{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T15:25:49Z","timestamp":1760369149745,"version":"build-2065373602"},"reference-count":51,"publisher":"Wiley","issue":"12","license":[{"start":{"date-parts":[[2014,2,13]],"date-time":"2014-02-13T00:00:00Z","timestamp":1392249600000},"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":[[2014,3,17]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We describe the thermodynamic characterisation of the self\u2010sorting process experienced by two homodimers assembled by hydrogen\u2010bonding interactions through their cyclopeptide scaffolds and decorated with Zn\u2013porphyrin and fullerene units into a heterodimeric assembly that contains one electron\u2010donor (Zn\u2013porphyrin) and one electron\u2010acceptor group (fullerene). The fluorescence of the Zn\u2013porphyrin unit is strongly quenched upon heterodimer formation. This phenomenon is demonstrated to be the result of an efficient photoinduced electron\u2010transfer (PET) process occurring between the Zn\u2013porphyrin and the fullerene units of the heterodimeric system. The recombination lifetime of the charge\u2010separated state of the heterodimer complex is in the order of 180\u2005ns. In solution, both homo\u2010 and heterodimers are present as a mixture of three regioisomers: two staggered and one eclipsed. At the concentration used for this study, the high stability constant determined for the heterodimer suggests that the eclipsed conformer is the main component in solution. The application of the bound\u2010state scenario allowed us to calculate that the heterodimer exists mainly as the eclipsed regioisomer (75\u201390\u2009%). The attractive interaction that exists between the donor and acceptor chromophores in the heterodimeric assembly favours their arrangement in close contact. This is confirmed by the presence of charge\u2010transfer bands centred at 720\u2005nm in the absorption spectrum of the heterodimer. PET occurs in approximately 75\u2009% of the chromophores after excitation of both Zn\u2013porphyrin and fullerene chromophores. Conversely, analogous systems, reported previously, decorated with extended tetrathiafulvalene and fullerene units showed a PET process in a significantly reduced extent (33\u2009%). We conclude that the strength (stability constant (<jats:italic>K<\/jats:italic>)\u00d7effective molarity (EM)) of the intramolecular interaction established between the two chromophores in the Zn\u2013porphyrin\/fullerene cyclopeptide\u2010based heterodimers controls the regioisomeric distribution and regulates the high extent to which the PET process takes place in this system.<\/jats:p>","DOI":"10.1002\/chem.201304200","type":"journal-article","created":{"date-parts":[[2014,2,15]],"date-time":"2014-02-15T05:12:01Z","timestamp":1392441121000},"page":"3427-3438","source":"Crossref","is-referenced-by-count":16,"title":["Self\u2010Sorting of Cyclic Peptide Homodimers into a Heterodimeric Assembly Featuring an Efficient Photoinduced Intramolecular Electron\u2010Transfer Process"],"prefix":"10.1002","volume":"20","author":[{"given":"Gemma","family":"Aragay","sequence":"first","affiliation":[]},{"given":"Barbara","family":"Ventura","sequence":"additional","affiliation":[]},{"given":"Arcadio","family":"Guerra","sequence":"additional","affiliation":[]},{"given":"Inmaculada","family":"Pintre","sequence":"additional","affiliation":[]},{"given":"Claudio","family":"Chiorboli","sequence":"additional","affiliation":[]},{"given":"Rebeca","family":"Garc\u00eda\u2010Fandi\u00f1o","sequence":"additional","affiliation":[]},{"given":"Lucia","family":"Flamigni","sequence":"additional","affiliation":[]},{"given":"Juan R.","family":"Granja","sequence":"additional","affiliation":[]},{"given":"Pablo","family":"Ballester","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2014,2,13]]},"reference":[{"volume-title":"Ionic Channels of Excitable Membranes","year":"2001","author":"Hille B.","key":"e_1_2_5_1_2"},{"key":"e_1_2_5_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/B603256G"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar4000136"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19980807)4:8<1367::AID-CHEM1367>3.0.CO;2-B"},{"key":"e_1_2_5_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010316)113:6<1016::AID-ANGE10160>3.0.CO;2-8"},{"key":"e_1_2_5_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010316)40:6<988::AID-ANIE9880>3.0.CO;2-N"},{"key":"e_1_2_5_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs35172b"},{"key":"e_1_2_5_7_2","first-page":"2149","volume-title":"Synthesis of Supramolecular Nanotubes. In Supramolecular Chemistry: From Molecules to Nanomaterials, Vol.