771514"},{"@type":"NRID","@value":"9000258595080"},{"@type":"NRID","@value":"9000258597021"},{"@type":"NRID","@value":"9000258596993"},{"@type":"NRID","@value":"9000258594243"},{"@type":"NRID","@value":"9000000659699"},{"@type":"NRID","@value":"9000356673721"},{"@type":"NRID","@value":"9000403828089"},{"@type":"NRID","@value":"9000404110796"},{"@type":"NRID","@value":"9000283123326"},{"@type":"NRID","@value":"9000283741743"},{"@type":"NRID","@value":"9000258594422"},{"@type":"NRID","@value":"9000258602152"},{"@type":"NRID","@value":"9000388490935"},{"@type":"NRID","@value":"9000304624042"},{"@type":"NRID","@value":"9000258419660"},{"@type":"NRID","@value":"9000258595452"},{"@type":"NRID","@value":"9000258597009"},{"@type":"NRID","@value":"9000258596772"},{"@type":"RESEARCHMAP","@value":"https://researchmap.jp/Kei_Ohkubo"}],"foaf:name":[{"@value":"Kei Ohkubo"}],"jpcoar:affiliationName":[{"@value":"Department\rof Material and Life Science, Graduate School of Engineering, Osaka University, and ALCA, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1380004233236435201","@type":"Researcher","foaf:name":[{"@value":"Vicente Manuel Blas-Ferrando"}],"jpcoar:affiliationName":[{"@value":"Área\rde Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. 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Universidad s/n, Elche E-03202, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1380004233236435208","@type":"Researcher","foaf:name":[{"@value":"Javier Ortíz"}],"jpcoar:affiliationName":[{"@value":"Área\rde Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. Universidad s/n, Elche E-03202, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1380004233236435200","@type":"Researcher","foaf:name":[{"@value":"Fernando Fernández-Lázaro"}],"jpcoar:affiliationName":[{"@value":"Área\rde Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. Universidad s/n, Elche E-03202, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1420001326223948672","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"70418698"},{"@type":"NRID","@value":"1000070418698"},{"@type":"NRID","@value":"9000017327647"},{"@type":"NRID","@value":"9000025082692"},{"@type":"NRID","@value":"9000413472415"},{"@type":"NRID","@value":"9000024630710"},{"@type":"NRID","@value":"9000022311322"},{"@type":"NRID","@value":"9000412115331"},{"@type":"NRID","@value":"9000022263719"},{"@type":"NRID","@value":"9000022758867"},{"@type":"NRID","@value":"9000257716852"},{"@type":"NRID","@value":"9000000537130"},{"@type":"NRID","@value":"9000414491217"},{"@type":"NRID","@value":"9000022760038"},{"@type":"NRID","@value":"9000401766943"},{"@type":"NRID","@value":"9000022725019"},{"@type":"NRID","@value":"9000411105173"},{"@type":"RESEARCHMAP","@value":"https://researchmap.jp/takuhasobe"}],"foaf:name":[{"@value":"Taku Hasobe"}],"jpcoar:affiliationName":[{"@value":"Department\rof Chemistry, Faculty of Science and Technology, Keio University, Yokohama 223-8522, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1380004233236435204","@type":"Researcher","foaf:name":[{"@value":"Ángela Sastre-Santos"}],"jpcoar:affiliationName":[{"@value":"Área\rde Química Orgánica, Instituto de Bioingeniería, Universidad Miguel Hernández, Edificio Vinalopó, Avda. Universidad s/n, Elche E-03202, Spain"}]},{"@id":"https://cir.nii.ac.jp/crid/1380004233236435202","@type":"Researcher","foaf:name":[{"@value":"Shunichi Fukuzumi"}],"jpcoar:affiliationName":[{"@value":"Department\rof Material and Life Science, Graduate School of Engineering, Osaka University, and ALCA, Japan Science and Technology Agency (JST), Suita, Osaka 565-0871, Japan"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"15206106"},{"@type":"EISSN","@value":"15205207"}],"prism:publicationName":[{"@value":"The Journal of Physical Chemistry B"}],"dc:publisher":[{"@value":"American Chemical Society (ACS)"}],"prism:publicationDate":"2015-02-09","prism:volume":"119","prism:number":"24","prism:startingPage":"7690","prism:endingPage":"7697"},"reviewed":"false","url":[{"@id":"https://pubs.acs.org/doi/pdf/10.1021/jp5123163"}],"createdAt":"2015-01-23","modifiedAt":"2023-04-28","foaf:topic":[{"@id":"https://cir.nii.ac.jp/all?q=Anions","dc:title":"Anions"},{"@id":"https://cir.nii.ac.jp/all?q=Indoles","dc:title":"Indoles"},{"@id":"https://cir.nii.ac.jp/all?q=Molecular%20Structure","dc:title":"Molecular Structure"},{"@id":"https://cir.nii.ac.jp/all?q=Infrared%20Rays","dc:title":"Infrared Rays"},{"@id":"https://cir.nii.ac.jp/all?q=Electrochemical%20Techniques","dc:title":"Electrochemical Techniques"},{"@id":"https://cir.nii.ac.jp/all?q=Isoindoles","dc:title":"Isoindoles"},{"@id":"https://cir.nii.ac.jp/all?q=Lithium","dc:title":"Lithium"},{"@id":"https://cir.nii.ac.jp/all?q=Photochemical%20Processes","dc:title":"Photochemical Processes"},{"@id":"https://cir.nii.ac.jp/all?q=Organometallic%20Compounds","dc:title":"Organometallic Compounds"},{"@id":"https://cir.nii.ac.jp/all?q=Fullerenes","dc:title":"Fullerenes"},{"@id":"https://cir.nii.ac.jp/all?q=Electrodes","dc:title":"Electrodes"}],"project":[{"@id":"https://cir.nii.ac.jp/crid/1040000782285946624","@type":"Project","projectIdentifier":[{"@type":"KAKEN","@value":"26286017"},{"@type":"JGN","@value":"JP26286017"},{"@type":"URI","@value":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-26286017/"}],"notation":[{"@language":"ja","@value":"特異な光触媒能を有する超分子型ナノ細孔体の創製"},{"@language":"en","@value":"Construction of Novel Supramolecular Nanoarrays for Photocatalytic Applications"}]},{"@id":"https://cir.nii.ac.jp/crid/1040000782310541568","@type":"Project","projectIdentifier":[{"@type":"KAKEN","@value":"26620159"},{"@type":"JGN","@value":"JP26620159"},{"@type":"URI","@value":"https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-26620159/"}],"notation":[{"@language":"ja","@value":"超分子集積化による励起ダイナミクス制御と革新的光エネルギー変換機能発現"},{"@language":"en","@value":"Preparation and Photophysical Property  of Organized Molecular Assemblies Having Light Energy Conversion 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