{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,6]],"date-time":"2026-02-06T20:51:08Z","timestamp":1770411068892,"version":"3.49.0"},"reference-count":133,"publisher":"Wiley","issue":"36","license":[{"start":{"date-parts":[[2009,7,30]],"date-time":"2009-07-30T00:00:00Z","timestamp":1248912000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2009,9,14]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Cup\u2010shaped nanocarbons (CNC) generated by the electron\u2010transfer reduction of cup\u2010stacked carbon nanotubes have been functionalized with porphyrins (H<jats:sub>2<\/jats:sub>P) as light\u2010capturing chromophores. The resulting donor\u2013acceptor nanohybrid has been characterized by thermogravimetric analysis (TGA), Raman and IR spectroscopy, transmission electron microscopy, elemental analysis, and UV\/Vis spectroscopy. The weight of the porphyrins attached to the cup\u2010shaped nanocarbons was determined as 20\u2009% by TGA and elemental analysis. The UV\/Vis absorption spectrum of CNC\uf8ff(H<jats:sub>2<\/jats:sub>P)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> in DMF agrees well with that obtained by the superposition of reference porphyrin (ref\u2010H<jats:sub>2<\/jats:sub>P) and cup\u2010shaped nanocarbons. The photoexcitation of the CNC\uf8ff(H<jats:sub>2<\/jats:sub>P)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> nanohybrid results in formation of the charge\u2010separated (CS) state to attain the longest CS lifetime (0.64\u00b10.01\u2005ms) ever reported for donor\u2013acceptor nanohybrids, which may arise from efficient electron migration following the charge separation. The formation of a radical ion pair was detected directly by electron spin resonance (ESR) measurements under photoirradiation of CNC\uf8ff(H<jats:sub>2<\/jats:sub>P)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> with a high\u2010pressure mercury lamp in frozen DMF at 153\u2005K. The observed ESR signal at <jats:italic>g<\/jats:italic>=2.0044 agrees with that of ref\u2010H<jats:sub>2<\/jats:sub>P<jats:sup>.+<\/jats:sup> produced by one\u2010electron oxidation with [Ru(bpy)<jats:sub>3<\/jats:sub>]<jats:sup>3+<\/jats:sup> in deaerated CHCl<jats:sub>3<\/jats:sub>, indicating the formation of H<jats:sub>2<\/jats:sub>P<jats:sup>.+<\/jats:sup>. The electron\u2010acceptor ability of the reference CNC compound (ref\u2010CNC) was also examined by the electron\u2010transfer reduction of ref\u2010CNC by a series of semiquinone radical anions.<\/jats:p>","DOI":"10.1002\/chem.200900427","type":"journal-article","created":{"date-parts":[[2009,7,30]],"date-time":"2009-07-30T10:49:39Z","timestamp":1248950979000},"page":"9160-9168","source":"Crossref","is-referenced-by-count":18,"title":["Synthesis, Characterization, Redox Properties, and Photodynamics of Donor\u2013Acceptor Nanohybrids Composed of Size\u2010Controlled Cup\u2010Shaped Nanocarbons and Porphyrins"],"prefix":"10.1002","volume":"15","author":[{"given":"Masataka","family":"Ohtani","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kenji","family":"Saito","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Shunichi","family":"Fukuzumi","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2009,9,3]]},"reference":[{"key":"e_1_2_6_1_2","volume-title":"Carbon Nanotubes and Related Structures\u2014New Materials for the Twenty\u2010First Century","author":"Harris P. 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blurred shadow around a carbon structure is a trace of vapored DMF solvent."},{"key":"e_1_2_6_86_2","unstructured":"The two\u2010step thermal degradation curve of CNC\uf8ff(H2P)nsample in TGA agree well with that of other nanohybrid systems composed of nanocarbons and porphyrins; see: ref.\u2005[26b] and"},{"key":"e_1_2_6_87_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja063697i"},{"key":"e_1_2_6_88_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp072075w"},{"key":"e_1_2_6_89_2","unstructured":"Elemental analysis calcd for C640H55(C108H145N8O4): C 90.57; H 2.07; N 1.13; found: C 90.36; H 2.06; N 1.13. This indicates that one porphyrin is attached per 640\u2005carbon atoms."},{"key":"e_1_2_6_90_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp010642o"},{"key":"e_1_2_6_91_2","unstructured":"For Raman spectroscopy of carbon nanostructures see:"},{"key":"e_1_2_6_92_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp003081u"},{"key":"e_1_2_6_93_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.65.165433"},{"key":"e_1_2_6_94_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.physrep.2004.10.006"},{"key":"e_1_2_6_95_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp071378n"},{"key":"e_1_2_6_96_2","unstructured":"The nanocup moiety in CNC\uf8ff(H2P)nwas also absorbed a light at 426\u2005nm. Thus the actual ratio of fluorescence quenching that can be estimated from absorption ratio is about 80\u2009%."