title: Self-Sorting of cyclic peptide homodimers into a heterodimeric assembly featuring an efficient photoinduced intramolecular electron-transfer process.
abstract: We describe the thermodynamic characterisation of the self-sorting process experienced by two homodimers assembled by hydrogen-bonding interactions through their cyclopeptide scaffolds and decorated with Zn-porphyrin and fullerene units into a heterodimeric assembly that contains one electron-donor (Zn–porphyrin) and one electron-acceptor group (fullerene). The fluorescence of the Zn-porphyrin unit is strongly quenched upon heterodimer formation. This phenomenon is demonstrated to be the result of an efficient photoinduced electron-transfer (PET) process occurring between the Zn-porphyrin and the fullerene units of the heterodimeric system. The recombination lifetime of the charge-separated state of the heterodimer complex is in the order of 180 ns. In solution, both homo- 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-state scenario allowed us to calculate that the heterodimer exists mainly as the eclipsed regioisomer (75-90 %). 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-transfer bands centred at 720 nm in the absorption spectrum of the heterodimer. PET occurs in approximately 75% of the chromophores after excitation of both Zn-porphyrin 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%). We conclude that the strength (stability constant (K) x effective molarity (EM)) of the intramolecular interaction established between the two chromophores in the Zn-porphyrin/fullerene cyclopeptide-based heterodimers controls the regioisomeric distribution and regulates the high extent to which the PET process takes place in this system.
authors.forename: Gemma
authors.initials: G
authors.lastname: Aragay
authors.forename: Barbara
authors.initials: B
authors.lastname: Ventura
authors.forename: Arcadio
authors.initials: A
authors.lastname: Guerra
authors.forename: Inmaculada
authors.initials: I
authors.lastname: Pintre
authors.forename: Claudio
authors.initials: C
authors.lastname: Chiorboli
authors.forename: Rebeca
authors.initials: R
authors.lastname: García-Fandiño
authors.forename: Lucia
authors.initials: L
authors.lastname: Flamigni
authors.forename: Juan R
authors.initials: JR
authors.lastname: Granja
authors.forename: Pablo
authors.initials: P
authors.lastname: Ballester
mesh_terms: D004579:Electron Transport; D006860:Hydrogen Bonding; D008665:Metalloporphyrins / Q000737:chemistry*; D015394:Molecular Structure; D010456:Peptides, Cyclic / Q000737:chemistry*; D010777:Photochemistry; D015032:Zinc / Q000737:chemistry*
chemical_list: D008665:Metalloporphyrins; D010456:Peptides, Cyclic; D015032:Zinc