\u20055","author":"Garcia\u2010Fandi\u00f1o R.","year":"2012"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1038\/366324a0"},{"key":"e_1_2_5_9_2","doi-asserted-by":"publisher","DOI":"10.1038\/369301a0"},{"key":"e_1_2_5_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00092a079"},{"key":"e_1_2_5_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja002436k"},{"key":"e_1_2_5_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/B805753M"},{"key":"e_1_2_5_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar000147v"},{"key":"e_1_2_5_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00102a054"},{"key":"e_1_2_5_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja310064v"},{"key":"e_1_2_5_16_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1NR11068C"},{"key":"e_1_2_5_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja981485i"},{"key":"e_1_2_5_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja904548q"},{"key":"e_1_2_5_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0296273"},{"key":"e_1_2_5_20_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201201565"},{"key":"e_1_2_5_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200501555"},{"key":"e_1_2_5_21_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200501555"},{"key":"e_1_2_5_22_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp910919k"},{"key":"e_1_2_5_23_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar9001735"},{"key":"e_1_2_5_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar900127h"},{"key":"e_1_2_5_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700282n"},{"key":"e_1_2_5_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar900209b"},{"key":"e_1_2_5_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700026t"},{"key":"e_1_2_5_28_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0609506104"},{"key":"e_1_2_5_29_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201002271"},{"key":"e_1_2_5_30_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201101511"},{"key":"e_1_2_5_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp309149s"},{"key":"e_1_2_5_32_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201102819"},{"key":"e_1_2_5_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200500478"},{"key":"e_1_2_5_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja066885h"},{"key":"e_1_2_5_35_2","unstructured":"The monomer of the fullerene derivativeCP7has very low extinction coefficients and is present in small concentration during the titration experiment. For these reasons and to reduce the number of variables of the fit we considered that this species does not contribute significantly to the registered absorption spectra (not coloured)."},{"key":"e_1_2_5_36_2","doi-asserted-by":"publisher","DOI":"10.1039\/B614883M"},{"key":"e_1_2_5_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol101393h"},{"key":"e_1_2_5_38_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja803434z"},{"key":"e_1_2_5_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja1084783"},{"key":"e_1_2_5_40_2","unstructured":"We have observed that assuming an increase of one order of magnitude in the dimerisation constant of homodimers (107\u2009M\u22121) has a minimum impact in the stability\u2010constant value determined for the heterodimer (2.1\u00d7108\u2009M\u22121). However this increase is inherently associated with a rise onK0(108\u2009M\u22121). The use ofK0=108\u2009M\u22121in the calculation of the distribution of bound states provides a complete inversion of the population mixture that does not explain the experimental results obtained in the photophysical studies."},{"key":"e_1_2_5_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja066031x"},{"key":"e_1_2_5_42_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp400796n"},{"key":"e_1_2_5_43_2","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.200400558"},{"key":"e_1_2_5_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol062666p"},{"key":"e_1_2_5_45_2","doi-asserted-by":"publisher","DOI":"10.1039\/b819496c"},{"key":"e_1_2_5_46_2","unstructured":"By introducing the usual corrections for Coulombic interactions and assuming a centre\u2010to\u2010centre distance between partners of the order of 10\u2005\u00c5 a value of 1.3\u2005eV would be obtained for the CS state energy level. At the present level of discussion this value can be considered equivalent to the used one of 1.4\u2005eV."},{"key":"e_1_2_5_47_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201202245"},{"key":"e_1_2_5_48_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp900835s"},{"key":"e_1_2_5_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja903467w"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201304200","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201304200","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T11:22:11Z","timestamp":1760268131000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201304200"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,2,13]]},"references-count":51,"journal-issue":{"issue":"12","published-print":{"date-parts":[[2014,3,17]]}},"alternative-id":["10.1002\/chem.201304200"],"URL":"https:\/\/doi.org\/10.1002\/chem.201304200","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"type":"print","value":"0947-6539"},{"type":"electronic","value":"1521-3765"}],"subject":[],"published":{"date-parts":[[2014,2,13]]}}}