},{"key":"e_1_2_6_97_2","unstructured":"For fluorescence lifetime of ameso\u2010substituted porphyrin see:"},{"key":"e_1_2_6_98_2","doi-asserted-by":"publisher","DOI":"10.1016\/0047-2670(81)85008-3"},{"key":"e_1_2_6_99_2","doi-asserted-by":"publisher","DOI":"10.1039\/f29817701695"},{"key":"e_1_2_6_100_2","unstructured":"For spectroscopic characterization of photogenerated porphyrin redical cation in nanocarbon\u2010based hybrid system ref.\u2005[18b 20b] see:"},{"key":"e_1_2_6_101_2","doi-asserted-by":"publisher","DOI":"10.1039\/b406933a"},{"key":"e_1_2_6_102_2","doi-asserted-by":"publisher","DOI":"10.1002\/adma.200400641"},{"key":"e_1_2_6_103_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja050930o"},{"key":"e_1_2_6_104_2","doi-asserted-by":"publisher","DOI":"10.1039\/B515394H"},{"key":"e_1_2_6_105_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja063697i"},{"key":"e_1_2_6_106_2","unstructured":"Free\u2010base porphyrin radical cation see:"},{"key":"e_1_2_6_107_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic00209a025"},{"key":"e_1_2_6_108_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja064678b"},{"key":"e_1_2_6_109_2","doi-asserted-by":"publisher","DOI":"10.1039\/a803974g"},{"key":"e_1_2_6_110_2","unstructured":"The CS lifetime was also determined from the decay time profiles at 750\u2005nm as 0.64\u00b10.01\u2005ms."},{"key":"e_1_2_6_111_2","unstructured":"The CNC\uf8ff(H2P)nsolution was irradiated with a high\u2010pressure mercury lamp (\u03bb>380\u2005nm) equipped with a UV\u2010light cut filter accompanied by rapidly falling temperature."},{"key":"e_1_2_6_112_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00711a025"},{"key":"e_1_2_6_112_3","doi-asserted-by":"publisher","DOI":"10.1021\/ja982136r"},{"key":"e_1_2_6_113_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00193a023"},{"key":"e_1_2_6_114_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja039918r"},{"key":"e_1_2_6_115_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0211611"},{"key":"e_1_2_6_116_2","unstructured":"No direct electron transfer from singlet\u2010excited H2P to TCNQ occurs under the present experimental conditions with small concentrations of TCNQ."},{"key":"e_1_2_6_117_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0114891"},{"key":"e_1_2_6_118_2","doi-asserted-by":"publisher","DOI":"10.1016\/B978-075067571-0\/50007-7"},{"key":"e_1_2_6_119_2","unstructured":"\u00a0"},{"key":"e_1_2_6_120_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja02206a016"},{"key":"e_1_2_6_121_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00876a029"},{"key":"e_1_2_6_122_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00878a017"},{"key":"e_1_2_6_123_2","unstructured":"The ET reduction of cup\u2010shaped nanocarbon causes them to disperse in a polar organic solvent (such as THF or DMF) leading to covalently functionalization of functional groups through radical addition. Reduced carbon nanotubes were also arylated by the reaction with 4\u2010iodoaniline see:"},{"key":"e_1_2_6_124_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol050862a"},{"key":"e_1_2_6_125_2","doi-asserted-by":"publisher","DOI":"10.1021\/cm060832h"},{"key":"e_1_2_6_126_2","unstructured":"The other substituted TCPP (di\u2010 and tetra\u2010substituted TCPP) is also formed as a by\u2010product. After the reaction tetra\u2010substituted TCPP and trace of di\u2010substituted TCPP were detected by MALDI\u2010TOF mass spectroscopy. These by\u2010products can be easily removed by silica gel column chromatography. The characterization of tri\u2010substituted TCPP also has been carried out by MALDI\u2010TOF mass spectroscopy after the purification. See the Supporting Information (Figure\u2005S1)."},{"key":"e_1_2_6_127_2","unstructured":"The dialysis was carried out for 3\u2005days with frequent replacement of the solvent. In order to confirm the progress of the dialysis the absorbance of the outer solution was recorded with an UV\/Vis spectrophotometer to ensure that excess free porphyrin was removed from the CNC\uf8ff(H2P)nsolution."},{"key":"e_1_2_6_128_2","unstructured":"For synthesis of tetrakis(N\u2010octadecyl\u20104\u2010aminocarbonylphenyl)porphyrin see"},{"key":"e_1_2_6_129_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja036155z"},{"key":"e_1_2_6_130_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.65.715"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200900427","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200900427","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T18:30:47Z","timestamp":1760293847000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200900427"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,9,3]]},"references-count":133,"journal-issue":{"issue":"36","published-print":{"date-parts":[[2009,9,14]]}},"alternative-id":["10.1002\/chem.200900427"],"URL":"https:\/\/doi.org\/10.1002\/chem.200900427","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,9,3]]}}}